CA2074098A1 - Copolymerizable imidazolidinone monomer - Google Patents
Copolymerizable imidazolidinone monomerInfo
- Publication number
- CA2074098A1 CA2074098A1 CA 2074098 CA2074098A CA2074098A1 CA 2074098 A1 CA2074098 A1 CA 2074098A1 CA 2074098 CA2074098 CA 2074098 CA 2074098 A CA2074098 A CA 2074098A CA 2074098 A1 CA2074098 A1 CA 2074098A1
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- CA
- Canada
- Prior art keywords
- monomer
- latex
- copolymer
- alkyl
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
- C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D205/06—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D205/08—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with one oxygen atom directly attached in position 2, e.g. beta-lactams
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/36—One oxygen atom with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/42—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A monomer and polymers resulting therefrom, the monomer comprising (I), wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -alkyl, -aryl, -CH2(CH2)y-C = N, -CH2O alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; A
= phenylene or alkylene; Y = -O-, -NH-, -NHNH, -O-M-, -NH-M-, or -NH-NH-M-; Z = -O- or -S-, and M = (a), (b), (c), and (d) wherein x = 2 - 5.
= phenylene or alkylene; Y = -O-, -NH-, -NHNH, -O-M-, -NH-M-, or -NH-NH-M-; Z = -O- or -S-, and M = (a), (b), (c), and (d) wherein x = 2 - 5.
Description
W091/l224~ PC'r/~59l/00939 ~r~
COPO~YMERIZABLE IMID~ZO~IDINONE MO~OMER
Field_o the,Invention This invention relates generally to polymer dispersions and solution.s and to monomers used.to prepare the~e dispersions and solutions. More specifically, the present invention relates to copolymerizable monomers which promo~e ; 10 wet adhesion in any variety of polymeric compositions including sealants, coatings, paints, and adhesives among others.
Backqround o the I~vontion In the formulation and application of coating and sealing compounds there are any number of physical properties which become relevant depending on the rina_ . application. For example, the properties of a pain~
composition may vary tremendously depending on the na~ure : of the surface of application, the location of this surface, and the amount of contact or use to which this surface is to be subjected. Generally, certain physical properties are more desirable than others including weL
adhesion and scrub resistance. :[n the past, various polymeric systems have been used to bolster any numbe~ o~
sealants, caulks, and paints to :Lncrease these characteristics ~lithin the end us;s composition.
~: For example, Haskins et al, IJ.S. Patent No. 2"-?,Gi~' disc~oses acrylamides of N-aminoalkyl alkylene urea polymers useful,in coating compositions. Hurwitz,~-U.~,.
Patent No. 3,369,008 also discloses~N(cyclic ureidoalkyl)crotonamides polymers useful in coatins : . compositions, Dixon et al, U.S. Patent No. 4,111,a7, disclose allyl,esters.of-N-alkyl-omega-(alkyleneureido) . amic acids useful for imparting wet adhesion properlies to 35 emulsion 6~stems. Sims, U.S. Patent`No. 4,104,220 discloses novel alkenyl 5uccinamic ureido compoundq useIul as functional,comonomers.for imparting wet adhesior.. Wong et al, U.S. Patent No. ~,722,965 di~clo~e a chal~-adh sion pol~mer latex for exterior coatings.
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:
COPO~YMERIZABLE IMID~ZO~IDINONE MO~OMER
Field_o the,Invention This invention relates generally to polymer dispersions and solution.s and to monomers used.to prepare the~e dispersions and solutions. More specifically, the present invention relates to copolymerizable monomers which promo~e ; 10 wet adhesion in any variety of polymeric compositions including sealants, coatings, paints, and adhesives among others.
Backqround o the I~vontion In the formulation and application of coating and sealing compounds there are any number of physical properties which become relevant depending on the rina_ . application. For example, the properties of a pain~
composition may vary tremendously depending on the na~ure : of the surface of application, the location of this surface, and the amount of contact or use to which this surface is to be subjected. Generally, certain physical properties are more desirable than others including weL
adhesion and scrub resistance. :[n the past, various polymeric systems have been used to bolster any numbe~ o~
sealants, caulks, and paints to :Lncrease these characteristics ~lithin the end us;s composition.
~: For example, Haskins et al, IJ.S. Patent No. 2"-?,Gi~' disc~oses acrylamides of N-aminoalkyl alkylene urea polymers useful,in coating compositions. Hurwitz,~-U.~,.
Patent No. 3,369,008 also discloses~N(cyclic ureidoalkyl)crotonamides polymers useful in coatins : . compositions, Dixon et al, U.S. Patent No. 4,111,a7, disclose allyl,esters.of-N-alkyl-omega-(alkyleneureido) . amic acids useful for imparting wet adhesion properlies to 35 emulsion 6~stems. Sims, U.S. Patent`No. 4,104,220 discloses novel alkenyl 5uccinamic ureido compoundq useIul as functional,comonomers.for imparting wet adhesior.. Wong et al, U.S. Patent No. ~,722,965 di~clo~e a chal~-adh sion pol~mer latex for exterior coatings.
, ~
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8UE~STITUTE 8HEET;
, . ,. , .", . ,, " ,., .. , , ,. . ",,,,,, , ,, ~ , . . .. . ... . . . . . . . .. . . . .. .
:
2~3 PCr/~'St)l/0093 2~ 7'~
Summary of the I~v~ntion The present invention provides a polymerizable monomer for the promotion of wet adhesion having the ormula:
R' O
\ "
~ -N~1-C-Y-CH~(CH2)~N (C~12)~
Z=C X
wherein n = l or 2; m = l or 2; R' = H or CH3; ~ = -O-, : l0 -CH2, -NR-; R ~ H, -Cl5 alkyl, -aryl, -CH2(CH2)~-C z N, -CH~OC 1_5 alkyl, -(CH2)~OH, -CH~CH(OH)C~I~; A = phenylene or C j_5 alkylene; Y = -O-, -NH-, -NHNH~, -O-M-, -MH-~,-, or -NH-NH-M-; and o R' O NH O
M = -COCH2-CH-O-, -NH-C-CH2-, -NH-C-, and -C(CH2)XO-wherein x = 2 - 5. The monomer may also be synthesized to have vinyl acrylic functionality.
The monvmer of the present invention can be used either alone or polymerized in any given polymer system. The polymerizable monomer of the preC;ent invention provides far superior wet adhesion when compared to polymers presen~
commercially available and commonly used in the coatings and paint industries.
Detailed ~ cription of the Invention ^~ The present invention discloses monomers useful in polymeric materials, the monomers-providing enhanced we4 .: adhesion and scrub resistance. The enhanced wet adhesion monomers of ~he present invention may be polymerized into polymeric materials or polymers that may be added to other polymers. The instant monomer can be used in polymeric matrices which result in any number of adhesives, caulks, : latexes, paints,-coatings, and-sealants among other matrices. . .
The wet adhesion monomers of the present invention can be used in polymeric compositLons that are applied to any number of substrates and subjected to any number of ., ` $1JBSTITUTE~ 8HEI~
, .
W091/1~243 2~ PCT/~S91/0093s) environmenkal factors. The instant wet adhesion monomer may be applied in any number o~ ways. Wet adhesion monomers can be copolymerized Ln la-tex cornpositions, paint compositions, coating compositions, and film compoCitions.
The Monomer The present invention is a monomer for the promotion of wet adhesion having the formula:
R~ o ,~A-NH-C-Y-CH2(cH2)rN--tC 112)G
Z=C X
wherein n = l or 2; m = l or 2; R' ~ H or CH~; X = -C-, -CH" -NR-; R = H, -Cl 5 alkyl, -aryl, -CH,(CHq)x-C = N, -CHqOC!5 alkyl, -( CH,)~OH, -CH,CH(OH)CH~; A = phenylen or C1s alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-~-; and O R' O NH O
" I ,- .. ..
M = -COCH2-CH-O-, -NH-C-CH2 , -NH-C-, and -C(CH-,)xo-wherein x = 2 - 5. The monomer may hlso be synthesized to have vinyl acrylic functionality.
Synthesis of the monomer of the present inventior. is initiated by reacting any compound having an active ~inyl group and a reactive isocyana~e group with a bac~bone compound having an active hydrogen in the form of a reactive hydroxyl group or amine group. Generally, isocyanate-type compounds and monomers have been found useful to this end. The preferred isocyanate compound useful in the invention is a compound having a single polymerizable vinyl group and a single monoisocyana~e group. .
In preparation of the monomer of-the present inventior.
a vinyl compound such as alpha, alpha-diméthyl meta-isopropenyl benzyl isocyana~e (m-TMI) is combined with a backbone heterocyclic compounds ~uch as oxazolidinone in the presence of an organic ~olvent and heat. Generaliy, 5UBSTITUTE~ 8HEE~J j ~....................... .
WO91/1224~ PCr/~S91/0093~
~3~ 8 -4-any organic solvents found useful in synthesizing the monomer of the present lnvention include ethyl acetate, hexane, chloroform and the like. Optionally, a reaction catalyst such as dibutyl tin dilaurate may al50 be used Backbone compounds which may be allowed to react with m-TMI include any variety of heterocyclic or heteroaliphatic compounds including l-(2-hydroxye~hyl) imidazolidin-2-one, N,N-diethylethylenediamine, 2-(2-aminoethyl)imidazolidin-2-one and the like which when reacted with m-TMI produce polyme.rizable compounds which are capable of being used in all acrylic systems.
Alternatively, the monomer of the present invention mav be synthesized in any manner which permits its use in vinyl acrylic systems. In this instance, instead of using m-T~I, compounds such as 2-vinyl-4,4-dimethyl-2-oxazolin-S-one may be combined with backbone compounds such as N-(2-hydroxyethyl)oxazolidin-2-one, N,N-diethylethylenedi~mine and 2-(2-aminoethyl) imidazolidin-2-one in a manner that provides the polymerizable compound useful in vinyl acrylic systems. In : this instance, the 2-vinyl-4,4-dimethyl-2-oxazGlin-5-one has a reactive carbonyl in the five position which rssui~
in the five member ring opening when combined wit~. th~
` reactive amine moiety of the backbone compound. The resulting monomer is an imidazoline type compound having an amide linkage which is terminated by a polymerizable olefin group at one end of the monomer. This monomer may then be polymerized with compounds such as vinyl acetate and n-butyl acrylate to provide an emulsion polymer useful . 30 again in any type of latex, caulk, adhesive, or other film ,,,forming,compositions~
In preparation of the polymers of the invention, olyrnerization occurs through the vinyl group Comonomers The polymerizable compound of the present invention may ' SUBSTITUTE 8HEE~-~
.
WO91/12~43 PCr/~S91/0093~) 2 ~ o L' ~ ~ ~
-5- ;
be combined with any number of monomers to form a copolymer. The monomer of the present invention may be polymerized with virtually any other vinyl monomer Examples of the broad classes of such vinyl monomers include alpha-olefins, vinyl chlorides, vinylidene chlorides, vinyl aromatic monomers, polymerizable alpha, beta-unsaturated carboxylic acids and esters, and other well known monomers.
The vinyl unsaturated monomer can be an alpha-olefin monomer such as ethylene, propylene, butylene, isobutylene, hexene; styrene, alpha methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, ricinoleic acid, oleic acid, linoleic acid, butadiene, and the like. Alpha-olefins tha can also be used in the invention include other Cit alpha-olefins such as cyclopentene, cyclopentadiene, 1,3-butadiene, l-hexene, norbornene, etc.
Useful acrylic monomers include methylacrylate, methyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, butyl acrylat~, hexyl acrylate, cyclohexylacrylate, (2-hydroxyethyl) methacrylate, (2-hydroxyethyl) acrylate, (3-hydroxypropyl) methacrylata, (3-hydroxypropyl) acrylate, (pipiridinoethyl) methacrylat_, (morpholinoethyl) methacrylate, and the like.
Useful unsaturated dicarboxylic acids include i~aconic acid, cinnamic acid, crotonic acid, mesaconic acld, maleic acid, fumaric acid, and the like; alpha, beta unsaturaled dicarboxylic acid esters of the dicarboxylic acid es~ers described above inc-~uding aromatic esters, cycloal~yl esters, alkyl esters, hydroxy alkyl esters, alkoxy alkyl esters, and the like.
,, Vinyl aromatic monomers that can be used with the monomer of this invention include monomers that comprise a~
least one aromatic group and at least one polymerizable vinyl group. Typical examples of aromatic groups include ; 35 phenyl, substituted phenyl, naphthyl, phenanthryl, and 8VBS'rlTUTE~ 8HEEr~.
,. ... ... ...
W091/12243 PCr/~S91/0093t) 2~7~ 6-others. Preferred vinyl aromatic monomers include the styrene family including such monoMers as styrene, me~hyl styrene (vi.nyl toluene), ethyl styrene, isopropyl s~yrene, tertiary butyl styrene, etc 4-hydroxy C2tyrene, 4-chlorostyrene, and styrene with other common ring substituents.
~ he proportions of each monomer can vary widely. The vinyl monomer may range generally from 1-99 mole-~ and the monomer of the present invention may generally range rom 0.05-15 mole-~, preferably from about 0.1 mole-% to 9 mole-% and most preferably for reasons of economy and efficacy from about 0.5 mole-% to 3 mole-~. The molar proportions will vary according to the necessary wet adhesion action and scrub properties desired, and the economics of employing a larger amount of the active monomer of the present invention and the requirements of the physical properties.
The monomer of the present invention may be polymerized into ~ither a latex or solution compositions.
Polymerization can generally be carried out in a closed vessel under heated conditions. The solution polymeriza-tion reaction is generally carried ou~ with the monomer3 ir.
solution in an inert organic solvent such as tetrahydrG-furan, methyl ethyl ketone, acetone, ethyl acetate, or 25 other suitable oryanic solvents such as organic C-C2 -~
alkanols. Organic solvents can also be mixed with-compatible amounts of water in emulsions or inverse emulsion systems. Prererred solvents are non-tox.ic and odorless. Pre-polymer monomeric-starting materials used to form polymeric pre-emulsion compositions using the monomer of the present invention are typically dissolved or su~pended in the solvent to a deslred concentration.
Preferably, the polymerization of the-invention i~
typically performed at a concentration of about 10 w~-~ to 70 wt-% of the monomers in the solven~ material, althougn 8UBSTlTUTe 8HEET
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somewhat higher or lower concentrations may be employed in some cases.
Polymerization reactions are typically initiated in a conventional manner, preerably by u5e of a suitable initiator. Examples of suitable initiators include 2,2~-azobis(2-methylpropane nitrile)(AIB~), dibenzoyi peroxide tertiary butyl peroctoate, cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se or in combination with a reducing agent in the form of an oxidation reduction catalyst system.
During the course of the reaction, the reaction mixtura may be agitated and heated preferably in an inert atmosphere (purging with nitrogen, argon, etc.), to about 50-lOO~C., controlling the reaction temperature to a:oid destructive exotherms, preferably to about 75-95C.
Generally, depending upon the final application cf the polymeric composition, the polymer may contain anywhere from about 0.05 wt-~ to 15.0 wt-% of the monomer of the present invention, preferably from about .lO wt-% to 9.0 -20 wt~ of the present monomer, and most preferably abou_ .5 wt-~ to 3.0 wt-% of the monomer of the present inver.-ion.
However, it should be understood that this concentra-ior.
may vary given the physical properties to be imparce~ tG
the final system.
-The molecular weights of the resulting polymers may vary. However, the molecular weight of the resultinc solution copolymer is preferably at least approximately ; 3000. However the molecular weight of these polymer3 may generally range from lO00 to l,000,000.
Polymerization towards the formulation of latex or dispersion polymers may be completed under substanti-lly similar circumstances except ~hat the medium of polymerization is aqueous instead of organic. The molecular weights of the resulting latex polymers may vary generally from lO00 to 2 million with about 50,000 bsing a 8UBSTITUTE 8HEI~T
,, ., " , ,~ .... .. . .......... . . . .
WO91~12243 PCr/~'S91/01)93') 2~37 ~ 8-preferred weight. Depending on the comonomers used in the polymers of the present invention, these polymers form a colloidal dispersion suspended in an aqueous carrier ~,rhich, once applied, forms a readily wetting and scrub resistan~
film.
Once a monomer of the present invention system is polymerized with comonomers, the emulsion polymer may be formulated into any number of compositions including paints, film coatings, sealants, adhesives, caulks, or the like. The formulation of these systems will vary depending upon the application of the system, i.e., the systems final end use. However, formulation processes include those found within the following examples, as well as those generally known within the art. Generally, again dependins upon the physical properties to be imparted to the final system, the monomer will have a concentration ~ith the final system which may range from about 0.00l wt-~ to 10.0 wt-~, preferably from about .01 wt-~ to 7.0 wt-~, and mos.
preferably from about .10 wt-% to 5.0 wt-%.
The following examples illustrate the prepar~tions of monomers, and polymers utilizing ~:he present invention ir.
the preparation of films, caulks, coatings, aqueous latices, and aqueous systems.
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WO 91/1224?s P~r/~S41/0093~) . , WORRING EXAMP~ES SET I
The wet adhesion monomer of the present invention was synthesized using various feed stocks including N-(2-hydroxyethyl)oxazolidin~2-one or N,N-diethylethylenediamine in combination with alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) in the presencé of an organic solvent.
Monomer Synthesis Workin~ Example 1 The monomer R ~
H3 o (ICH2)~ o C-NHCOCH~CH~N -- -C
synthesized from N-(2-hydroxyelhyl)oxazolidin-2-one, and m-TMI using the following procedure. Using a LOO ml 3-necked round bottom flash equipped with a N~ inlet and magnetic spin bar, m-TMI (10.1 grams, 0.05 moles) w,~s added in 25 ml of ethyl acetate. A solution of N-(2-hydroxyethyl)oxazolidin-2-one (6.6 g, 0.05 mol) in ~5 mi of ethyl acetate was added to the mix over a 45 minut-interva}. After approximately 7 hours at 25C., ~ha , 25 reaction mixture was slightly cloudy and af~er an additional 30 minutes at 25~C., the entire reaction mixture formed a white,c~ystalline mass. The reaction mix~urs was allowed to stand at 25C. overnight. The solid was dissolved in about 150 ml hot ethyl acetate. Some - 30 insoluble material (about 1 gram) was removed by filtration. The solution was allowed to slowly cocl lo 25C. White crystals formed. The produce was placed in a ' 'freezer and the cryskals were collected by suction' '~
filtration, The cry9tals,had a melting point`of 129-130C.
Melting point, Carbon 13 nuclear'magnetic'resonance 8UBSTITUT~ 8HEET
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Summary of the I~v~ntion The present invention provides a polymerizable monomer for the promotion of wet adhesion having the ormula:
R' O
\ "
~ -N~1-C-Y-CH~(CH2)~N (C~12)~
Z=C X
wherein n = l or 2; m = l or 2; R' = H or CH3; ~ = -O-, : l0 -CH2, -NR-; R ~ H, -Cl5 alkyl, -aryl, -CH2(CH2)~-C z N, -CH~OC 1_5 alkyl, -(CH2)~OH, -CH~CH(OH)C~I~; A = phenylene or C j_5 alkylene; Y = -O-, -NH-, -NHNH~, -O-M-, -MH-~,-, or -NH-NH-M-; and o R' O NH O
M = -COCH2-CH-O-, -NH-C-CH2-, -NH-C-, and -C(CH2)XO-wherein x = 2 - 5. The monomer may also be synthesized to have vinyl acrylic functionality.
The monvmer of the present invention can be used either alone or polymerized in any given polymer system. The polymerizable monomer of the preC;ent invention provides far superior wet adhesion when compared to polymers presen~
commercially available and commonly used in the coatings and paint industries.
Detailed ~ cription of the Invention ^~ The present invention discloses monomers useful in polymeric materials, the monomers-providing enhanced we4 .: adhesion and scrub resistance. The enhanced wet adhesion monomers of ~he present invention may be polymerized into polymeric materials or polymers that may be added to other polymers. The instant monomer can be used in polymeric matrices which result in any number of adhesives, caulks, : latexes, paints,-coatings, and-sealants among other matrices. . .
The wet adhesion monomers of the present invention can be used in polymeric compositLons that are applied to any number of substrates and subjected to any number of ., ` $1JBSTITUTE~ 8HEI~
, .
W091/1~243 2~ PCT/~S91/0093s) environmenkal factors. The instant wet adhesion monomer may be applied in any number o~ ways. Wet adhesion monomers can be copolymerized Ln la-tex cornpositions, paint compositions, coating compositions, and film compoCitions.
The Monomer The present invention is a monomer for the promotion of wet adhesion having the formula:
R~ o ,~A-NH-C-Y-CH2(cH2)rN--tC 112)G
Z=C X
wherein n = l or 2; m = l or 2; R' ~ H or CH~; X = -C-, -CH" -NR-; R = H, -Cl 5 alkyl, -aryl, -CH,(CHq)x-C = N, -CHqOC!5 alkyl, -( CH,)~OH, -CH,CH(OH)CH~; A = phenylen or C1s alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-~-; and O R' O NH O
" I ,- .. ..
M = -COCH2-CH-O-, -NH-C-CH2 , -NH-C-, and -C(CH-,)xo-wherein x = 2 - 5. The monomer may hlso be synthesized to have vinyl acrylic functionality.
Synthesis of the monomer of the present inventior. is initiated by reacting any compound having an active ~inyl group and a reactive isocyana~e group with a bac~bone compound having an active hydrogen in the form of a reactive hydroxyl group or amine group. Generally, isocyanate-type compounds and monomers have been found useful to this end. The preferred isocyanate compound useful in the invention is a compound having a single polymerizable vinyl group and a single monoisocyana~e group. .
In preparation of the monomer of-the present inventior.
a vinyl compound such as alpha, alpha-diméthyl meta-isopropenyl benzyl isocyana~e (m-TMI) is combined with a backbone heterocyclic compounds ~uch as oxazolidinone in the presence of an organic ~olvent and heat. Generaliy, 5UBSTITUTE~ 8HEE~J j ~....................... .
WO91/1224~ PCr/~S91/0093~
~3~ 8 -4-any organic solvents found useful in synthesizing the monomer of the present lnvention include ethyl acetate, hexane, chloroform and the like. Optionally, a reaction catalyst such as dibutyl tin dilaurate may al50 be used Backbone compounds which may be allowed to react with m-TMI include any variety of heterocyclic or heteroaliphatic compounds including l-(2-hydroxye~hyl) imidazolidin-2-one, N,N-diethylethylenediamine, 2-(2-aminoethyl)imidazolidin-2-one and the like which when reacted with m-TMI produce polyme.rizable compounds which are capable of being used in all acrylic systems.
Alternatively, the monomer of the present invention mav be synthesized in any manner which permits its use in vinyl acrylic systems. In this instance, instead of using m-T~I, compounds such as 2-vinyl-4,4-dimethyl-2-oxazolin-S-one may be combined with backbone compounds such as N-(2-hydroxyethyl)oxazolidin-2-one, N,N-diethylethylenedi~mine and 2-(2-aminoethyl) imidazolidin-2-one in a manner that provides the polymerizable compound useful in vinyl acrylic systems. In : this instance, the 2-vinyl-4,4-dimethyl-2-oxazGlin-5-one has a reactive carbonyl in the five position which rssui~
in the five member ring opening when combined wit~. th~
` reactive amine moiety of the backbone compound. The resulting monomer is an imidazoline type compound having an amide linkage which is terminated by a polymerizable olefin group at one end of the monomer. This monomer may then be polymerized with compounds such as vinyl acetate and n-butyl acrylate to provide an emulsion polymer useful . 30 again in any type of latex, caulk, adhesive, or other film ,,,forming,compositions~
In preparation of the polymers of the invention, olyrnerization occurs through the vinyl group Comonomers The polymerizable compound of the present invention may ' SUBSTITUTE 8HEE~-~
.
WO91/12~43 PCr/~S91/0093~) 2 ~ o L' ~ ~ ~
-5- ;
be combined with any number of monomers to form a copolymer. The monomer of the present invention may be polymerized with virtually any other vinyl monomer Examples of the broad classes of such vinyl monomers include alpha-olefins, vinyl chlorides, vinylidene chlorides, vinyl aromatic monomers, polymerizable alpha, beta-unsaturated carboxylic acids and esters, and other well known monomers.
The vinyl unsaturated monomer can be an alpha-olefin monomer such as ethylene, propylene, butylene, isobutylene, hexene; styrene, alpha methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, ricinoleic acid, oleic acid, linoleic acid, butadiene, and the like. Alpha-olefins tha can also be used in the invention include other Cit alpha-olefins such as cyclopentene, cyclopentadiene, 1,3-butadiene, l-hexene, norbornene, etc.
Useful acrylic monomers include methylacrylate, methyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, butyl acrylat~, hexyl acrylate, cyclohexylacrylate, (2-hydroxyethyl) methacrylate, (2-hydroxyethyl) acrylate, (3-hydroxypropyl) methacrylata, (3-hydroxypropyl) acrylate, (pipiridinoethyl) methacrylat_, (morpholinoethyl) methacrylate, and the like.
Useful unsaturated dicarboxylic acids include i~aconic acid, cinnamic acid, crotonic acid, mesaconic acld, maleic acid, fumaric acid, and the like; alpha, beta unsaturaled dicarboxylic acid esters of the dicarboxylic acid es~ers described above inc-~uding aromatic esters, cycloal~yl esters, alkyl esters, hydroxy alkyl esters, alkoxy alkyl esters, and the like.
,, Vinyl aromatic monomers that can be used with the monomer of this invention include monomers that comprise a~
least one aromatic group and at least one polymerizable vinyl group. Typical examples of aromatic groups include ; 35 phenyl, substituted phenyl, naphthyl, phenanthryl, and 8VBS'rlTUTE~ 8HEEr~.
,. ... ... ...
W091/12243 PCr/~S91/0093t) 2~7~ 6-others. Preferred vinyl aromatic monomers include the styrene family including such monoMers as styrene, me~hyl styrene (vi.nyl toluene), ethyl styrene, isopropyl s~yrene, tertiary butyl styrene, etc 4-hydroxy C2tyrene, 4-chlorostyrene, and styrene with other common ring substituents.
~ he proportions of each monomer can vary widely. The vinyl monomer may range generally from 1-99 mole-~ and the monomer of the present invention may generally range rom 0.05-15 mole-~, preferably from about 0.1 mole-% to 9 mole-% and most preferably for reasons of economy and efficacy from about 0.5 mole-% to 3 mole-~. The molar proportions will vary according to the necessary wet adhesion action and scrub properties desired, and the economics of employing a larger amount of the active monomer of the present invention and the requirements of the physical properties.
The monomer of the present invention may be polymerized into ~ither a latex or solution compositions.
Polymerization can generally be carried out in a closed vessel under heated conditions. The solution polymeriza-tion reaction is generally carried ou~ with the monomer3 ir.
solution in an inert organic solvent such as tetrahydrG-furan, methyl ethyl ketone, acetone, ethyl acetate, or 25 other suitable oryanic solvents such as organic C-C2 -~
alkanols. Organic solvents can also be mixed with-compatible amounts of water in emulsions or inverse emulsion systems. Prererred solvents are non-tox.ic and odorless. Pre-polymer monomeric-starting materials used to form polymeric pre-emulsion compositions using the monomer of the present invention are typically dissolved or su~pended in the solvent to a deslred concentration.
Preferably, the polymerization of the-invention i~
typically performed at a concentration of about 10 w~-~ to 70 wt-% of the monomers in the solven~ material, althougn 8UBSTlTUTe 8HEET
,, .,, .. , . ,, " ~, . ", , , WO91/1224~ PCr/~'S91/00~3' ~". ~ J~
somewhat higher or lower concentrations may be employed in some cases.
Polymerization reactions are typically initiated in a conventional manner, preerably by u5e of a suitable initiator. Examples of suitable initiators include 2,2~-azobis(2-methylpropane nitrile)(AIB~), dibenzoyi peroxide tertiary butyl peroctoate, cumene hydroperoxide, diisopropyl percarbonate, ammonium persulfate, and the like, per se or in combination with a reducing agent in the form of an oxidation reduction catalyst system.
During the course of the reaction, the reaction mixtura may be agitated and heated preferably in an inert atmosphere (purging with nitrogen, argon, etc.), to about 50-lOO~C., controlling the reaction temperature to a:oid destructive exotherms, preferably to about 75-95C.
Generally, depending upon the final application cf the polymeric composition, the polymer may contain anywhere from about 0.05 wt-~ to 15.0 wt-% of the monomer of the present invention, preferably from about .lO wt-% to 9.0 -20 wt~ of the present monomer, and most preferably abou_ .5 wt-~ to 3.0 wt-% of the monomer of the present inver.-ion.
However, it should be understood that this concentra-ior.
may vary given the physical properties to be imparce~ tG
the final system.
-The molecular weights of the resulting polymers may vary. However, the molecular weight of the resultinc solution copolymer is preferably at least approximately ; 3000. However the molecular weight of these polymer3 may generally range from lO00 to l,000,000.
Polymerization towards the formulation of latex or dispersion polymers may be completed under substanti-lly similar circumstances except ~hat the medium of polymerization is aqueous instead of organic. The molecular weights of the resulting latex polymers may vary generally from lO00 to 2 million with about 50,000 bsing a 8UBSTITUTE 8HEI~T
,, ., " , ,~ .... .. . .......... . . . .
WO91~12243 PCr/~'S91/01)93') 2~37 ~ 8-preferred weight. Depending on the comonomers used in the polymers of the present invention, these polymers form a colloidal dispersion suspended in an aqueous carrier ~,rhich, once applied, forms a readily wetting and scrub resistan~
film.
Once a monomer of the present invention system is polymerized with comonomers, the emulsion polymer may be formulated into any number of compositions including paints, film coatings, sealants, adhesives, caulks, or the like. The formulation of these systems will vary depending upon the application of the system, i.e., the systems final end use. However, formulation processes include those found within the following examples, as well as those generally known within the art. Generally, again dependins upon the physical properties to be imparted to the final system, the monomer will have a concentration ~ith the final system which may range from about 0.00l wt-~ to 10.0 wt-~, preferably from about .01 wt-~ to 7.0 wt-~, and mos.
preferably from about .10 wt-% to 5.0 wt-%.
The following examples illustrate the prepar~tions of monomers, and polymers utilizing ~:he present invention ir.
the preparation of films, caulks, coatings, aqueous latices, and aqueous systems.
- . . :, . ,:, . .
, ~
"
:
, 8U~3STITUTE. 8HEET
, ,, ,, ,,, ~, .. .. . . . .
WO 91/1224?s P~r/~S41/0093~) . , WORRING EXAMP~ES SET I
The wet adhesion monomer of the present invention was synthesized using various feed stocks including N-(2-hydroxyethyl)oxazolidin~2-one or N,N-diethylethylenediamine in combination with alpha, alpha-dimethyl meta-isopropenyl benzyl isocyanate (m-TMI) in the presencé of an organic solvent.
Monomer Synthesis Workin~ Example 1 The monomer R ~
H3 o (ICH2)~ o C-NHCOCH~CH~N -- -C
synthesized from N-(2-hydroxyelhyl)oxazolidin-2-one, and m-TMI using the following procedure. Using a LOO ml 3-necked round bottom flash equipped with a N~ inlet and magnetic spin bar, m-TMI (10.1 grams, 0.05 moles) w,~s added in 25 ml of ethyl acetate. A solution of N-(2-hydroxyethyl)oxazolidin-2-one (6.6 g, 0.05 mol) in ~5 mi of ethyl acetate was added to the mix over a 45 minut-interva}. After approximately 7 hours at 25C., ~ha , 25 reaction mixture was slightly cloudy and af~er an additional 30 minutes at 25~C., the entire reaction mixture formed a white,c~ystalline mass. The reaction mix~urs was allowed to stand at 25C. overnight. The solid was dissolved in about 150 ml hot ethyl acetate. Some - 30 insoluble material (about 1 gram) was removed by filtration. The solution was allowed to slowly cocl lo 25C. White crystals formed. The produce was placed in a ' 'freezer and the cryskals were collected by suction' '~
filtration, The cry9tals,had a melting point`of 129-130C.
Melting point, Carbon 13 nuclear'magnetic'resonance 8UBSTITUT~ 8HEET
'~ ' '' ' , ' ' ' ' ' " '7',' ' '.' ' ' ' ' ' ' ' ' : ' ' ' ' ' . .
3 Pcr/~S9l/~o939 2~t'~ 1O-spectroscopy, and infrared analysis were completed on the monomer of Example 1 with the following results. Referring to Figure 1, nuclear magnetic resonance spe~troscopy (N~R) provided the following data reported by chemical shlft (PPM): Carbon No. 1 at 21.~; Carbon No. 2 at 29.4; Carbon No. 3 or 4 at 43.8; Carbon No. ~ or 3 at 44.7; Carbon No. 5 at 55.3; Carbon No. 6 at 51.1; Carbon No. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 8 at 122.0; Carbon No. 10 at 123.9; Carbon No. 11 at 124.0; Carbon No. 12 at 128.3;
Carbon No. 13 at 141.3; Carbon No. 14 at 143.5; Carbon No 15 at 147.1; Carbon No. 16 at 154.5; Carbon No. 17 at 158.6.
The Carbon 13 spectra of the sample exhibits both the proper number of nonequivalent carbons and the correct number of attached protons recorded by the monomer. Upon determination, the melting point of the monomer was 129.0 to 130.0C.
Infrared scan provided the following results using a KBr pellet: NH amine at 3314 cm~l C = O (oxazolidinone) at 1737 cm~'; C = O (urethan) at 1715 cm~l; C = C at 89~ cm~
C = C (aromatic) at 812 cm~l.
work~3g_~sj~ 2 ~n analogue of the wet aclhesion monomer naving tne J formula:
2 5 ~ CH3 0 ~';' rO`L I " CH~CH;
~-NHCNHCH,CH7N~
CH3 ~CH,CH3 was prepared using m-TMI and N,N~diethylethylenediamine in hexane by the following procedure.
Using a 250 ml 3-necked roundbottom flask equipped with ' a reflux condenser, N2 inlet, magnetic spin bar, temperature probe, and a pressure equalizing addition funnel, m-TMI (20.1 g, 0.10 mol) was added in 50 ml hexane.
A solution of H~NCH7CH7N(CH2CH3)2 (11.6 g, 0.10 mol) in 50 ml of hexane was then added over a q5 minute interval. An 81JBSTITUTE 8HET. -W091/l2243 PCT/~1591lOO~39 ice-water bath was used to keep the reaction mixture between 20C. and 25C. The slightly cloudy reaction mixture was stirred ~or 2 hours at 25C. Ethyl acetate, lS
ml, was added and the clear solution was ~iltered ana S placed in the freezer overnight. The white crystals were collected by suction filtration and had a melting poin~ =
63.5-64.5C.
The monomer of Example 2 was then characterized using NMR spectroscopy melting point, and infrared scan.
Referring to Figure 2, C13 NMR spectxo~copy was completed and resulted in the following data (C-13 PPM): Carbcn No.
- l at ll.S; Carbon No. 2 at 21.9; Carbon No. 3 at 30.~;
Carbon No. 4 at 38.2; Carbon No, 5 at 46.6; Carbon No. 6 at 52.3; Carbon No. 7 at 54.8; Carbon No. 8 at 112.6; Ca~bon No. 9 at 122.6; Carbon No. 10 at 124 ! 2; Carbon NO. li at 124.6; Carbon No. 12 at 128.5; Carbon No. 13 at 141.6;
Carbon No. 14 at 143.6; Carbon No. 15 at 147.2; and Carbon No. 16 at 158.2.
Upon analysis, the melting point of the compound was 63.5 to 64.5C. Infrared analysis through KBr p_ilet showed: NH at 3359 and 3322 Cm~i; C = O at 1633 cm~; _ = C
at 882 cml; C = C (aromatic) at 802 cm .
' 8U~3STlTUTe 8HEE~
..... . . .............. .. .. .. ...... . . . .. . . ..
WO91/12243 PCr/~'S9l/00~39 Workinq Example 3 Synthesis of the monomer having the formula ~CH3 0 f ~12C~
f N~COCH~C~I~N~ ~, ~, CH3,~! "
o was then attempted using m-TMI, 1-(2-hydroxyethyl) imidazolidin-2-one, and the following process.
Using a 1 liter 3-necked roundbottom flask ~ equipped with a N~ inlet, magnetic spin bar and a pressure ; equalizing addition funnel, m-TMI (224.6 9, 1.12 mol)l was added with 150 rnl CHC13 and l.0 g of dibutyl tin dilaura~_.
A solution cf the cyclic urea (154.0 g. 1.17 mol) was ther.
~ added in 250 ml of CHCl3 over a one hour interval. The flas~ was cooled once with cold water to maintain a ~ temperature less than 30C. After 2 hours at ambient i~ temperature the CHCl3 was removed from the reaction mixture with a rotary evaporator to yield an oil. The oil was dissolved in an ethyl acetate/hexane mixture and filtered while hot. White crystals began l:o form upon coolins.
Evaluation of the monomer resulting from Working Example 3 was then at~empted usin~ nuclear magne~ic resonance spectroscopy, melting pc~int and infrared analysis. Referring to Figure 3, NMR spectra provided the following data (C-13, PPM): Carbon No. 1 at 21.9; Carbon ~` No. 2 at 29.5; Carbon No. 3 at 38.2; Carbon No. 4 or 5 at 43.1; Carbon No. 5 or 4 at 45.4; Carbon No. 6 at 55.2;
Carbon NO. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 5 at 122.1; Carbon No. 10 at 124.0; Carbon No. ll at 124.1;
Carbon No. 12 at 128.3; Carbon No. 13 at 141.4; Carbon No.
14 at 143.6; Carbon No. 15 at 147.3; Carbon Mo. 16 at 154.9; Carbon No. 17 at 163.1.
Upon analysis, the meltlng point of this monomer was determined to be 94.5 to 95.5C. An infrared analysis waC
then completed using a potassium bromide pellet and ,, .~
8UE~STITUTE~ 8HEEl~
.... ... .......... . . . . .
W09l/1224~ PCI/~:S91/0093') -13- 2 ~7 h ~ 9 ~
provided the following data: NH at 3423 and 3264 cm ; C =
o at 1713 cm~-; NH at 1679 cm~~; C = C at ~96 cm~~; and C = C
(aromatic) at 802 cm~l.
The NMR spectra of the sample clearly indicated that the desired reaction product was obtained in high purity.
8UBSTITUTE~ 8HE~Fr ... ....... . . .. . . . .
WO91/l2243 PCr/~S91/00939 Workinq Example 4 ~01 1 "
CNH-CNHCH2CH,N ~ CH2 ) ~, CH3 O=C ~ NH
A similar monomer synthesized in Example 3 was then synthesized using meta-TMI and 2-(2-aminoethyl) imidazolidin-2-one (AEI) using the following procedure, Using a 500 ml 3-necked roundbottom 1ask equipped with a pressure equalizing addition ~unnel, magneti.c spin bar, thermometer and a N7 inlet was added m-'rMI ~80.4 g, 0.40 mol.) was added to the flask with 100 ml of chloroform. A
solution of AEI (5S.6 g, 0.40 mol) in 100 ml of chlorororm was added dropwise to the flask over a 1 hour interval while maintaining the reaction temperature between 20-25C
with an ice/water bath. The reaction mixture was slirred at 24C overnight and then filtered. The chloroform was removed on a rotary evaporator to yield 140 g or crude product (lQ3~). Recrystallization from ethyl acetate/ethanol afforded a white crystalline solid, having a melting point of 143.5-44.5C.
8VBSTI,TUTE~8HEE~ I
, WO 91/~224?s PC~/l,;S~)1/0093') ;~ 9~
Workinq Example 5 A scale up of Example 4 was then attempted using 1-(2-aminoethyl)imidazolidin~2-one, m-T~I, and the following procedure.
Using a 2 liter 3-necked roundbottom flask e~uipped with a mechanical stirrer, reflux condenser, pressure equalizing addition funnel and a N2 inlet, a solution of 1-(2-aminoethyl)imidazolidin-2-one (173.6 g, 1.34 mol) was added in 500 ml of chloroform to the flask.. A solution of m-TMI (275.5 g, 1.38 mol) i.n 250 ml of chloroform was added to the flask at a rate such that tho temperature of the reaction mixture did not exceed 25C. The flask was cooled with an ice-water bath. Once completely added, the mix~ure crystallized. An additional 300 ml CHC13 was added and the mixture was stirred at 25C. for 2 hours. The mixture was then analyzed by TLC. The slurry of the product in CHC13 was dissolved by warming with a hot water bath. The clear solution was filtered into an Erlenmeyer flask and allowed to cool to 25C., and subsequently placed in the freezer.
A white crystalline solid was isolated by suction filtration and the crude product ;had a melting point of 138-143C. The solid was recrystallized and recover6~ rro~
ethyl acetate/isopropanol (60:40). The recovered -rvs~ai3 ad a melting point of 143.0 to 144.5C.
The monomer reaction product of Example 5 was ther.
submitted for structural evaluation by C13 N~R and in-rarea spectroscopy. Referring to Pigure ~, C13 NMR spectroscopy provided the following chemical shift data: Carbon No. 1, 21.5; Carbon No. 2, 30.0; Carbon Nos. 3 or 4, 37.2; Carbon 30 Nos. 4 or 3, 37.4; Carbon Nos. 5 or 6, 43.6; Carbon Nos. o or 5, 44.7; Carbon Nos. 7, 54.0; Carbon No. 8, 112.1;
Carbon No. 9, 121.7; Carbon No. 10, 122.7; Carbon No. 11, 124.1; Carbon No. 12, 127.7; Carbon No. 13, 139.9; Carbor.
No. 14, 143.0; Carbon No. 15, 149.0; Carbon No. 16, 1;6.9;
35 and Carbon No. 17, 16.'.2.
8UE~STITUTF 8HE~ET
Carbon No. 13 at 141.3; Carbon No. 14 at 143.5; Carbon No 15 at 147.1; Carbon No. 16 at 154.5; Carbon No. 17 at 158.6.
The Carbon 13 spectra of the sample exhibits both the proper number of nonequivalent carbons and the correct number of attached protons recorded by the monomer. Upon determination, the melting point of the monomer was 129.0 to 130.0C.
Infrared scan provided the following results using a KBr pellet: NH amine at 3314 cm~l C = O (oxazolidinone) at 1737 cm~'; C = O (urethan) at 1715 cm~l; C = C at 89~ cm~
C = C (aromatic) at 812 cm~l.
work~3g_~sj~ 2 ~n analogue of the wet aclhesion monomer naving tne J formula:
2 5 ~ CH3 0 ~';' rO`L I " CH~CH;
~-NHCNHCH,CH7N~
CH3 ~CH,CH3 was prepared using m-TMI and N,N~diethylethylenediamine in hexane by the following procedure.
Using a 250 ml 3-necked roundbottom flask equipped with ' a reflux condenser, N2 inlet, magnetic spin bar, temperature probe, and a pressure equalizing addition funnel, m-TMI (20.1 g, 0.10 mol) was added in 50 ml hexane.
A solution of H~NCH7CH7N(CH2CH3)2 (11.6 g, 0.10 mol) in 50 ml of hexane was then added over a q5 minute interval. An 81JBSTITUTE 8HET. -W091/l2243 PCT/~1591lOO~39 ice-water bath was used to keep the reaction mixture between 20C. and 25C. The slightly cloudy reaction mixture was stirred ~or 2 hours at 25C. Ethyl acetate, lS
ml, was added and the clear solution was ~iltered ana S placed in the freezer overnight. The white crystals were collected by suction filtration and had a melting poin~ =
63.5-64.5C.
The monomer of Example 2 was then characterized using NMR spectroscopy melting point, and infrared scan.
Referring to Figure 2, C13 NMR spectxo~copy was completed and resulted in the following data (C-13 PPM): Carbcn No.
- l at ll.S; Carbon No. 2 at 21.9; Carbon No. 3 at 30.~;
Carbon No. 4 at 38.2; Carbon No, 5 at 46.6; Carbon No. 6 at 52.3; Carbon No. 7 at 54.8; Carbon No. 8 at 112.6; Ca~bon No. 9 at 122.6; Carbon No. 10 at 124 ! 2; Carbon NO. li at 124.6; Carbon No. 12 at 128.5; Carbon No. 13 at 141.6;
Carbon No. 14 at 143.6; Carbon No. 15 at 147.2; and Carbon No. 16 at 158.2.
Upon analysis, the melting point of the compound was 63.5 to 64.5C. Infrared analysis through KBr p_ilet showed: NH at 3359 and 3322 Cm~i; C = O at 1633 cm~; _ = C
at 882 cml; C = C (aromatic) at 802 cm .
' 8U~3STlTUTe 8HEE~
..... . . .............. .. .. .. ...... . . . .. . . ..
WO91/12243 PCr/~'S9l/00~39 Workinq Example 3 Synthesis of the monomer having the formula ~CH3 0 f ~12C~
f N~COCH~C~I~N~ ~, ~, CH3,~! "
o was then attempted using m-TMI, 1-(2-hydroxyethyl) imidazolidin-2-one, and the following process.
Using a 1 liter 3-necked roundbottom flask ~ equipped with a N~ inlet, magnetic spin bar and a pressure ; equalizing addition funnel, m-TMI (224.6 9, 1.12 mol)l was added with 150 rnl CHC13 and l.0 g of dibutyl tin dilaura~_.
A solution cf the cyclic urea (154.0 g. 1.17 mol) was ther.
~ added in 250 ml of CHCl3 over a one hour interval. The flas~ was cooled once with cold water to maintain a ~ temperature less than 30C. After 2 hours at ambient i~ temperature the CHCl3 was removed from the reaction mixture with a rotary evaporator to yield an oil. The oil was dissolved in an ethyl acetate/hexane mixture and filtered while hot. White crystals began l:o form upon coolins.
Evaluation of the monomer resulting from Working Example 3 was then at~empted usin~ nuclear magne~ic resonance spectroscopy, melting pc~int and infrared analysis. Referring to Figure 3, NMR spectra provided the following data (C-13, PPM): Carbon No. 1 at 21.9; Carbon ~` No. 2 at 29.5; Carbon No. 3 at 38.2; Carbon No. 4 or 5 at 43.1; Carbon No. 5 or 4 at 45.4; Carbon No. 6 at 55.2;
Carbon NO. 7 at 61.9; Carbon No. 8 at 112.5; Carbon No. 5 at 122.1; Carbon No. 10 at 124.0; Carbon No. ll at 124.1;
Carbon No. 12 at 128.3; Carbon No. 13 at 141.4; Carbon No.
14 at 143.6; Carbon No. 15 at 147.3; Carbon Mo. 16 at 154.9; Carbon No. 17 at 163.1.
Upon analysis, the meltlng point of this monomer was determined to be 94.5 to 95.5C. An infrared analysis waC
then completed using a potassium bromide pellet and ,, .~
8UE~STITUTE~ 8HEEl~
.... ... .......... . . . . .
W09l/1224~ PCI/~:S91/0093') -13- 2 ~7 h ~ 9 ~
provided the following data: NH at 3423 and 3264 cm ; C =
o at 1713 cm~-; NH at 1679 cm~~; C = C at ~96 cm~~; and C = C
(aromatic) at 802 cm~l.
The NMR spectra of the sample clearly indicated that the desired reaction product was obtained in high purity.
8UBSTITUTE~ 8HE~Fr ... ....... . . .. . . . .
WO91/l2243 PCr/~S91/00939 Workinq Example 4 ~01 1 "
CNH-CNHCH2CH,N ~ CH2 ) ~, CH3 O=C ~ NH
A similar monomer synthesized in Example 3 was then synthesized using meta-TMI and 2-(2-aminoethyl) imidazolidin-2-one (AEI) using the following procedure, Using a 500 ml 3-necked roundbottom 1ask equipped with a pressure equalizing addition ~unnel, magneti.c spin bar, thermometer and a N7 inlet was added m-'rMI ~80.4 g, 0.40 mol.) was added to the flask with 100 ml of chloroform. A
solution of AEI (5S.6 g, 0.40 mol) in 100 ml of chlorororm was added dropwise to the flask over a 1 hour interval while maintaining the reaction temperature between 20-25C
with an ice/water bath. The reaction mixture was slirred at 24C overnight and then filtered. The chloroform was removed on a rotary evaporator to yield 140 g or crude product (lQ3~). Recrystallization from ethyl acetate/ethanol afforded a white crystalline solid, having a melting point of 143.5-44.5C.
8VBSTI,TUTE~8HEE~ I
, WO 91/~224?s PC~/l,;S~)1/0093') ;~ 9~
Workinq Example 5 A scale up of Example 4 was then attempted using 1-(2-aminoethyl)imidazolidin~2-one, m-T~I, and the following procedure.
Using a 2 liter 3-necked roundbottom flask e~uipped with a mechanical stirrer, reflux condenser, pressure equalizing addition funnel and a N2 inlet, a solution of 1-(2-aminoethyl)imidazolidin-2-one (173.6 g, 1.34 mol) was added in 500 ml of chloroform to the flask.. A solution of m-TMI (275.5 g, 1.38 mol) i.n 250 ml of chloroform was added to the flask at a rate such that tho temperature of the reaction mixture did not exceed 25C. The flask was cooled with an ice-water bath. Once completely added, the mix~ure crystallized. An additional 300 ml CHC13 was added and the mixture was stirred at 25C. for 2 hours. The mixture was then analyzed by TLC. The slurry of the product in CHC13 was dissolved by warming with a hot water bath. The clear solution was filtered into an Erlenmeyer flask and allowed to cool to 25C., and subsequently placed in the freezer.
A white crystalline solid was isolated by suction filtration and the crude product ;had a melting point of 138-143C. The solid was recrystallized and recover6~ rro~
ethyl acetate/isopropanol (60:40). The recovered -rvs~ai3 ad a melting point of 143.0 to 144.5C.
The monomer reaction product of Example 5 was ther.
submitted for structural evaluation by C13 N~R and in-rarea spectroscopy. Referring to Pigure ~, C13 NMR spectroscopy provided the following chemical shift data: Carbon No. 1, 21.5; Carbon No. 2, 30.0; Carbon Nos. 3 or 4, 37.2; Carbon 30 Nos. 4 or 3, 37.4; Carbon Nos. 5 or 6, 43.6; Carbon Nos. o or 5, 44.7; Carbon Nos. 7, 54.0; Carbon No. 8, 112.1;
Carbon No. 9, 121.7; Carbon No. 10, 122.7; Carbon No. 11, 124.1; Carbon No. 12, 127.7; Carbon No. 13, 139.9; Carbor.
No. 14, 143.0; Carbon No. 15, 149.0; Carbon No. 16, 1;6.9;
35 and Carbon No. 17, 16.'.2.
8UE~STITUTF 8HE~ET
4~ I'Cr/L'~')1/~0')3') 2~7~ 16-A melting point for the sample was determined to be 143.5-144.5C. and an infrarecl scan was run of the sample using a KBr pellet. The infrared scan provided the following data: NH at 3349, 3242 cm !; C = O at 1685 cm ;
NH at 1680 cm~!; NH at 1660 cm~l; C = C at 890 cm~'; and C =
C aromatic at 804 cm-~.
The Carbon 13 spectra of the sample exhibit both the proper number of nonequivalent carhons and the correct number of attached protons required by the formula of this monomex.
8UB9TITUTE 8HEE~
.... ... . ..
WO91~12243 PCT/~591/00939 -17- ~ :
Workinq Example 6 A synthesis of a solid monomer having the formula ~ I_NHCNHCH~CH~N /NH
CH3 "
- O
was then attempted using m-TMI, and l-(2-aminoethyl) imidazoline-2-one (AEI) using the following process. Using ; a l liter 3-necked roundbottom flask equipped with a ~
; inlet, mechanical s~irrer, pressure equalizing addition ~; funnel and a thermometer (AEI) (64.5 g, 0.50 mol) was added in 200 ml of ethyl acetate to the flas~. A solution of m-TMI (lOl.5 g, 0.505 mol) in lO0 ml of ethyl acetate was added dropwise to the cloudy amine/ethyl acetate mixture.
After the addition of about lO ml of the m-TMI soiution, ~; ~ the reaction mixture became clear. The reaction mi~ture was cooled with a cold water bath to maintain the temperature between 25-30C.
A few white crystals began to form on the side of the reaction flask after about 35 ml of the m-TMI solu~ion had been added. Fine crystals were disper~ed in the reactior.
mixture after about 50 ml of the m-T~I solution hz~ beer;
added. A white crystalline slurry was obtained a~er tne addition of 60 to 65 ml of the m-T~I solution. The m-T~I
solution was added dropwise over a l hour interva . The reaction mixture was stirred with some difficulty upon completion of the addition of the m-T~.I solution. An additional 25 ml of ethyl acetate was added to ths reaction mixture to facilitate mixing. The mixture was s~irred for -3 hours àt 25C. and the white solid was isolated by suction filtration with a Buchner funnel.
The reaction flask was rinsed with lO0 ml of ethyl ; 35 acetate and then it was poured over the crystals in the Buchner funnel. The melting point of the recovere~ white solid was 138.5-142 0~C
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The fil~er cake was broken up and dried by pullinq air through the pulverized 501id for 30 minutes with a water aspirator. The weight of the solid was 232.4 g. The solid was air dried overnight, weight = 201.3 g. The filtrate was concentrated and an additional 6.8 g of solid was obtained. The solid was further dried by spreading on a sheet of release paper to obtain 159.8 g of product. Total recovery = 159.8 ~ 6.8 = 166.6 g (100.9~). The residue collected by concentrating the mother liquor was a mixture of a crystalline compound and an oil. The material was no~
characterized further.
E lsion P~mers Emulsion polymeric compositions were then synthesized using the monomers of Working Examples 1, 2, 3 and 6.
Generally, emulsion polymers containing the monomer of the present invention were polymerized by charging a reactor with water, a surfactant based defoamer such as Balab 748, commercially available from Witco Chemical Co., and diammonium phosphate. A catalyst was then charged into the reactor over a delayed period of time as a water carried system of ammonium persulfate and sodium metabisulfite. Thc pre-emulsion was prepared by ~irst forming a solu~ion of the monomer of the present invent.Lon with a surfactant sucr.
as Igepal CA897 (from GAF) and other polymerizable monomer~i constituents listed in Working Examples 7-10 and subseguently adding the solution of monomers and surfactanr to a beaker containing water ~Ihich was being agitated with a paddle-type blade stirrer. The pre-emulsion composition was then added to the reactor and over a delayed period or time, an additional amount of the same catalyst was added to thé reactor.
.
.... . . . .
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8UBSTI~UTE 8HEEr~
W091/1224~ PCT/USl)l/0~939 ~
Z~ J~3 , Workinq Example 7 The monomer of Example 6 was used to prepare a pre emulsion polymer base for use in a paint composition. The `` pre-emulsion polymer base had the following compouncl and 5 monomer constituents in the reaction.
Pre-Emulsion Constituents (Parts By_Weiqht) H,O 206.4 206.4 IGEPAL CA897 lethyoxylated 60.88 60.88 phenol surfactant from GAF Corporation) Example 6 Monomer 8.19 --~:: Example 6 Monomer (unrecrystallized) -- 8.19 : 15 Diammonium Phosphate l.0 1.0 n-butyl acrylate 336.8 336.8 Me~hyl methacrylate 333,4 333,4 Methacrylic Acid 12.77 i2.77 : , 5., '. ~.
' ' .
, ' : WO91/1224~ PC'r/~:S~I/U0~39 2 ~ 7 ~ 20--Workinq ExamPle 8 Using the same process as Example 7 the monomers of Examples 2 and 3 wore usecl to ~orm a pre-emulslon ~' composition.
5 Pre-Emulsion Constituents Parts By Weiqht 8A _ 8B
H~O 206,4 206.4 IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 60.88 10 Example 2 8.19 --Example 3 -- ô.19 Diammonium Phosphate 1.0 l.C
.:., n-butyl acrylate 336.8 336.8 Methyl methacrylate 333,4 333,4 15 Methacrylic Acid 12.77 12.77 Using the process of the two preceding Examples the monomers of Example 1 and 6 we:re used to form a pre-emulsion composition base for Examples 9 and 10.
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Workinq Example 9 Pre-Emulsion Constituents Parts By Weiqht H~O 206,4 206.4 IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 60.88 Example 1 Monomer 8.19 --Example 6 Monomer -- 8.19 Diammonium Phosphate 1.0 2.0 10 n-butyl acrylate 336.8 336.8 Methyl methacrylate 333,4 333,4 Methacrylic Acid 12,77 12.77 .
SU~3STITUT~ 8HEEl' ~`:
: WO91/12243 PCT/~S91/0093~3 2~ ~22-Workinq Example 10 Pre-Emulsion Constituents Parts BY Welqht H2O 206.
IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 Example 6 Monomer 4.10 Diammonium Phosphate 1.0 : ~ n-butyl acrylate 336.8 Methyl methacrylate 330.2 10 Methacrylic Acid 12,77 :;
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WO91/1224~ ~Cr/~'S')l/~0939 -23- 2~7 ~
Piqment ~rlnds In preparation of paint systems having a polymer containing the wet adhesion monomer of the present invention pigments grinds were forrnulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Ti~anium dioxide was added to the liquid phase first, then adding the extenders in any order after the TiO-,. Once the pigment had been wet out, the remaining amount of defoamer was added. The pigment`
composition was then ground at high speed (about ~,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.
~UBST~TUTe 8HE@~
..... . . . . . . ... ...... . .. .. . .....
W091/1224~ PCT/~'S91/~)0939 ~ 8 -2~-Exterior Flat GrindParts By Weiqht Water, DI 9l,6 Nopcosperse 44 (dispersant, 7,7 Henkel Corp.) 5 Nuosept 95 (preservative, l.5 Nuodox Inc.) Polyphase AF-l (mildewcide 4.8 Troy Chemical Corp.) Igepal C0-630 (from GA~ Corp.) 3,5 lO AMP 95 (dispersant, l.5 Augus Chemical Co.) TiO~ 250.0 Feldspar (available from l90.0 Indusmin, Inc.) 15 Drew-L464 (Defoamer availablel.98 from Drew Industries) 8UE~S~'ITUTE~ 8HEE~
, . .. ..... . .
WO 91/12243 Pc~r/~s9ll()o~3~) -25-2~tît~1 ~r3~3, Exterior Semiqloss Grind Parts By Weiqh~
Water, DI 58.3 Tamol 73l (dispersant, 8.6 Rohm & Haas) Igepal C0-630 ~surfactant, 3 5 GAF Corp.) AMP 95 (dispersant, l.O
Augus Chemical Co.) Nuosept 95 (preservative, l.5 Nuodex Inc.) Polyphase AF-l (mildewcida, 4.8 Troy Chemical) Ethylene Glycol l8.6 TiO1 250.0 Clay 25.0 Drew L464 ~defoamer, Drew l.8 Industries) 373.l 8UBSTITUTE 8HeFr ., ,,, ,,,,~,.. , ~, , , W09ltl224~ T'C't'/~S')l/00')31) 2~
S~mi-Gloss and Flat Paints . .
Paint systems, semigloss as well as flat, were then formulated using the polymeric systern3 of Working Examples 7-10 and pigment grinds previously formulated by weighing the latex polymer and defoamer into a lined can or stainless steel beaker. The system was then mixed with a three bladed paddle and the pigment grind and water was added to the latex. Cellulosic Natrosol~U thickeners were added along with the propylene glycol and TexanolT~.
The mixture was slowly and continuously mixed until a vortex formed with agitation increased as needed. The composition was mixed for 10 minutes or until the thickene~-dissolved. Once formulated, the paint was covered and le~
stand for 24 hours prior to testing. This process was used to formulate the exterior flat and semi-gloss paint of Examples 11 and 12.
8UBSTITUTE~ 8~1E~
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" , W~91/1224~ PC~/~'S9l/00~39 2~i7 ~
The term "latex" is provided below and both ~7Orkin~
Examples 12 and 13 is a generic reference with the polymers within each of the Working Examples llA through llJ and 12A
through 12J being defLned as follow~:
5 Workinq Examples Latex llA 12A Control Latex from Rohm and Haas llB 12B Control Latex from H. B. Fuller PD-442 containing Sipomer WAM3 from Alcolac 10 llC 12C Example 7A Latex Polymer llD 12D Example 7A Latex Polymer (Aged weeks at 50C) llE 12E Example 7B Latex Polymer llF 12F Example 8A Latex Polymer 15 llG 12G Example 8B Lat~x Polymer llH 12H Example 9A Latex Polymer llI 12I Example 9B Latex Polymer llJ 12J Example 10 Latex PO1Ym~L
SUBSTITUTE~ 8~1EE;T
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Examples llA-llJ
Constituents Parts By Weiaht _ lA 113-llJ
Semi-Gloss Piyment Grind373.1 373.1 AC-64 (latex polymer from Rohm389.5 ----and Haas) Latex ____ 453 5 Propylene Glycol 43.2 43.2 Texanol (coalescent, 11.9 11.5 from Texaco Inc.) RM-825 (associative thickener, 3.0 3.0 from Rohm ~ Haas) Nat 250 MHBR thickener,1.5 1._ from Aqualon Co.) Water 239.3 179.1 Drew L464 (defoamer, from 3.1 3.1 ~ Drew Industries) j ~?
., ., "
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WO91/1224~ ~CI/~;S91/~)0~3') . .
2~7 L~98 Workinq Examples 12A-12J
Constituents Far~s B~ Weiqht Flat Pigment Grind 1 552.1552.1 AC-64 (polymer from Rohm 305.5 ---_ and Haas) Latex ---- 356.0 Propylene Glycol 30.3 30.3 Texanol (from Texaco Inc.) 10.9 10.9 Nat 250MHBR (from Aqualon Co.) 3.8 3.8 ~ater, DI 258.0212.1 Drew L464 (defoamer, from 3.7 3 7 Drew Industries) ' " , 8UBSJIJUTE 8HEE~T
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, WO91/1224~ f'r/~;$1)l/~093~) ,~., ., . ~
Analysis was then undertaken to determine the relative resistance of each of the ex.amples in Example 12 and 13 towards scrub resistance and wet ~nd dry adhesion me~sured in gram weight. The results are shown in Tables 1 and 2.
E~TERIOR SEMI-GLOSS PAINT
Adhesion Grams Workinq Example Scrub Result Wet_ Dr~_ llA 900 2000 3000-, 10llB 750 400 600 llC 900 2000 3000 llD 920 1500 2500 llE 1200 1500 2000 llF 1110 0 200 15llG 830 1500 1500 llH 1070 0 200 llI 1180 2200 3000t llJ 1070 800 1000 ,:
8uBsrJ~uTe 8HEF~
.. .. ....
WO 91/12243 PC~/~'S91/00939 . ..~
2~ 7 h~.;~3 EXTERIOR FLAT PAINT
Adhes ion Wet Dry 5 Workinq ExampleScrub Result Gms qms lZE 1150 1500 3000 , .
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Caulk Compositions Caulk compositions were then prepared using the wet adhesion monomer synthesized in Example 6. Generally, th~
caulk of Working Examples 13A and 13B were synthesized by charging a reactor with 400 parts of water, 10 parts of acrylic acid, adjusting with a buffer to a pH of 7 or 8 and then raising the reactor temperature to 80C under a nitrogen purge. At 50C, 3.3 parts of Igepal CA-520 ~rrom GAF Corp.) were added to a reactor. At 80C the pre-emulsion composition was added to the reactor with the immediate addition of a potassium persulfate catalyst. The pre-emulsion composition was added at a rate of 5~ OVQ- 15 minutes with the remaining 95% being completely added at the end of 3-1/2 hours. During the additions the reaclor temperature was maintained at a temperature of between 78-80C. The temperature of the reaction was held for 30 minutes and then allowed to cool.
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Workinn Example _13 Weigh~-~
Pre-Emulsion Composition 13A____ _ 13B
Water 120 120 5 Igepal CA 897 (from GAP Corp.) 5.04 5~20 n-Butyl acrylate 667.0 659 2-Ethyl Hexyl Acrylate 90 90 Methacrylic Acid 20 20 Methacrylonitrile 16 16 10 Example 6 Monomer --- 9.6 ~ .
The caulk compositions containing emulsion polymers having the monomer o~ the present invention (Example 13B) were i shown to improve adhesion to a variety or surfaces when compared to caulk ~ormulations containing polymers without a wet adhesion monomer (Example 13A).
.
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WO91/12243 PCr/~9~/00939 2~7 ~9~ - 34-Workin~ Example 14 A solution polymer for a coating composi~Lon was then prepared using the monomer of Example 6 in a 1 liter three-necked roundbottom flask equipped with a mechanlcal stirrer, addition funnels, reflux condenser and a thermometer. Toluene (150 gm) and the Pre-Solution Composition (50 gm) was then added to the flask. The reaction mixture was warmed to reflux (approx. 110C) and the remainder of the Pre-Solution mixture was added over a 4 hour interval and the peroxide initiator was added over a 4-1/2 hour interval.
Pre-Solution Composition Parts bv ~7eiqht Butyl acrylate 150 Hydroxyethyl acrylate 125 15 Butyl methacrylate 100 Methyl Methacrylate 60 Styrene 50 Methacrylic acid 15 Example 6 Monomer 6.5 20 Toluene 150 Lupersol 575M75 (peroxide, from 24.0 ; Penwalt Chemical Co.
A clear, viscous solution was obtained -8UBSTITUTE 8HE~
W091/1224~ PC,r/~S91/nO939 -35- 7 ~7 ~
Workin~ Example 15 A coati.ng was then prepared wi.th tho resin of ~10rking Example 14 for evaluation as an adheslon promoter.
Constituents Parts By Weiqht 5 Working Example 14 Prepolymer 32.3 Cymel 303 (crosslinking resin 7.5 f rom American Cyanamid) n-Butanol 4,0 Aromatic 100 (hydrocarbon solvent 4.0 from Worum) DBE Solvent (coalescent from DuPont~ 4.0 Cycat 4040 (acid catalyst from 0.3 American Cyanamid 15The coating samples were prepared in a glass jar and applied to a green alkyd base painted wood surface with a ~; bird type applicator. Wet film thickness was 6 ml. The samples were placed in a drying oven at 140C for 20 minutes. The samples were allowed to e~uilibrate for tWO
days at ambient temperature and h~midity. A crosshatcn was scxibed into the coating with a razor blade and 1!'2 or the board was immersed in water for 30 minutes. The adhesior:
of the coating to the alkyd was determined with a 3?~, Company, 610 tape test. No delamination from the alkyd coated surface was noted from the control or ~he J
experimen~al coatLng.
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WC)Rl~ING E.XAMPLES SET I I
An additional set of experiments was undertaken to attempt to develop a vinyl acrylic latex useful in coatinys or paint formulations which would exhibLt the enhanced wet adhesion found with the previous examples. Initially, the wet adhesion monomer of the present invention was synthesized. This wet adhesion monomer was then further applied within polymer compositions. The polymer compositions were then introduced into semigloss and flat latex paints. The resultiny paint formulations were then tested against controls to determine -their relative wet adhesion, dry adhesion, and scrub re~istance Monomer SYnthesis Generally, the vinyl monomer of this set was synthesized from feed compounds such as 2-vinyl-~dime~hyl-2-oxazolin-5-one which were then allo~ed to react with a feed stock of an imidazolidine compound such as 1-(2-amino ethyl)-imidazolidin-2-one (AEI). After a given reaction period in an organic medium, the solid precipitate was generally isolated by filtration. The preci~ tate was then generally purified by washing and characterized through chemical analysis.
" - , WOgl/1224~ PCr/~:S'3l/0093') :
-37_ 2~7~3~3 Work~gLExample 1 An attempt to synthesize a wet adhesion monomer having the formula O O (-C~zt~N}
CH2=CHCNHC(CH3)2CN~CH7CH7N C
o using 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDM), and AEI
and the following process.
Using a 300 ml 3-necked roundbottom flask equipped ~lith an addition funnel, magnetic spin bar, temperature probé
and a N7 inlet, the azlactone ~13.1 g., 0.10 mol) was added in 75 ml of CH7Cl . A solution of AEI (12.9 g., 0.10 mol) in 75 ml of CH,Cl, was added to the azlactone over a 60 minute interval. After approximately 10-15 minutes, tAe clear reaction mixture became slightly cloudy and a white precipitate began to form. The reaction mixture became difficult to stir with the precipitate and an additional 50 -20 ml CH2Cl2 was added. A slight exotherm occurred during the reaction and the temperature increased from 236C. ~o 30~C.
The reaction mixture was stirred at 25'C. for 4 hour~ and the white solid was isolated by suction filtration. Tne filter cake was washed once ~7ith lO0 ml of hexane. TAe melting point of the solid was 188.5-189.5'C. Tha compounc was soluble in water.
Thë monomer of Working Example 1, Set II, was ; characterized to carbon 13 nuclear magnetic resonance spectra, me-lting point, and infrared scan. Referrlng to Figure 5, the NMR spectrum provided the following data (reported in carbon 13 ppm): Carbon number 1 at 27.2;
- carbon number 2 at 40.1; carbon number 3 at 40.8; carbon number 4 at 44.9; carbon number 5 at 48.7; carbon number 6 at 59.5; carbon number 7 at 130.5; carbon number 8 a~
132.8; carbon number 9 at 167.5; carbon number 10 a~ 170.';
and carbon number 11 at 179.9.
Upon analysi~, the melting point of the monomsr wa~
8UBSTlrUTE~ 81~1EEr , .
WO91/1224~ ~'Cr'/-'S91t0()'~39 9~3 `
found to be 188.5 to 189.5C. Infrarecl scan showed NH
amine character at 3386, 3323, anci 3359 cm'~; C ~ O
character at 1688 cml; NH amine 1656 cm~; and C = C at 1629 cm~~.
,, ~
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, 81.JBSJ!TUTe 8HEFr ~ j WO91/1224~ PCr/~'S')1/00~3') Workinq Example 2 ~' An attempt to scale up the synthesis of Working Example l was then attempted.
Using a 2 liter 3-necked roundbottom flask equipped with a mechanical stirrer, addition funnel, N~ inlet and a thermometer, vinyl dimethyl azlactone (VDN) (lOS.0 g, 0.80 mol) was added in 400 ml of ethyl acetate. A disperslon of AEI (103.3 g, 0.80 mol) in 450 ml of ethylacetate wa~ added dropwise over a one hour interval while maintaining the temperature of the reaction mixture between 15-25C. with - an ice-water bath. A white precipitate began to form as soon as the AEI solution was added. The reaction mix~ur~
was stirred for an additional 3 hours at 25C. and tne ;~ white crystalline solid was isolated by suction filtra~ior.
and washed with lO0 ml of hexane. The crude material nad a melting point of 182-185C. The crude product was recrystallized from a mixture of isopropanol and methanol to afford white crystals having a melting point of l95.0-196.0C.
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Workin~ ExarnPle 3 - ~he pre-emulsion was prepared by first forming a solution of the monomer of the pres~nt invention with a surfactant such as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed below and subsequently adding the solution of monomers and surfactant to a beaker containing water which was being agitated with a paddle-type blade stirrer. The reactor was then charged with 4.24 parts of potassium persulfate catalyst and heated to 80C. with a nitrogen purge. The pre-emulsion composition was then fed into the reactor at a rate OI 3%
o~er 15 minutes, another 5 wt-% over the next 30 minules, and the remaining 92 wt-~ over the ~alance of 3 l!2 hours.
The reactor was maintained at about 80C. during the feed 15 and the nitrogen purge was shut off.
. Pre-Emulsion Constituents Parts By:Weiqht H~O 152 . Igepal CA897 (ethoxylated phenol surfactant from GAF Corporation) 5.3 20 TRITON X200 (sodium alkyl aryl , polyether sulIonate surfactant - from Rohm & ~laas) 2l.2 :~ Sodium bicarbonate l.55 , ,~
`. Vinyl acetate 625.8 25 n-butylacrylate 187.5 Example l Monomer 9.76 8UBSTITUTE~ 8H8ET .
'' ' ' .
, W091/]2243 PCr/~:S~l/0093') Z~ 39~
Pi~ment Grinds In preparation for the ormulation of paint systems having the wet adhesion monomer of the present invention pigment grinds were ormulated by ~irst weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first adding the extenders in any order àfter TiO~.
Once the pigment had been wet out any remaining amount of defoamer was added. The pigment composition was then ground a~ high speed (about ~,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.
15 Interior Flat Grind (Parts BY ~eiaht) Water, DI 125.0 Nuosept 95 (preservative, Nuodox Inc.) 2.5 Tamol 731 (dispersant, Rohm & Haas) 9.2 Igepal C0-630 (GAF Corp.) 3 5 20 AMP 95 (dispersant, Angus Chemical Co.) 2.0 TiO2 190.0 Clay 125.0 Calcium Carbonate 60.0 Attagel 50 (thickener, Engelhard Corp.) 3.
25 Drew L464 (defoamer, Drew Industrial Div.) 1.5 Interi_r_Semiqloss Grind ~Wt.-%) Water, DI 66.6 Nuosept 95 (preservative, Nuodox, Inc.) 2.0 30 Propylene Glycol 17.3 AMP 95 (dispersant, Angus Chemical Co.) 1.5 Tamol SG-1 (dispersant, Rohm & Haas) 7.2 Igepal C0~630 (~AF Corp.) 3.6 TiO2 250.0 35 Clay 35 0 8UBSTITI~TE 8HEEl-, , WO 91/1224~ YCr/~;S91/00939 2~
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WO91/1224~ PCr/~;S9l/00939 -~3-Workinq Example ~ and 5 Flat and semigloss paint systems were then formulated incorporating the po:Lymer system of Example 3 and con~rol polymers by first weighing the la~ex and defoamer in a lined can or stainless steel beaker. The latexes were mixed with the defoamer using a three bladed paddle s~irrer and their respective pigment grinds and water were added to the latex. Thickening constituents were then added to the compositions including a Natrosol (cellulosic thickener) as well as the ethylene glycol constituents and Texanol.
These constituents were slowly addod into the vor~ex c- th^
mix. Agitation was increased as needed to proviae rc-equal mixing of the vortex. The composition was mixei for 10 minutes until the thickener was dissolved. The composition was then covered and let stand for 2~ hours.
The term "Latex" as provided below is a generic reference with the polymer within each of Working Examples 4A-4C and 5A-5C being defined as follows:
Workinq ExamPle Latex 4A 5A Control PD-124/BHO-20 vinyl acetate butylacrylate copolymer from Y. E.
Fuller 4B SB Polymer of Example ~3 4C 5C Blend of 75~ control polymer and q5%
Example 3 polymer 8UBSTITUTE~ EE~
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, WO91/1~24~ PCT/~:S~l/0~39 ,_, ... .
Workinq Example 4 lParts By WeiqhtL
Constituents 4A - 4B 4C
Flat Pigment Grind 521.7 521 7 Water, DI 288.5 284.0 PD-124 (BHO-20)(latex, H.B. 243.0 -_~
Fuller) Latex --- 247.8 Ethylene Glycol 46.5 46.5 10 Natrosol Plus (thickener, 6.5 6.5 Aqualon Co.) Texanol (coalescent, Texaco 10.0 10.0 Co. ) Drew L464 (defoamer, Drew 2.0 2.0 Industrial Div.) .
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Semigloss Pigment Grind 385.2 385.2 Water, DI 214.7 207.1 PD-124/BHO-20 (latex, H.B. 414.0 ---Fuller) Latex --- 422.3 Texanol (coalescent, Texaco 11.9 11.9 Co.) Propylene Glycol 34.6 34.6 Acrysol ~M-825 10.8 10.8 Natrosol 250 MHBR (thickener, 2.0 2.0 Aqualon Co.) Drew L464 (defoamer, Drew 2.5 2.5 ; Industrial Div.) ' . . , . . .
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WO91/1224~ PCr/~'S')I/a0~3') 2~ ~Q5~ 6-., Working Examples 4A-4C and 5A-5C were then tested IO
compare the resistance to scrubbing, wet adhesion ~measured in grams) and dry adhesion (measured in grams). The results are reported below in Tables 3 and 4.
a_le 3 Interior Flat Paint Adhesion (Grams) WorkLn~ Example Scrubs Wet Dry -l0 4B 870 1200 2300 4C 360 900 ll00 Table 4 Semi-Gloss Paint Workinq Exam~le Adhesion (Grams) Scrubs Wet Dry 5A 3000 l00 l00 5B 1340 1500 l000 5C 900 200 l00 All samples were equivalent in their stability properties. Working Examples 4B and 4C had greater adhesion properties than control Working Example 5A.
Working Example 4B containing the monomer cf the presen~
invention had superior scrub resistance to the contro`
Working Example 4A.
Regarding the semi-gloss paint formulations, Working Examples 5B and 5C showed greatly improved adhesion compared to Working Example 5A, the control. Overall, the paint compositions having the monomer of the present invention showed superior scrub resistance as well as wet adhesion in both the flat and semi-gloss paint compositions.
The fore~oing 5pecification, Examples and data provide a basis for understanding the invention. The invention can be made in a variety of embodiments without depar~ing from ; 35 the spirit and scope of the invention. Accordingly, tne S~IBSTITUTE~ 8H~F~
,, " . " " ,, .,, ,~, ..... .... ... . .
WO~I/1224~ PC~ S')l/00~3~) -47- 2~ B
invention resides in the claims hereinafter appended, ,~ .
.. .. ,: . . , . -, .
,.
., 8U13STITUTE 8HEFr i~ . ,., ., . . ,, ,,. ~,,..,,~,.....
",
NH at 1680 cm~!; NH at 1660 cm~l; C = C at 890 cm~'; and C =
C aromatic at 804 cm-~.
The Carbon 13 spectra of the sample exhibit both the proper number of nonequivalent carhons and the correct number of attached protons required by the formula of this monomex.
8UB9TITUTE 8HEE~
.... ... . ..
WO91~12243 PCT/~591/00939 -17- ~ :
Workinq Example 6 A synthesis of a solid monomer having the formula ~ I_NHCNHCH~CH~N /NH
CH3 "
- O
was then attempted using m-TMI, and l-(2-aminoethyl) imidazoline-2-one (AEI) using the following process. Using ; a l liter 3-necked roundbottom flask equipped with a ~
; inlet, mechanical s~irrer, pressure equalizing addition ~; funnel and a thermometer (AEI) (64.5 g, 0.50 mol) was added in 200 ml of ethyl acetate to the flas~. A solution of m-TMI (lOl.5 g, 0.505 mol) in lO0 ml of ethyl acetate was added dropwise to the cloudy amine/ethyl acetate mixture.
After the addition of about lO ml of the m-TMI soiution, ~; ~ the reaction mixture became clear. The reaction mi~ture was cooled with a cold water bath to maintain the temperature between 25-30C.
A few white crystals began to form on the side of the reaction flask after about 35 ml of the m-TMI solu~ion had been added. Fine crystals were disper~ed in the reactior.
mixture after about 50 ml of the m-T~I solution hz~ beer;
added. A white crystalline slurry was obtained a~er tne addition of 60 to 65 ml of the m-T~I solution. The m-T~I
solution was added dropwise over a l hour interva . The reaction mixture was stirred with some difficulty upon completion of the addition of the m-T~.I solution. An additional 25 ml of ethyl acetate was added to ths reaction mixture to facilitate mixing. The mixture was s~irred for -3 hours àt 25C. and the white solid was isolated by suction filtration with a Buchner funnel.
The reaction flask was rinsed with lO0 ml of ethyl ; 35 acetate and then it was poured over the crystals in the Buchner funnel. The melting point of the recovere~ white solid was 138.5-142 0~C
SUB5TITUTE~ 8tlEE~
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~7`, ~
The fil~er cake was broken up and dried by pullinq air through the pulverized 501id for 30 minutes with a water aspirator. The weight of the solid was 232.4 g. The solid was air dried overnight, weight = 201.3 g. The filtrate was concentrated and an additional 6.8 g of solid was obtained. The solid was further dried by spreading on a sheet of release paper to obtain 159.8 g of product. Total recovery = 159.8 ~ 6.8 = 166.6 g (100.9~). The residue collected by concentrating the mother liquor was a mixture of a crystalline compound and an oil. The material was no~
characterized further.
E lsion P~mers Emulsion polymeric compositions were then synthesized using the monomers of Working Examples 1, 2, 3 and 6.
Generally, emulsion polymers containing the monomer of the present invention were polymerized by charging a reactor with water, a surfactant based defoamer such as Balab 748, commercially available from Witco Chemical Co., and diammonium phosphate. A catalyst was then charged into the reactor over a delayed period of time as a water carried system of ammonium persulfate and sodium metabisulfite. Thc pre-emulsion was prepared by ~irst forming a solu~ion of the monomer of the present invent.Lon with a surfactant sucr.
as Igepal CA897 (from GAF) and other polymerizable monomer~i constituents listed in Working Examples 7-10 and subseguently adding the solution of monomers and surfactanr to a beaker containing water ~Ihich was being agitated with a paddle-type blade stirrer. The pre-emulsion composition was then added to the reactor and over a delayed period or time, an additional amount of the same catalyst was added to thé reactor.
.
.... . . . .
, : . . . .... .
8UBSTI~UTE 8HEEr~
W091/1224~ PCT/USl)l/0~939 ~
Z~ J~3 , Workinq Example 7 The monomer of Example 6 was used to prepare a pre emulsion polymer base for use in a paint composition. The `` pre-emulsion polymer base had the following compouncl and 5 monomer constituents in the reaction.
Pre-Emulsion Constituents (Parts By_Weiqht) H,O 206.4 206.4 IGEPAL CA897 lethyoxylated 60.88 60.88 phenol surfactant from GAF Corporation) Example 6 Monomer 8.19 --~:: Example 6 Monomer (unrecrystallized) -- 8.19 : 15 Diammonium Phosphate l.0 1.0 n-butyl acrylate 336.8 336.8 Me~hyl methacrylate 333,4 333,4 Methacrylic Acid 12.77 i2.77 : , 5., '. ~.
' ' .
, ' : WO91/1224~ PC'r/~:S~I/U0~39 2 ~ 7 ~ 20--Workinq ExamPle 8 Using the same process as Example 7 the monomers of Examples 2 and 3 wore usecl to ~orm a pre-emulslon ~' composition.
5 Pre-Emulsion Constituents Parts By Weiqht 8A _ 8B
H~O 206,4 206.4 IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 60.88 10 Example 2 8.19 --Example 3 -- ô.19 Diammonium Phosphate 1.0 l.C
.:., n-butyl acrylate 336.8 336.8 Methyl methacrylate 333,4 333,4 15 Methacrylic Acid 12.77 12.77 Using the process of the two preceding Examples the monomers of Example 1 and 6 we:re used to form a pre-emulsion composition base for Examples 9 and 10.
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W~9l/lt24~ PCT/~S91/0093() -21- ~ ~,~
Workinq Example 9 Pre-Emulsion Constituents Parts By Weiqht H~O 206,4 206.4 IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 60.88 Example 1 Monomer 8.19 --Example 6 Monomer -- 8.19 Diammonium Phosphate 1.0 2.0 10 n-butyl acrylate 336.8 336.8 Methyl methacrylate 333,4 333,4 Methacrylic Acid 12,77 12.77 .
SU~3STITUT~ 8HEEl' ~`:
: WO91/12243 PCT/~S91/0093~3 2~ ~22-Workinq Example 10 Pre-Emulsion Constituents Parts BY Welqht H2O 206.
IGEPAL CA897 (ethoxylated phenol from GAF Corp.) 60.88 Example 6 Monomer 4.10 Diammonium Phosphate 1.0 : ~ n-butyl acrylate 336.8 Methyl methacrylate 330.2 10 Methacrylic Acid 12,77 :;
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WO91/1224~ ~Cr/~'S')l/~0939 -23- 2~7 ~
Piqment ~rlnds In preparation of paint systems having a polymer containing the wet adhesion monomer of the present invention pigments grinds were forrnulated by first weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Ti~anium dioxide was added to the liquid phase first, then adding the extenders in any order after the TiO-,. Once the pigment had been wet out, the remaining amount of defoamer was added. The pigment`
composition was then ground at high speed (about ~,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.
~UBST~TUTe 8HE@~
..... . . . . . . ... ...... . .. .. . .....
W091/1224~ PCT/~'S91/~)0939 ~ 8 -2~-Exterior Flat GrindParts By Weiqht Water, DI 9l,6 Nopcosperse 44 (dispersant, 7,7 Henkel Corp.) 5 Nuosept 95 (preservative, l.5 Nuodox Inc.) Polyphase AF-l (mildewcide 4.8 Troy Chemical Corp.) Igepal C0-630 (from GA~ Corp.) 3,5 lO AMP 95 (dispersant, l.5 Augus Chemical Co.) TiO~ 250.0 Feldspar (available from l90.0 Indusmin, Inc.) 15 Drew-L464 (Defoamer availablel.98 from Drew Industries) 8UE~S~'ITUTE~ 8HEE~
, . .. ..... . .
WO 91/12243 Pc~r/~s9ll()o~3~) -25-2~tît~1 ~r3~3, Exterior Semiqloss Grind Parts By Weiqh~
Water, DI 58.3 Tamol 73l (dispersant, 8.6 Rohm & Haas) Igepal C0-630 ~surfactant, 3 5 GAF Corp.) AMP 95 (dispersant, l.O
Augus Chemical Co.) Nuosept 95 (preservative, l.5 Nuodex Inc.) Polyphase AF-l (mildewcida, 4.8 Troy Chemical) Ethylene Glycol l8.6 TiO1 250.0 Clay 25.0 Drew L464 ~defoamer, Drew l.8 Industries) 373.l 8UBSTITUTE 8HeFr ., ,,, ,,,,~,.. , ~, , , W09ltl224~ T'C't'/~S')l/00')31) 2~
S~mi-Gloss and Flat Paints . .
Paint systems, semigloss as well as flat, were then formulated using the polymeric systern3 of Working Examples 7-10 and pigment grinds previously formulated by weighing the latex polymer and defoamer into a lined can or stainless steel beaker. The system was then mixed with a three bladed paddle and the pigment grind and water was added to the latex. Cellulosic Natrosol~U thickeners were added along with the propylene glycol and TexanolT~.
The mixture was slowly and continuously mixed until a vortex formed with agitation increased as needed. The composition was mixed for 10 minutes or until the thickene~-dissolved. Once formulated, the paint was covered and le~
stand for 24 hours prior to testing. This process was used to formulate the exterior flat and semi-gloss paint of Examples 11 and 12.
8UBSTITUTE~ 8~1E~
. .
,"
" , W~91/1224~ PC~/~'S9l/00~39 2~i7 ~
The term "latex" is provided below and both ~7Orkin~
Examples 12 and 13 is a generic reference with the polymers within each of the Working Examples llA through llJ and 12A
through 12J being defLned as follow~:
5 Workinq Examples Latex llA 12A Control Latex from Rohm and Haas llB 12B Control Latex from H. B. Fuller PD-442 containing Sipomer WAM3 from Alcolac 10 llC 12C Example 7A Latex Polymer llD 12D Example 7A Latex Polymer (Aged weeks at 50C) llE 12E Example 7B Latex Polymer llF 12F Example 8A Latex Polymer 15 llG 12G Example 8B Lat~x Polymer llH 12H Example 9A Latex Polymer llI 12I Example 9B Latex Polymer llJ 12J Example 10 Latex PO1Ym~L
SUBSTITUTE~ 8~1EE;T
,. .
wo gl/1224~ Pcr/l~s9l/0093~) ,.
Examples llA-llJ
Constituents Parts By Weiaht _ lA 113-llJ
Semi-Gloss Piyment Grind373.1 373.1 AC-64 (latex polymer from Rohm389.5 ----and Haas) Latex ____ 453 5 Propylene Glycol 43.2 43.2 Texanol (coalescent, 11.9 11.5 from Texaco Inc.) RM-825 (associative thickener, 3.0 3.0 from Rohm ~ Haas) Nat 250 MHBR thickener,1.5 1._ from Aqualon Co.) Water 239.3 179.1 Drew L464 (defoamer, from 3.1 3.1 ~ Drew Industries) j ~?
., ., "
.
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... ..... . .
. . .
... .
WO91/1224~ ~CI/~;S91/~)0~3') . .
2~7 L~98 Workinq Examples 12A-12J
Constituents Far~s B~ Weiqht Flat Pigment Grind 1 552.1552.1 AC-64 (polymer from Rohm 305.5 ---_ and Haas) Latex ---- 356.0 Propylene Glycol 30.3 30.3 Texanol (from Texaco Inc.) 10.9 10.9 Nat 250MHBR (from Aqualon Co.) 3.8 3.8 ~ater, DI 258.0212.1 Drew L464 (defoamer, from 3.7 3 7 Drew Industries) ' " , 8UBSJIJUTE 8HEE~T
, ,.,, " ,... .... . .. .
, WO91/1224~ f'r/~;$1)l/~093~) ,~., ., . ~
Analysis was then undertaken to determine the relative resistance of each of the ex.amples in Example 12 and 13 towards scrub resistance and wet ~nd dry adhesion me~sured in gram weight. The results are shown in Tables 1 and 2.
E~TERIOR SEMI-GLOSS PAINT
Adhesion Grams Workinq Example Scrub Result Wet_ Dr~_ llA 900 2000 3000-, 10llB 750 400 600 llC 900 2000 3000 llD 920 1500 2500 llE 1200 1500 2000 llF 1110 0 200 15llG 830 1500 1500 llH 1070 0 200 llI 1180 2200 3000t llJ 1070 800 1000 ,:
8uBsrJ~uTe 8HEF~
.. .. ....
WO 91/12243 PC~/~'S91/00939 . ..~
2~ 7 h~.;~3 EXTERIOR FLAT PAINT
Adhes ion Wet Dry 5 Workinq ExampleScrub Result Gms qms lZE 1150 1500 3000 , .
' SUBSTI~VTE~ 8HEFI-. .. . ~
,.. ,.. .. -~- .
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WO9l/1224~ PCr/~S~l/00~)3~) 2~
Caulk Compositions Caulk compositions were then prepared using the wet adhesion monomer synthesized in Example 6. Generally, th~
caulk of Working Examples 13A and 13B were synthesized by charging a reactor with 400 parts of water, 10 parts of acrylic acid, adjusting with a buffer to a pH of 7 or 8 and then raising the reactor temperature to 80C under a nitrogen purge. At 50C, 3.3 parts of Igepal CA-520 ~rrom GAF Corp.) were added to a reactor. At 80C the pre-emulsion composition was added to the reactor with the immediate addition of a potassium persulfate catalyst. The pre-emulsion composition was added at a rate of 5~ OVQ- 15 minutes with the remaining 95% being completely added at the end of 3-1/2 hours. During the additions the reaclor temperature was maintained at a temperature of between 78-80C. The temperature of the reaction was held for 30 minutes and then allowed to cool.
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WO91/1224~ ~'Cr/~'S9l/0093') :
. -33~
2~?7 ~
Workinn Example _13 Weigh~-~
Pre-Emulsion Composition 13A____ _ 13B
Water 120 120 5 Igepal CA 897 (from GAP Corp.) 5.04 5~20 n-Butyl acrylate 667.0 659 2-Ethyl Hexyl Acrylate 90 90 Methacrylic Acid 20 20 Methacrylonitrile 16 16 10 Example 6 Monomer --- 9.6 ~ .
The caulk compositions containing emulsion polymers having the monomer o~ the present invention (Example 13B) were i shown to improve adhesion to a variety or surfaces when compared to caulk ~ormulations containing polymers without a wet adhesion monomer (Example 13A).
.
. ...
, ~' .
8UE3STIl~UTE~ #3HE!E~T
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WO91/12243 PCr/~9~/00939 2~7 ~9~ - 34-Workin~ Example 14 A solution polymer for a coating composi~Lon was then prepared using the monomer of Example 6 in a 1 liter three-necked roundbottom flask equipped with a mechanlcal stirrer, addition funnels, reflux condenser and a thermometer. Toluene (150 gm) and the Pre-Solution Composition (50 gm) was then added to the flask. The reaction mixture was warmed to reflux (approx. 110C) and the remainder of the Pre-Solution mixture was added over a 4 hour interval and the peroxide initiator was added over a 4-1/2 hour interval.
Pre-Solution Composition Parts bv ~7eiqht Butyl acrylate 150 Hydroxyethyl acrylate 125 15 Butyl methacrylate 100 Methyl Methacrylate 60 Styrene 50 Methacrylic acid 15 Example 6 Monomer 6.5 20 Toluene 150 Lupersol 575M75 (peroxide, from 24.0 ; Penwalt Chemical Co.
A clear, viscous solution was obtained -8UBSTITUTE 8HE~
W091/1224~ PC,r/~S91/nO939 -35- 7 ~7 ~
Workin~ Example 15 A coati.ng was then prepared wi.th tho resin of ~10rking Example 14 for evaluation as an adheslon promoter.
Constituents Parts By Weiqht 5 Working Example 14 Prepolymer 32.3 Cymel 303 (crosslinking resin 7.5 f rom American Cyanamid) n-Butanol 4,0 Aromatic 100 (hydrocarbon solvent 4.0 from Worum) DBE Solvent (coalescent from DuPont~ 4.0 Cycat 4040 (acid catalyst from 0.3 American Cyanamid 15The coating samples were prepared in a glass jar and applied to a green alkyd base painted wood surface with a ~; bird type applicator. Wet film thickness was 6 ml. The samples were placed in a drying oven at 140C for 20 minutes. The samples were allowed to e~uilibrate for tWO
days at ambient temperature and h~midity. A crosshatcn was scxibed into the coating with a razor blade and 1!'2 or the board was immersed in water for 30 minutes. The adhesior:
of the coating to the alkyd was determined with a 3?~, Company, 610 tape test. No delamination from the alkyd coated surface was noted from the control or ~he J
experimen~al coatLng.
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8UBSTITUTE~ 8HEEl~;
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WO ~1~1224~ PCr/~:S9]100939 ~7 ~
WC)Rl~ING E.XAMPLES SET I I
An additional set of experiments was undertaken to attempt to develop a vinyl acrylic latex useful in coatinys or paint formulations which would exhibLt the enhanced wet adhesion found with the previous examples. Initially, the wet adhesion monomer of the present invention was synthesized. This wet adhesion monomer was then further applied within polymer compositions. The polymer compositions were then introduced into semigloss and flat latex paints. The resultiny paint formulations were then tested against controls to determine -their relative wet adhesion, dry adhesion, and scrub re~istance Monomer SYnthesis Generally, the vinyl monomer of this set was synthesized from feed compounds such as 2-vinyl-~dime~hyl-2-oxazolin-5-one which were then allo~ed to react with a feed stock of an imidazolidine compound such as 1-(2-amino ethyl)-imidazolidin-2-one (AEI). After a given reaction period in an organic medium, the solid precipitate was generally isolated by filtration. The preci~ tate was then generally purified by washing and characterized through chemical analysis.
" - , WOgl/1224~ PCr/~:S'3l/0093') :
-37_ 2~7~3~3 Work~gLExample 1 An attempt to synthesize a wet adhesion monomer having the formula O O (-C~zt~N}
CH2=CHCNHC(CH3)2CN~CH7CH7N C
o using 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDM), and AEI
and the following process.
Using a 300 ml 3-necked roundbottom flask equipped ~lith an addition funnel, magnetic spin bar, temperature probé
and a N7 inlet, the azlactone ~13.1 g., 0.10 mol) was added in 75 ml of CH7Cl . A solution of AEI (12.9 g., 0.10 mol) in 75 ml of CH,Cl, was added to the azlactone over a 60 minute interval. After approximately 10-15 minutes, tAe clear reaction mixture became slightly cloudy and a white precipitate began to form. The reaction mixture became difficult to stir with the precipitate and an additional 50 -20 ml CH2Cl2 was added. A slight exotherm occurred during the reaction and the temperature increased from 236C. ~o 30~C.
The reaction mixture was stirred at 25'C. for 4 hour~ and the white solid was isolated by suction filtration. Tne filter cake was washed once ~7ith lO0 ml of hexane. TAe melting point of the solid was 188.5-189.5'C. Tha compounc was soluble in water.
Thë monomer of Working Example 1, Set II, was ; characterized to carbon 13 nuclear magnetic resonance spectra, me-lting point, and infrared scan. Referrlng to Figure 5, the NMR spectrum provided the following data (reported in carbon 13 ppm): Carbon number 1 at 27.2;
- carbon number 2 at 40.1; carbon number 3 at 40.8; carbon number 4 at 44.9; carbon number 5 at 48.7; carbon number 6 at 59.5; carbon number 7 at 130.5; carbon number 8 a~
132.8; carbon number 9 at 167.5; carbon number 10 a~ 170.';
and carbon number 11 at 179.9.
Upon analysi~, the melting point of the monomsr wa~
8UBSTlrUTE~ 81~1EEr , .
WO91/1224~ ~'Cr'/-'S91t0()'~39 9~3 `
found to be 188.5 to 189.5C. Infrarecl scan showed NH
amine character at 3386, 3323, anci 3359 cm'~; C ~ O
character at 1688 cml; NH amine 1656 cm~; and C = C at 1629 cm~~.
,, ~
. , - ; , , ,, , . . , .: .
, 81.JBSJ!TUTe 8HEFr ~ j WO91/1224~ PCr/~'S')1/00~3') Workinq Example 2 ~' An attempt to scale up the synthesis of Working Example l was then attempted.
Using a 2 liter 3-necked roundbottom flask equipped with a mechanical stirrer, addition funnel, N~ inlet and a thermometer, vinyl dimethyl azlactone (VDN) (lOS.0 g, 0.80 mol) was added in 400 ml of ethyl acetate. A disperslon of AEI (103.3 g, 0.80 mol) in 450 ml of ethylacetate wa~ added dropwise over a one hour interval while maintaining the temperature of the reaction mixture between 15-25C. with - an ice-water bath. A white precipitate began to form as soon as the AEI solution was added. The reaction mix~ur~
was stirred for an additional 3 hours at 25C. and tne ;~ white crystalline solid was isolated by suction filtra~ior.
and washed with lO0 ml of hexane. The crude material nad a melting point of 182-185C. The crude product was recrystallized from a mixture of isopropanol and methanol to afford white crystals having a melting point of l95.0-196.0C.
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WO91/1224~ PCr/~'S91/00~39 ~:~?7.~
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Workin~ ExarnPle 3 - ~he pre-emulsion was prepared by first forming a solution of the monomer of the pres~nt invention with a surfactant such as Igepal CA897 (from GAF) and other polymerizable monomers constituents listed below and subsequently adding the solution of monomers and surfactant to a beaker containing water which was being agitated with a paddle-type blade stirrer. The reactor was then charged with 4.24 parts of potassium persulfate catalyst and heated to 80C. with a nitrogen purge. The pre-emulsion composition was then fed into the reactor at a rate OI 3%
o~er 15 minutes, another 5 wt-% over the next 30 minules, and the remaining 92 wt-~ over the ~alance of 3 l!2 hours.
The reactor was maintained at about 80C. during the feed 15 and the nitrogen purge was shut off.
. Pre-Emulsion Constituents Parts By:Weiqht H~O 152 . Igepal CA897 (ethoxylated phenol surfactant from GAF Corporation) 5.3 20 TRITON X200 (sodium alkyl aryl , polyether sulIonate surfactant - from Rohm & ~laas) 2l.2 :~ Sodium bicarbonate l.55 , ,~
`. Vinyl acetate 625.8 25 n-butylacrylate 187.5 Example l Monomer 9.76 8UBSTITUTE~ 8H8ET .
'' ' ' .
, W091/]2243 PCr/~:S~l/0093') Z~ 39~
Pi~ment Grinds In preparation for the ormulation of paint systems having the wet adhesion monomer of the present invention pigment grinds were ormulated by ~irst weighing water, a dispersant, preservative, surfactants, and defoamers to the composition. The pigments were weighed in a separate container and using a cowles blade gradually added to the liquid phase. Titanium dioxide was added to the liquid phase first adding the extenders in any order àfter TiO~.
Once the pigment had been wet out any remaining amount of defoamer was added. The pigment composition was then ground a~ high speed (about ~,000 rpms) for 15 to 20 minutes. Listed below are the constituents of the individual grinds.
15 Interior Flat Grind (Parts BY ~eiaht) Water, DI 125.0 Nuosept 95 (preservative, Nuodox Inc.) 2.5 Tamol 731 (dispersant, Rohm & Haas) 9.2 Igepal C0-630 (GAF Corp.) 3 5 20 AMP 95 (dispersant, Angus Chemical Co.) 2.0 TiO2 190.0 Clay 125.0 Calcium Carbonate 60.0 Attagel 50 (thickener, Engelhard Corp.) 3.
25 Drew L464 (defoamer, Drew Industrial Div.) 1.5 Interi_r_Semiqloss Grind ~Wt.-%) Water, DI 66.6 Nuosept 95 (preservative, Nuodox, Inc.) 2.0 30 Propylene Glycol 17.3 AMP 95 (dispersant, Angus Chemical Co.) 1.5 Tamol SG-1 (dispersant, Rohm & Haas) 7.2 Igepal C0~630 (~AF Corp.) 3.6 TiO2 250.0 35 Clay 35 0 8UBSTITI~TE 8HEEl-, , WO 91/1224~ YCr/~;S91/00939 2~
Drew L464 (defoamer, Drew Industrial Div. ) 2 . O
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WO91/1224~ PCr/~;S9l/00939 -~3-Workinq Example ~ and 5 Flat and semigloss paint systems were then formulated incorporating the po:Lymer system of Example 3 and con~rol polymers by first weighing the la~ex and defoamer in a lined can or stainless steel beaker. The latexes were mixed with the defoamer using a three bladed paddle s~irrer and their respective pigment grinds and water were added to the latex. Thickening constituents were then added to the compositions including a Natrosol (cellulosic thickener) as well as the ethylene glycol constituents and Texanol.
These constituents were slowly addod into the vor~ex c- th^
mix. Agitation was increased as needed to proviae rc-equal mixing of the vortex. The composition was mixei for 10 minutes until the thickener was dissolved. The composition was then covered and let stand for 2~ hours.
The term "Latex" as provided below is a generic reference with the polymer within each of Working Examples 4A-4C and 5A-5C being defined as follows:
Workinq ExamPle Latex 4A 5A Control PD-124/BHO-20 vinyl acetate butylacrylate copolymer from Y. E.
Fuller 4B SB Polymer of Example ~3 4C 5C Blend of 75~ control polymer and q5%
Example 3 polymer 8UBSTITUTE~ EE~
,~ . -.
, WO91/1~24~ PCT/~:S~l/0~39 ,_, ... .
Workinq Example 4 lParts By WeiqhtL
Constituents 4A - 4B 4C
Flat Pigment Grind 521.7 521 7 Water, DI 288.5 284.0 PD-124 (BHO-20)(latex, H.B. 243.0 -_~
Fuller) Latex --- 247.8 Ethylene Glycol 46.5 46.5 10 Natrosol Plus (thickener, 6.5 6.5 Aqualon Co.) Texanol (coalescent, Texaco 10.0 10.0 Co. ) Drew L464 (defoamer, Drew 2.0 2.0 Industrial Div.) .
._~;..
, , ~
,~ :
, , .. j . - -:-, WO91/l224~ ~'Cr/~ )l/0093~) . ~ " ,, Workinq Example 5 (Parts By Wei~ht) Constituents 5A ~nd 5B 5C
Semigloss Pigment Grind 385.2 385.2 Water, DI 214.7 207.1 PD-124/BHO-20 (latex, H.B. 414.0 ---Fuller) Latex --- 422.3 Texanol (coalescent, Texaco 11.9 11.9 Co.) Propylene Glycol 34.6 34.6 Acrysol ~M-825 10.8 10.8 Natrosol 250 MHBR (thickener, 2.0 2.0 Aqualon Co.) Drew L464 (defoamer, Drew 2.5 2.5 ; Industrial Div.) ' . . , . . .
"
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WO91/1224~ PCr/~'S')I/a0~3') 2~ ~Q5~ 6-., Working Examples 4A-4C and 5A-5C were then tested IO
compare the resistance to scrubbing, wet adhesion ~measured in grams) and dry adhesion (measured in grams). The results are reported below in Tables 3 and 4.
a_le 3 Interior Flat Paint Adhesion (Grams) WorkLn~ Example Scrubs Wet Dry -l0 4B 870 1200 2300 4C 360 900 ll00 Table 4 Semi-Gloss Paint Workinq Exam~le Adhesion (Grams) Scrubs Wet Dry 5A 3000 l00 l00 5B 1340 1500 l000 5C 900 200 l00 All samples were equivalent in their stability properties. Working Examples 4B and 4C had greater adhesion properties than control Working Example 5A.
Working Example 4B containing the monomer cf the presen~
invention had superior scrub resistance to the contro`
Working Example 4A.
Regarding the semi-gloss paint formulations, Working Examples 5B and 5C showed greatly improved adhesion compared to Working Example 5A, the control. Overall, the paint compositions having the monomer of the present invention showed superior scrub resistance as well as wet adhesion in both the flat and semi-gloss paint compositions.
The fore~oing 5pecification, Examples and data provide a basis for understanding the invention. The invention can be made in a variety of embodiments without depar~ing from ; 35 the spirit and scope of the invention. Accordingly, tne S~IBSTITUTE~ 8H~F~
,, " . " " ,, .,, ,~, ..... .... ... . .
WO~I/1224~ PC~ S')l/00~3~) -47- 2~ B
invention resides in the claims hereinafter appended, ,~ .
.. .. ,: . . , . -, .
,.
., 8U13STITUTE 8HEFr i~ . ,., ., . . ,, ,,. ~,,..,,~,.....
",
Claims (36)
1. A monomer comprising:
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
2. The monomer of claim 1 wherein , or .
3. The monomer of claim 1 wherein and .
4. A monomer comprising: **
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
5. The monomer of claim 4 wherein R = H and R' = CH3;
Z = -O-; n = 1; and Y = -NH-.
Z = -O-; n = 1; and Y = -NH-.
6. A monomer comprising:
wherein Y = -O- or -NH- and m = 2.
wherein Y = -O- or -NH- and m = 2.
7. The monomer of claim 6 wherein Y = -NH-.
8. A monomer comprising:
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-;
R = H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-;
R = H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
9. The monomer of claim 8 wherein X = -NR-; R = H; R' = individually H or -CH3; m = 2; n = 1; and Z = 0.
10. A wet adhesion copolymer comprising a major.
portion of a first monomer and from about 0.01 mol-% to 15 mol-% of a second monomer of the formula wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
portion of a first monomer and from about 0.01 mol-% to 15 mol-% of a second monomer of the formula wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
11. The wet adhesion copolymer of claim 10 wherein the second monomer comprises:
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R - H or CH3.
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R - H or CH3.
12. The wet adhesion copolymer of claim 10 wherein the second monomer comprises:
wherein Y = -O- or -NH- and m = 2.
wherein Y = -O- or -NH- and m = 2.
13. The copolymer of claim 10 wherein the first monomer comprises a vinyl monomer selected from the group consisting of alpha-olefin monomers, acrylic monomers, vinyl aromatic monomers, and alpha-beta unsaturated mono-and di-carboxylic acids and esters thereof.
14. The copolymer of claim 13 wherein the first monomer comprises a vinyl acrylic monomer
15. A wet adhesion copolymer comprising a major portion of a first monomer and from about 0.01 mol-% to 15 mol-% of a second monomer of the formula wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-;
R = H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH3CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
R = H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH3CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
16. The polymer of claim 15 wherein X = -NR-; R = H;
R' = individually -H or -CH3; m = 2; n = 1; and Z = 0,
R' = individually -H or -CH3; m = 2; n = 1; and Z = 0,
17. The copolymer of claim 15 wherein the first monomer comprises a vinyl monomer selected from the group consisting of alpha-olefin monomers, acrylic monomers, vinyl aromatic monomers, and alpha-beta unsaturated mono-and di-carboxylic acids and esters thereof.
18. The copolymer of claim 15 wherein the first monomer comprises a vinyl acrylic monomer.
19. An aqueous copolymer latex having enhanced wet adhesion, said latex comprising a major portion of water and dispersed therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-3 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-3 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
20. The latex of claim 19 wherein the second monomer comprises:
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
21. The latex of claim 20 wherein the second monomer comprises:
wherein Y = -O- or -NH- and m = 2.
wherein Y = -O- or -NH- and m = 2.
22. An adhesive composition comprising the latex of claim 19.
23. A coating composition comprising the latex of claim 19.
24. A sealant composition comprising the latex of claim 19.
25. A solution copolymer having enhanced wet adhesion, said solution comprising a major portion of organic solvent and solubilized therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
wherein n = 1 or 2; m = 1 or 2; R' = H or CH3; X = -O-, -CH2, -NR-; R = H, -C1-5 alkyl, -aryl, -CH2(CH2)y-C = N, -CH2OC1-5 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12;
A = phenylene or C1-5 alkylene; Y = -O-, -NH-, -NHNH-, -O-M-, -NH-M-, or -NH-NH-M-; and , , , and wherein x = 2 - 5.
26. The solution copolymer of claim 25, wherein the second monomer comprises:
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
wherein n = 1 or 2; m = 2; each of R' = independently H or CH3; Y = -NH- or -O-; Z = -O- or -S-; and R = H or CH3.
27. The solution copolymer of claim 25, wherein the second monomer comprises:
wherein Y = -O- or -NH- and m = 2.
wherein Y = -O- or -NH- and m = 2.
28. An adhesive composition comprising the latex of claim 25.
29. A coating composition comprising the latex of claim 25.
30. A sealant composition comprising the latex of claim 25.
31. An aqueous copolymer latex having enhanced wet adhesion, said latex comprising a major portion of water and dispersed therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-; R =
H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-; R =
H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
32. The latex of claim 31 wherein X = -NR=; R = H;
R' = individually -H or -CH3; m = 2; n = 1; and Z = 0.
R' = individually -H or -CH3; m = 2; n = 1; and Z = 0.
33. An adhesive composition comprising the latex of claim 31.
34. A coating composition comprising the latex of claim 31.
35. A sealant composition comprising the latex of claim 31.
36. A solution copolymer having enhanced wet adhesion, said solution comprising a major portion of organic solvent and dissolved therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-; R =
H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
37. The solution copolymer of claim 36 wherein X =
-NR-; R = H; R' = individually -H or -CH3; m = 2; n = 1;
and Z = 0.
38. An adhesive composition comprising the latex of claim 36.
39. A coating composition comprising the latex of claim 36.
40. A sealant composition comprising the latex of
36. A solution copolymer having enhanced wet adhesion, said solution comprising a major portion of organic solvent and dissolved therein a copolymer comprising a first vinyl monomer and a second monomer of the formula:
wherein n = 1 or 2; m = 1 or 2; X = -O-, -CH2-, -NR-; R =
H, -C1-5 alkyl, -(CH2)yOH, -CH2(CH2)-C = N, -CH2OC1-15 alkyl, -(CH2)yOH, -CH2CH(OH)CH3 wherein y = 1 - 12; R' individually = -H or -CH3.
37. The solution copolymer of claim 36 wherein X =
-NR-; R = H; R' = individually -H or -CH3; m = 2; n = 1;
and Z = 0.
38. An adhesive composition comprising the latex of claim 36.
39. A coating composition comprising the latex of claim 36.
40. A sealant composition comprising the latex of
claim 36.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US47971890A | 1990-02-14 | 1990-02-14 | |
| US479,718 | 1990-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2074098A1 true CA2074098A1 (en) | 1991-08-15 |
Family
ID=23905129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2074098 Abandoned CA2074098A1 (en) | 1990-02-14 | 1991-02-12 | Copolymerizable imidazolidinone monomer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0594596A1 (en) |
| JP (1) | JPH05503941A (en) |
| CA (1) | CA2074098A1 (en) |
| WO (1) | WO1991012243A2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399706A (en) * | 1993-03-02 | 1995-03-21 | H. B. Fuller Licensing & Financing, Inc. | Imidazolidinone diamine and derivatives thereof |
| US5496907A (en) * | 1993-03-02 | 1996-03-05 | H. B. Fuller Licensing & Financing, Inc. | Wet adhesion monomers with ureido functionality and polymers prepared therefrom |
| ATE254109T1 (en) | 1996-06-24 | 2003-11-15 | Cytec Tech Corp | NEW POLYMERIZABLE ACYLIMIDAZOLIDINONE MONOMERS |
| DE69725444T2 (en) * | 1996-06-24 | 2004-07-22 | Cytec Technology Corp., Wilmington | POLYFUNCTIONAL CROSSLINKING ACYLIMIDAZOLIDINONE DERIVATIVES |
| US6166220A (en) * | 1996-06-24 | 2000-12-26 | Cytec Technology Corp. | Ethylenically unsaturated imidazidolidinone monomers |
| US6630599B1 (en) | 1998-01-06 | 2003-10-07 | Cytec Technology Corp. | Process for preparing derivatives of isopropenyl-α, α-dimethylbenzyl isocyanate |
| US6069275A (en) * | 1998-01-28 | 2000-05-30 | Rhodia Inc. | Monomers and polymers and latices therefrom |
| DE19830555A1 (en) | 1998-07-08 | 2000-01-13 | Basf Ag | Use of aqueous polymer preparations for the coating of polyurethane-containing substances |
| DE19924790A1 (en) * | 1999-05-29 | 2000-11-30 | Bayer Ag | Polymerizable, olefinically unsaturated monomers |
| JP6572208B2 (en) * | 2014-06-12 | 2019-09-04 | 広栄化学工業株式会社 | Onium salt, acrylic acid copolymer containing the onium salt, and antistatic agent containing the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2727016A (en) * | 1955-12-13 | Hjnan | ||
| US3369008A (en) * | 1964-05-26 | 1968-02-13 | Rohm & Haas | N-(cyclic ureidoalkyl) crotonamides and polymers thereof |
| US4032638A (en) * | 1974-10-29 | 1977-06-28 | E. I. Du Pont De Nemours And Company | Heterocyclic ureas |
| US4111877A (en) * | 1976-07-29 | 1978-09-05 | Air Products & Chemicals, Inc. | Allyl esters of n-alkyl-omega-(alkyleneureido) amic acids and their synthesis and use in aqueous emulsion polymer systems |
| US4104220A (en) * | 1976-07-29 | 1978-08-01 | Air Products & Chemicals, Inc. | Alkenyl 1-(2-Aminoethyl) alkyleneureido succinamates, their synthesis, and use in aqueous emulsion polymer systems |
| US4632957A (en) * | 1984-09-04 | 1986-12-30 | Ppg Industries, Inc. | Ethylenically unsaturated ethylene and propylene ureas containing alkylene urea groups or alkylene urethane groups, useful in coating compositions |
-
1991
- 1991-02-12 WO PCT/US1991/000939 patent/WO1991012243A2/en not_active Application Discontinuation
- 1991-02-12 JP JP3504715A patent/JPH05503941A/en active Pending
- 1991-02-12 EP EP91904976A patent/EP0594596A1/en not_active Withdrawn
- 1991-02-12 CA CA 2074098 patent/CA2074098A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO1991012243A3 (en) | 1991-10-03 |
| WO1991012243A2 (en) | 1991-08-22 |
| EP0594596A1 (en) | 1994-05-04 |
| JPH05503941A (en) | 1993-06-24 |
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