FI57119C - FREQUENCY REFRIGERATION FOR ALKALISCARTAINING AERTAIN CHARACTER ACYLESTERSAMPOLYMERISATDISPERSIONER - Google Patents

Description

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Patent ni? Ddelat ^ T ^ (51) Kw.ik. * / Int.ci. » C 08 * 220/18 C 08 F 220/44 '' C 08 F 218/04 FINLAND — FINLAND (H) P * t * nttlhtk «mu« - PatMtarafiknlnf 1523/73 (22) H «k« ml (pltvi - Antttknlnpdtg H.05.73 (23) Starting date — Glltl | h * tfda | 11.05.73 (41) Tullut JulklMkal - Bllvlt offvntllg l6.11.73 _ '(44) Date of nihaviktlpanon and kuLululkaiau -

Patent · och ragistaratyraisan v 'AniOkan utlagd och utl. * KrtfMn pubUevnd 29.02.80 (32) (33) (31) Pnrfattjr Kuotkws — Begird prlorlttt 15.05. J2

The Federal Republic of Germany, the Federal Republic of Germany (DE) P 2223630.2 (71) Hoechst Aktiengesellschaft, Postfach 80 03 20, 6230 Frankfurt (Main) 80, the Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Rolf Reinecke, Wiesbaden, Karl Josef Rauterkus, Kelkheim / Taunus,

Werner Schmieder, Kelkheim / Taunus, Eleonore Lutz, Frankfurt / Main,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 ^) Oy Kolster Ab (5 * +) Method for the preparation of alkali-crosslinking aqueous acrylic ester copolymer dispersions

The invention relates to a process for the preparation of crosslinkable acrylic ester copolymers.

Crosslinkable acrylic ester copolymers are known per se. Combinations of crosslinking possibilities are described, for example, in DE-A-1 805 370 and in J. Paint Technology 1 + 2, (1970) 3½ and J. Paint Technology U2, (1971) 1 + 5-50. In principle, a distinction is made between the two cross-linking procedures.

Cross-linking during and after cross-linking.

Crosslinking during manufacture with multifunctional monomers such as diallyl compounds, diacrylates or dimethacrylates results in copolymers which have a certain cohesion but which can no longer be influenced afterwards. Subsequent crosslinking of the copolymers with reactive monomers, on the other hand, offers an advantageous opportunity to possibly refine the cohesion of the copolymers. Such reactive 57119 monomers include, for example, hydroxy, epoxy, halohydrin-activated halogen compounds. Copolymers containing these reactive monomers can be subsequently crosslinked with suitable components and optionally with the addition of suitable catalysts. Examples are crosslinking of copolymers containing hydroxyl groups with diisocyanates or crosslinking of copolymers containing epoxy groups with diamines. Depending on the type of reaction (addition, condensation) and the catalyst system, crosslinking takes place at room temperature or at elevated temperature.

Thermal crosslinking mechanisms are not suitable for many applications because unwanted discoloration (yellowing) often occurs. In many applications, increasing amounts of polymers are used in the form of their aqueous dispersions due to their advantageous handling properties, such as odorlessness and no need for solvent. For such plastic dispersions, crosslinking mechanisms that are directly useful in the dispersion are desirable, and that is advantageous for many uses of these dispersions that do not require thermal activation.

From DE patent 1 20U 1 + 07, aqueous dispersions of acrylic acid esters, monochloroacetic acid vinyl ester and possibly other copolymerizable monomers are known. However, after separation of the aqueous phase, the polymer is mixed with the same rubber additives as in the artificial rubber and vulcanized at a temperature of about 160 ° C, whereby elastomer-forming masses are formed.

SE patent publication 386,190 discloses acrylic ester copolymers which, however, differ from those prepared by the process according to the invention. Their monomer components are not haloalkanecarboxylic acid esters, as in the copolymers prepared according to the invention; they are used for lacquer powders, while the copolymers prepared according to the invention are mainly used as adhesives for labels or the like, the manufacturing methods differ, since the process according to the invention uses dispersion copolymerization and the process according to SE is carried out without water.

The invention relates to a process for the preparation of alkali-crosslinking aqueous copolymer dispersions by polymerizing a mixture of a) from 50 to 95% by weight, based on the monomer mixture, of at least one saturated aliphatic alcohol having U-12 C atoms, acrylic acid and / or methacrylic acid ester h) O-UO by weight, based on the monomer mixture, monomers with glass transition temperatures of homopolymers of -U0 ° C to + 150 ° C, and c) 0.5-8 by weight, based on the monomer mixture, e <-halogen 3,571,9 carboxylic acid vinyl ester of formula (i)

B

H-C-COOCH CH (I) i d

X

wherein X is fluorine, chlorine, bromine or iodine, in aqueous dispersion in the presence of emulsifiers and / or protective colloids and radical initiators.

The process according to the invention is characterized in that the other reactive monomers used are d) 0.5 to 5% by weight, based on the monomer mixture, of er, β-ethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms, or partial esters thereof with saturated aliphatic with alcohols having 1 to 20 carbon atoms, and e) 0.1 to 5% by weight, based on the monomer mixture, of monomers containing hydroxyl groups of the formula (II) R -CH * C-COO-CHp-CH-R ( il) OI * t 7

Ru OH

wherein R 1 is hydrogen, a methyl group or a group -COOR 8, R 1 and R 2 represent hydrogen or a methyl group and R 8 is hydrogen or an alkyl group having 1 to 12 carbon atoms.

Suitable esters of acrylic acid or methacrylic acid are esters of saturated straight-chain or branched aliphatic alcohols having U-12 C atoms, e.g. n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and / or lauryl acrylate and / or lauryl acrylate.

Other copolymerizable monomers are those whose homopolymers have settling temperatures of -U0 ° C to + 150 ° C, preferably 0 ° C to 110 ° C, and which do not participate in any of the other reactions of the other groups a), c), d) under the polymerization conditions. ) and e) with monomers. Examples of these are styrene, methyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide or methacrylamide. They are used in O-UO weight-?, Preferably 0.5-25 weight-? calculated on the monomer mixture.

X-halo alkanecarboxylic acid vinyl esters of formula (I) used from 0.5 to 8% by weight calculated on the monomer mixture, for example vinyl ester of monohaleacetic acid and halopropionic acid. Preferred are monofluoro, monochloro, monobromo and monoacetic acid vinyl ester, especially monochloroacetic acid vinyl ester.

Examples of other? *,? -Ethylenically unsaturated carboxylic acids used as reactive monomers include monocarboxylic acids acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acids as maleic acid and fatty acid monomylate and fumaric acid, and their half-esters with alcohols having chain length. and itaconic acid. Preferably monocarboxylic acids are used, in particular acrylic acid. Unsaturated carboxylic acids are used in an amount of 0.5 to 5% by weight, based on the monomer mixture.

As the monomers containing the hydroxyl groups of the formula (II), for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, crotonic acid 2-oxyethyl ester, 2-oxyethyl esters, 2-oxyethyl ester, 2-oxyethyl ester, 2-oxyethyl ester, can be used. The amount of hilda is 0.1-5 by weight of nonomeric Baoxeta.

The dispersions according to the invention are prepared by radical polymerization of monomers in aqueous dispersion using emulsifiers, protective colloids and * optionally regulators, using methods known in the art for dosing (e.g. * pre-emulsification or monomer dosing).

The initiators used are inorganic and organic per-compounds such as ammonium persulfate, potassium persulfate, sodium perphosphate, organic peroxides such as dibenzoyl peroxide, peresters such as perisooctylate oxydamine amineate sulfate, with amounts of accelerators such as iron, cobalt cerium taladyl salts. The polymerization temperature is 0 to + 100 ° C, preferably 20 to 80 ° C. Preferably, anionic emulsifiers are used, e.g. alkali salts of the sulfuric acid half-esters of alkylphenols or alcohols, the alkylphenols and alcohols possibly still being able to react in small amounts with ethylene oxide, and alkyl and arylsulfonates or sulfosuccinic acid mono- and diesters. Examples of these are the alkali metal salts of the sulfuric acid half-ester of nonylphenol which has reacted with 4-5 moles of ethylene oxide, sodium lauryl sulphate, the sodium salt of lauryl alcohol ether sulphate with 10 moles of ethylene oxide, sulphonate oxide, sodium dodecylbenzenesulphonate, The amount of wedding emulsifiers is preferably 0.1 to 5% by weight, based on the monomers. Optionally, nonionic emulsifiers of the oxyethylated alkylphenol type can also be used, e.g. with nonylphenol with 50 moles of ethylene oxide or condensation products of ethylene oxide and propylene oxide. As protective watches, for example, polyvinyl alcohol, poly-H-vinylpyrrolidone, hydroxyethylcellulose, carboxymethylcellulose or copolymers of maleic acid with amounts of vinyl compounds such as vinyl ethers, styrene, propylene, ethylene or ethylene can be used.

The dry matter content of the dispersion is between 50 and 70, preferably between 40 and 60

The dispersions prepared according to the invention are easily alkali-crosslinkable, in which case the degree of cohesion or cross-linking can be adjusted by the amount of alkali or pH added. In addition, the polymerization of monomers containing hydroxyl groups also achieves the optimum adhesion and cohesion properties.

The dispersions thus prepared are crosslinked with ammonium hydroxide, alkali hydroxide or alkaline earth hydroxide, preferably sodium hydroxide or potassium hydroxide, which are added to the dispersion in the form of aqueous solutions. The pH of the dispersion is then initially set between 2-3 and 6-12, preferably between T "H", depending on the desired cohesion and adhesion.

The crosslinked copolymers prepared by the process of the invention are characterized by an excellent cohesion. They can be used as raw materials for varnishes, adhesives, pigment binders, cardboard gauze binders and sealing and coating compositions. Compatibility with common additives such as pigments, fillers, resins and plasticizers is good.

The copolymers prepared according to the invention are particularly suitable as adhesive adhesives for self-adhesive floor coverings, self-adhesive paper or metal film labels, foams, wallpaper or adhesive tapes. The heat resistance of the adhesives is excellent, adhesion fracture is also observed as a fracture image at elevated temperatures. There is a slight tendency for yellowing films to turn yellow. If necessary, the polymers can be further modified by the addition of pigments, fillers or tacky resins.

The usefulness of the polymers of the invention requires that the general causal relationships between the structure and properties of the polymers known to those skilled in the art be taken into account. This applies in particular to the glass transition temperature of the copolymer, which is adjusted according to the respective use of these copolymers by known methods, so that a polymer with optimal properties can be prepared for each application.

The invention is further illustrated by the following examples.

Example 1

Prepare a stable monomer emulsion from the following ingredients: 2-ethylhexyl acrylate 688 parts by weight of acrylonitrile 7U of "acrylic acid 2k" of monochloroacetic acid-vinyl ester 12 "1 + -5 moles of ethylene oxide sulfuric acid

A three-necked flask purged with nitrogen and refluxed with a thermometer is charged with 150 parts by weight of water, 5 parts by weight of the emulsifier prepared above and 100 parts by weight of the monomer emulsion. It is heated to 60 ° C and initiator solutions containing 0.56 parts by weight of ammonium lumpersulfate in 7.5 parts by weight of H 0 and 2 0.15 parts by weight of sodium disulfite in 7.5 parts by weight of HgO are added.

After 15 minutes, the final aonomer emulsion is metered in under a nitrogen atmosphere, in which case initiator solutions containing 0.66 parts by weight of ammonium lump persulphate in 60 parts by weight of water and 0.53 parts by weight of sodium disulphate in 60 parts by weight of water are added.

After a reaction time of 2 hours, cool to 60 ° C. The pH is adjusted to the desired value with 5-10 NaOH solution.

The resulting dispersion is coagulate-free and stable. The pE value is about 2.5. The dry matter content of the dispersion is 53.5

In the following examples, the procedure was as in Example 1, adding the following with a monomer mixture:

Example 2 84 1> 2-Ethylhexyl acrylate, 9.5 96 acrylonitrile, 3> acrylic acid and $ 3.5 monochloroacetic acid vinyl ester.

Example 3 83 i> 2-ethylhexyl acrylate, $ 9> acrylonitrile, 3 96 acrylic acid, 1.5 hydroxypropyl methacrylate, $ 3.5 monochloroacetic acid vinyl grains.

Example 4 85 56 2-Ethylhexyl acrylate, 9.5% acrylonitrile, 2.5 96 acrylic acid, 2.0 L monochloroacetic acid vinyl ether and 1.0 N hydroxypropyl methacrylate.

Example 5 86 I »2-ethylhexyl acrylate, 9.5 l> acrylonitrile, 3.0 96 acrylic acid, 1.0 96 monochloroacetic acid vinyl ester, 0.5 96 hydroxypropyl methacrylate.

Example 6 85 $ 2-ethylhexyl acrylate, $ 9.5 methyl methacrylate, $ 2.5 acrylic acid, 2.0 monochloroacetic acid vinyl ethers and 1.0 N hydroxypropyl methacrylate.

Example 7 85 # 2-ethylhexyl acrylate, 9.5 l »styrene, 2.5 l» acrylic acid, 2 # 0 l »monochloroacetic acid vinyl ethers and 1.0 96 hydroxypropyl methacrylate.

7 5711 9

Example 8 85 l of 2-ethylhexyl acrylate, 9.5 l of acrylonitrile, 2.5% of acrylic acid, 2.0% of monochloroacetic acid vinyl ester and 1.0 l of hydroxyethyl methacrylate.

Example 9 85-> 2-Ethylhexyl acrylic, 9.5 # acrylonitrile, 2.5 N-acrylic acid, 2.0 L of monochloroacetic acid vinyl ester and 1.0 L of hydroxyethyl acrylate.

Example 10 85 l of 2-ethylhexyl acrylate, 9.5 l of acrylonitrile, 2.5 l of acrylic acid, 2.0 l of monochloroacetic acid vinyl ether, 1.0 l of maleic acid methyl 2-oxyethyl ester.

Example 11 85 l of 2-ethylhexyl acrylate, 9.5 l of acrylonitrile, 2.5 l of acrylic acid, 2.0 l of vinyl acetate of monochloroacetic acid and 1.0 l of crotonic acid oxyethyl ester.

Example 12 84.5 l of 2-ethylhexyl acrylate, 9.5 g of acrylonitrile, 2.5 l of 6 acrylic acid, 2.0 l of monochloroacetic acid vinyl ester and 1.5 l of maleic acid 2-ethylhexyl octyl ethyl ester.

Example 15 84.2 l of 2-ethylhexyl acrylate, 9.4 l of acrylonitrile, 2.8 l of acrylic acid, 2.8 l of monoiodoacetic acid vinyl ester and 0.8 l of hydroxypropyl methacrylic.

Example 14 84.2 and 2-ethylhexyl acrylate, 9.4 .mu.l of acrylonitrile, 2.8 .mu.l of acrylic acid, 2.8 .mu.l of achloroacetic acid vinyl ester and 0.8 .mu.l of hydroxypropyl methacrylate.

Example 15 94.5 l of lauryl methacrylate, 2.5 l of acrylic acid, 2 # monochloroacetic acid vinyl grains and 1.0 l of hydroxypropyl methacrylate.

Comparative Example 1 86 and 2-ethylhexyl lacrylate, 9.5 # acrylonitrile, 5.0 # acrylic acid, 1.5 L hydroxypropyl methacrylate.

Comparative Example 2 87.5 # 2-ethylhexyl acrylate, 9.5 # acrylonitrile, 5.0 # acrylic acid '* 5711 9 8

Reference Example 3 88.5 # 2-Ethylhexyl acrylate, 9.5 ^ acrylonitrile, 2.0 96 mono-chloroacetic acid vinyl ester.

The following test methods were used to test the self-adhesive properties of these polynerates: a) Measurement of peel strength (kp / 2.5 cm):

The polyethylene terephthalate film, measuring 2.5 cm x 20 cm, is coated with an adhesive coating with a thickness of 0.3 mm (mark application). After drying, the film is glued lightly to a carefully cleaned steel sheet.

After maturing for one hour at room temperature, the gluing is removed at a 90 ° tea angle at a removal rate of -30Φ 'mm / min. In addition, the fracture image of the adhesive is criticized. This measurement is performed at both + 70 ° C and + 10 ° C.

h) Heat resistance (hours):

The polyethylene terephthalate film is coated with an adhesive as in the previous case, and after drying the cloth layer, it is glued to the steel sheet 2 so as to form an overlapping surface of 2.5 .mu.m. The gluing is loaded to an angle of 0 with a weight of 500 g. The measuring temperature is 100 c. Determine the time at which the adhesive comes off, c) Determination of cross-linking:

The dispersion and the film ground from the dispersion are extracted with dioxane. Determine the percentage by mass of dissolved matter in the dry matter on the basis of the loss in weight of the dry matter. Within the grain limits, both extraction values are the same.

The properties of the adhesives are shown in the following tables.

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• t »o i g! 5711 9 12 The effect of pH on cross-linking is clearly significant.

The solubilities of all polymers containing monohaloacetic acid vinyl ester and non-β-unsaturated acids decrease with increasing pH.

That this dependence must be attributed to the combination of reactive monomers is apparent from the comparative examples. Thus, neither the 2-ethylhexyl acrylate / acrylonitrile / acrylic acid formulation nor the test, which further contains hydroxypropyl methacrylate, nor the test, which contains monohalin vinyl ester but no acid, show such an effect of pH on the solubility of the copolymer.

In addition to the halogen ester / acid combination of reactive monomers, the concentration of hydroxyl-containing monomers has a positive effect on the adhesion and cohesion properties of the copolymer. Thus, due to their high cohesion, the measured peel strengths are still very high even at 70 ° C, in which case adhesion fracture (pH adjusted to 7) is observed as the fracture type. When the pH is adjusted to 3, pure cohesion fracture is observed, as expected, at 70 ° C because the cohesion of the polymer is insufficient due to the lack of crosslinking.

Examples 16-21

According to Example 1, the following monomer mixtures were reacted with each other:

Example 16 73% octyl acrylate, 21% vinyl acetate, 5% vinyl chloroacetate, 0.5% methacrylic acid, 0.5% hydroxymethyl methacrylate.

Example 17 60% octyl acrylate, 30% vinyl acetate, 7% vinyl chloroacetate, 1% crotonic acid, 0.5% hydroxyethyl methacrylate.

Example 18 60% octyl acrylate, 3 μl vinyl acetate, 2% vinyl chloroacetate, 2% maleic acid, 2% hydroxyethyl methacrylate.

Example 19 90% hutyl acylate, 1% methacrylonitrile, 1% vinyl chloroacetate, 3% methacrylic acid, 5% hydroxyethyl methacrylate.

Example 20 71.5% octyl acrylate, 20% vinyl acetate, 5% vinyl chloroacetate, 3% methacrylic acid, 0.5% hydroxyethyl methacrylate.

Example 21 85 »5% octyl acrylate, 3 * 5% methacrylonitrile, 7% vinyl chloroacetate, 3% methacrylic acid, 1 f hydroxyethyl methacrylate.

13 571 1 9

After the reaction, the pH of the samples of each mixture was adjusted to about 2, 7 and 10.

In the same manner as in Examples 1-15 (however, the temperature was 23 ° C and 70 ° C), a peel strength measurement was performed. The results were as follows:

Example pH Peel strength at 23 ° C at 70 ° C 16 2.5 5 (K) 0.86 (K) 7 2.6 (A) 1.1 (A) 10 1.95 (A) 0.8 (A) 17 7 1.3 (A) 0.6 (A) 10 1.5 (A) 0.65 (A) 18 2.1+ 2.5 (K) 3.1 + 5 (K) 7 2.0 (A) 2.6 (A) 10 1.5 (A) 3.2 (A) 19 2.5 1.5 (A) 3.1 + 5 (K) 7 1.6 (A) 2.6 (K) 10 1.2 (A) 3.2 (A) 20 1.7 2.0 (A) 0.8 (A) 7 2.1 (A) 0.9 (A) 10 0 .7 (A) 0.2 (A) 21 1.7 2.1 (A) 0.1 + 8 (A) 7 0.8 (A) 0.5 (A)

Fracture image: adhesion fracture (A), cohesion fracture (K)

Claims (2)

57119 A process for preparing alkali-crosslinking aqueous copolymer dispersions by polymerizing a mixture of a) from 50 to 95% by weight, based on the monomer mixture, of at least one saturated aliphatic alcohol having U-C 12 atoms, acrylic acid and / or methacrylic acid ester h) O-UO by weight, based on the monomer mixture, monomers with glass transition temperatures of homo-polymers of -4 ° C to + 150 ° C, and o) 0.5-8% by weight, based on the monomer mixture, of <x -haloalkane a carboxylic acid vinyl ester of the formula (I) H HC-COOCH - CH «(I) 1 * X in which X is fluorine, chlorine, chromium or iodine, in aqueous dispersion in the presence of emulsifiers or protective colloids and radical initiators, characterized in that other the reactivity as parent monomers is used d) from 0.5 to 5% by weight, based on the monomer mixture, of β, β-ethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms, or their partial esters of saturated aliphatic alcohols. with 1 to 20 carbon atoms, and e) 0.1 to 5% by weight, based on the monomer mixture, of monomers containing hydroxyl groups of the formula (XI) R -CH C-COO-CH 2 -CH-R 2. (Il) J t £ \ J Ru OH having hydrogen, a methyl group or a group -COORg, R1 and R1. represent a hydrogen or methyl group and Rg is a hydrogen or alkyl group having 1 to 12 carbon atoms. Process according to Claim 1, characterized in that the pH of the dispersion after polymerization is adjusted to between 6 and 12 with alkali, alkaline earth or ammonium hydroxide.