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WO1996021687A1 - Procede de production de copolymeres contenant des groupes aldehyde - Google Patents

Procede de production de copolymeres contenant des groupes aldehyde Download PDF

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Publication number
WO1996021687A1
WO1996021687A1 PCT/EP1995/005080 EP9505080W WO9621687A1 WO 1996021687 A1 WO1996021687 A1 WO 1996021687A1 EP 9505080 W EP9505080 W EP 9505080W WO 9621687 A1 WO9621687 A1 WO 9621687A1
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WO
WIPO (PCT)
Prior art keywords
formula
copolymers
emulsion
acrolein
acetals
Prior art date
Application number
PCT/EP1995/005080
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German (de)
English (en)
Inventor
Hermann Piana
Thomas Hasskerl
Ingo Troltsch
Dietrich Arntz
Original Assignee
Degussa Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Degussa Aktiengesellschaft filed Critical Degussa Aktiengesellschaft
Publication of WO1996021687A1 publication Critical patent/WO1996021687A1/fr

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    • 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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/34—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an aldehydo radical
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/38—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an acetal or ketal radical

Definitions

  • the invention relates to a process for the preparation of copolymers bearing pendant aldehyde groups in the emulsion or suspension polymerization process, the copolymers having, in addition to any structures resulting from the processes mentioned from unsaturated monomers, at least one structural unit of the general formula I,
  • R is H, C- j _-C4-alkyl, linear or unbranched.
  • the invention is directed to a process for the preparation of copolymers of acrolein in the emulsion copolymerization process.
  • Acrolein is a well known monomer that is found in
  • Emulsion polymers in particular in latices for the formation of leather, are used.
  • the leather varnishes modified with acrolein are particularly characterized by their improved resistance to moisture and solvents. Furthermore, leather workpieces treated with it can be more easily removed from the processing tools after further processing (US-A-4, 016, 127 or US-A-3,896,085).
  • leather and synthetic leather articles are coated with a leather finish after the application of a (pigmented) latex coating.
  • a (pigmented) latex coating This is mainly due to the aesthetic and optical effects achieved, but also to increase the flexibility low temperatures down to -40 ° C. This is to prevent damage to the latex coating at low temperatures.
  • the coating serves to increase the abrasion resistance and wearing comfort as well as to avoid caking of the leather items during the manufacturing process.
  • Such leather finishing lacquers contain amino groups which only lead to the desired properties if the leather base lacquers are modified with aldehyde groups and so optimal crosslinking with the amino groups of the leather clear lacquers is possible (US Pat. No. 4,256,809).
  • acrolein splitter There has been no shortage of attempts to use acrolein in the form of an easier and safer to handle, storage-stable and less toxic depot compound, a so-called "acrolein splitter".
  • French patent FR-A-1, 546,472 describes a process for the purification of glycerol which contains cyclic acrolein acetals. The treatment is carried out with acidic ion exchangers, followed by another
  • acrolein acetals can be regarded as a depot compound for the purpose of obtaining acrolein.
  • acrolein can be released from acrolein acetals by acid-catalyzed deacetalization (US Pat. No. 4,851,583).
  • acrolein acetals are cleaved using a strongly acidic ion exchanger.
  • mineral acids did not lead to a satisfactory result.
  • the solutions obtained in the deacetalization according to the US patent in question which contain acrolein and the corresponding alcohols, are biocidal and pesticidal and are used for the treatment of water.
  • EP-A-0 439 658 describes a process in which, for the purpose of doping aqueous solutions with acrolein in a biocidally effective concentration, the acrolein is formed by deacetalization in the aqueous phase in the presence of a strongly acidic catalyst.
  • the process according to this European patent is characterized in that the acrolein formed is continuously removed from the aqueous phase and transferred into the aqueous solution to be doped by continuously passing an inert gas stream through the strongly acidic solution containing acrolein acetal. The acrolein is stripped off with this gas stream, transferred into the aqueous phase to be doped and absorbed there. This process is comparatively complex since the deacetalization takes place only in contact with strong acids.
  • Ci-Cg-alkyl linear or branched, where R 1 and
  • R 2 can also be connected together to form a ring, according to the emulsion or
  • the acetals of the general formula II are split into aldehydes of the general formula III as the polymerization reaction proceeds,
  • R has the meaning given for formula I
  • the compounds of formula III are incorporated into the copolymer formed in the copolymerization to produce the structure of formula I.
  • This incorporation preferably takes place to the extent that the reactive aldehyde form of the general formula III is released from the depot form of the general formula II, so that a very low concentration of ⁇ , ⁇ -unsaturated aldehyde is constantly present in the reaction mixture.
  • the low concentration of free ⁇ , ⁇ -unsaturated aldehyde is preferably in a range from 1 to 1000 ppm.
  • the process according to the invention is advantageously distinguished in that the acetals of the general formula II are incorporated into the copolymer formed during the copolymerization and the resulting acetal structural units of the formula IV
  • part of the depot form is converted into the corresponding ⁇ , ⁇ -unsaturated aldehyde during the polymerization reaction, while another part of the depot form is acetal is built into the copolymer.
  • the aldehyde structural units of the formula I can then either be released during the polymerization reaction, but it is also possible to isolate the copolymer and then to release the acetal structures which may be present therein, for example by treatment with an acid.
  • acetal structures which may be present therein, for example by treatment with an acid.
  • acetal structures which may be present therein, for example by treatment with an acid.
  • a certain proportion of acetal structures can also result in the context of the invention modified copolymer remain without violating the principle of the invention.
  • at least part of the depot form of the ⁇ , ⁇ -unsaturated aldehyde as the side aldehyde group will always result in the copolymer produced according to the invention.
  • ⁇ , ⁇ -unsaturated aldehydes from corresponding acetals as a depot form
  • the ⁇ , ⁇ -unsaturated aldehydes being preferred by acetalization is formed from the corresponding acetals in an aqueous phase of the emulsion or suspension.
  • the emulsion polymerization processes in which the present invention can be effectively used include all conventional emulsion polymerization techniques known to those skilled in the art.
  • Emulsion polymerization processes normally use sparingly water-soluble monomers, but water-soluble monomers such as, for example, can also be used
  • Acrylamide methacrylic acid or hydroxyethyl methacrylate and others can be polymerized and copolymerized in emulsion.
  • all monomers familiar to the person skilled in the art, which are known according to Allow emulsion polymerization to polymerize also be modified with ⁇ , ⁇ -unsaturated aldehydes.
  • the groups or classes of monomers which can be used successfully include, for example, ⁇ , ⁇ -unsaturated carboxylic acids, alkyl (C1-C24) esters of ⁇ , ⁇ -unsaturated
  • Carboxylic acids unsaturated di- or polycarboxylic acids and their esters, mono-, di- or polyesters of ⁇ , ⁇ -unsaturated carboxylic acids or carboxylic acid mixtures of di- or polyols, ⁇ , ⁇ -unsaturated aldehydes, vinyl halides, ⁇ -olefins, vinyl ethers, styrenes, Vinyl aromatics and / or (meth) acrylonitrile.
  • Advantageously usable representatives of these classes include a.
  • Styrene and alkyl-substituted styrenes such as o-, m- and p-methylstyrenes, ⁇ -methylstyrene, p-ethylstyrene and p-tert.
  • alkyl-substituted styrenes such as o-, m- and p-methylstyrenes, ⁇ -methylstyrene, p-ethylstyrene and p-tert.
  • styrenes such as o-, m- and p-methylstyrenes, ⁇ -methylstyrene, p-ethylstyrene and p-tert.
  • -butylstyrene Vinyl aromatics like that
  • Vinyl naphthalenes Monoolefins such as ethylene, propylene, butylene and isobutylene; halogenated vinyl compounds such as vinyl fluoride and vinyl chloride; Vinyl esters such as vinyl acetate and vinyl butyrate; ethylenically unsaturated monocarboxylic acids and their esters such as acrylic acid, methyl acrylate,
  • vinyl monomers Of these vinyl monomers, styrene, o-, m- and p-methylstyrene, acrylates, methacrylates and vinyl acetates are preferred. Acrylates, methacrylates and / or styrene are very particularly preferred.
  • the monomers mentioned can be copolymerized with one another either alone or as a mixture of two or more and modified in situ with the compounds of the general formula II.
  • Radical generator is not particularly limited.
  • water-soluble radical formers such as sodium peroxodisulfate, or also water-soluble azo initiators or water-soluble peroxides and hydroperoxides can be used as starters for the
  • Preferred catalysts are peroxidic radical initiators such as alkali persulfates or ammonium persulfates, perborates, H2O 2 , organic
  • Hydroperoxides such as t-butyl hydroperoxide, or esters, such as t-butyl perbenzoate.
  • radical formers are often used together with reducing agents such as sodium sulfide, sodium formaldehyde sulfoxylate or others.
  • reducing agents such as sodium metabisulfate, water-soluble thiosulfates, sulfites, tertiary amines such as triethanolamine, thioureas and salts of polyvalent metals, such as, for. B. sulfates of cobalt, iron, nickel "and copper.
  • catalysts or catalyst systems which react weakly acidic in the aqueous emulsion solution and set a pH ⁇ 8, so that for the acetalization of the ⁇ , ⁇ -unsaturated acetal compounds of the general
  • Formula II no further acids or ion exchangers need to be added to the emulsion polymerization system.
  • the compounds particularly suitable for this include u. a. Alkali or ammonium persulfates.
  • copolymers according to the invention are also available as emulsion polymers in the batch process and seed latex process. These special techniques are u. a. used to better control the heat of polymerization released, but also to z. B. adjust the particle size of the dispersion particles.
  • Emulsifiers and dispersants are also required for the emulsion polymerization of the invention.
  • Neutral emulsifiers or dispersing agents are particularly preferred.
  • anionic dispersing aids are products such as alkali metal salts of longer-chain fatty acids, alkyl sulfates such as sodium lauryl sulfate, alkyl sulfonates, alkylated aryl sulfonates such as sodium or potassium isopropylbenzenesulfonate, alkali metal salts of sulfosuccinic acid such as sodium octylsulfonosuccinate, sodium-N-methyl-N-methyl-n-methylla Alkali salts of alkylaryl polyethoxyethanol sulfates or sulfonates with e.g. B. 1 - 5 oxoethylene units.
  • Suitable neutral dispersing aids are e.g. B. alkylphenoxypolyethoxyethanol with an alkyl chain length of C ⁇ to C-
  • Condensates of higher fatty alcohols polyether polyol derivatives of etherified or esterified polyhydroxy compounds with a hydrophobic alkyl chain, e.g. B. sorbitol monostearate with 4-50 oxoethylene units or oxopropylene units.
  • the emulsion polymerization can be carried out at temperatures of
  • the easiest way to prepare the emulsion copolymers is by reacting the aqueous suspension or emulsion of the mixture of the monomers to be copolymerized and the catalysts with vigorous mixing at room temperature or elevated temperature.
  • emulsion polymerization processes which work with a continuous feed of monomer pre-emulsion (s) and catalyst solution can also be used.
  • the amount of catalyst required is usually between 0.01 and 3% peroxide and the same or a smaller amount of
  • Reduction catalyst based on the content of monomers in the suspension or emulsion.
  • the copolymers obtained can be dispersed or emulsified in a concentration of 5 - 60% in the aqueous phase, usually the content is between 30 and 50%.
  • Charge transfer reagents can also be added if required. Further auxiliaries such as sodium hydroxide, buffers, rheological additives, stabilizers are possible and are used by the person skilled in the art depending on the desired effect.
  • the raw materials described above are combined with one another and polymerized out using one of the methods mentioned above or combinations thereof.
  • the dispersions or emulsions obtained can also be pigmented for further processing and with addition, thickeners, flow control agents,
  • the order of addition of the reagents is relatively uncritical in the invention.
  • the acetal can either be added to the mixture of the other monomers to be polymerized and introduced continuously into the reaction solution with vigorous stirring, or the acetal can be metered in separately to the reaction solution during the reaction and at the same time the peroxidic and / or redox catalysts required for the polymerization in one
  • Add the desired concentration preferably from 0.01 to 3%, based on the monomer concentration, or all components can be added to the aqueous phase and the reaction is carried out in a one-pot process.
  • the pH of the solution can also be kept at a value of ⁇ 8 without the addition of a strong acid or an acidic ion exchanger, the aldehyde formed during the deacetalization being (constantly) incorporated into the polymer, so that the The concentration of free, monomeric acrolein in the reaction solution is kept as low as possible.
  • Modified copolymers are also obtained in the context of the invention in the suspension polymerization process.
  • suspension or bead polymerization itself is a process known per se to the person skilled in the art.
  • the invention is not based on a special variant of the
  • Suspension polymerization processes of the invention are above all the esters of acrylic acid and methacrylic acid with monohydric alcohols, in particular those with 1-16 carbon atoms, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid -lauryl ester, methacrylic acid aryl ester, methacrylic acid stearyl ester, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester, acrylic acid t-butyl ester, acrylic acid 2-ethylhexyl ester, acrylic acid lauryl ester, and vinyl aromatics such as styrene, vinyl toluene, p-tert. -Butylstyrene, or ⁇ -methylstyrene.
  • Monomers with a further functional group ie'ester of acrylic acid or methacrylic acid with dihydric alcohols, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or Hydroxypropyl methacrylate.
  • Further suitable constituents of monomer mixtures are, for example, glycidyl acrylate or glycidyl methacrylate and monomers with more than one vinyl double bond, in particular acrylates or methacrylates of di- or trifunctional alcohols, such as, for. B. ethylene glycol dimethacrylate, diethylene glycol dimethacrylate,
  • Triethylene glycol dimethacrylate or aromatics with two vinyl groups, such as. B. Divinylbenzene.
  • a peroxide such as. B.
  • Peracid anhydride, perester or dialkyl peroxide used in amounts of 1 - 10% based on the total amount of monomers. To regulate the molecular weight z. B.
  • Suitable alkyl mercaptans in amounts of 0.1-5%, preferably 0.5-3%, based on the total amount of the monomers.
  • the polymerization temperature depends on the
  • Polymerization initiator and is usually between 60 and 120 ° C.
  • copolymers of the invention have a stated proportion of aldehyde groups, they are outstandingly suitable as a leather coating.
  • the invention therefore preferably provides stable emulsion copolymers from an aqueous dispersion or emulsion of copolymers, the
  • Solid to the wt .-% consists of acrolein.
  • acrolein acetals to be used according to the invention are open-chain and cyclic acetals, as are known from US Pat. No. 4,851,583. Those acrolein acetals are preferably used whose alcohol component boils sufficiently far, ie at least 20 ° C., preferably above 40 ° C., above the boiling point of acrolein. Primary alcohols with 3 to 5 carbon atoms are preferred among the monohydric alcohols. Alcohols with 2 or more hydroxyl groups, especially 2 and
  • 3 OH groups preferably contain 2 to 6 carbon atoms.
  • 1,2- and 1,3-diols with 2 to 4 carbon atoms, triols of the glycerol and trimethylethane or propane type, and pentaerythritol are used as alcohol components for cyclic acrolein acetals with a 1,3-dioxolane or 1,3-dioxane Ring structure preferred.
  • Mixtures of acrolein acetals can also be used, for example those which are obtainable from the acetalization of acrolein with glycerol.
  • the preparation of the acetals is known per se - reference is made, for example, to US Pat. No. 3,014,924.
  • Appropriately, acrolein acetals with the lowest possible toxicity are used as a source of acrolein. These include e.g. B. Cyclic acrolein glycerol acetals.
  • R H and R 3 completes a cyclic acetal of acrolein which is derived from diols.
  • the diol ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerol, a hexose or a polysaccharide is particularly advantageous.
  • the diol propylene glycol is very particularly preferred.
  • the pH was determined directly from the aqueous polymer emulsion / suspension.
  • the solids content was determined by drying the dispersion for 2 hours at 100 ° C. to constant weight. The quotient of the weight after and before drying times 100 corresponds to the solids content in percent.
  • the theoretical solids content is calculated from the sum of the weight of the chemicals used (apart from water), based on the total weight of the batch. The quotient of the actual solids content from the theoretical solids content times 100 corresponds to the conversion in percent.
  • the mean particle size is determined by means of turbidity photometry from a laboratory turbidity photometer LTP 5 from Lange using formazin calibration solutions.
  • the minimum film formation temperature is determined using a Coesfeld film formation tester Thermostair BL-ED.
  • the dynamic viscosity is measured with a
  • Brookfield BHT rotational viscometer with measuring body No. 1 at 20 ° C.
  • Emulsions / suspensions were determined using headspace GC.
  • the aqueous solution was diluted with DMF and the sample was analyzed on a Porapack Q column with an internal standard.
  • the aldehyde groups that were incorporated into the polymer were determined by oxime titration. For this purpose, the emulsion or suspension was completely dissolved in THF, the aldehyde groups were reacted with hydroxylammonium chloride to form the oxime and the hydrochloric acid released was determined potentiometrically with NaOH. To correct the
  • a pre-emulsion is made from the following ingredients:
  • VDL 2-vinyl-1,3-dioxolane
  • MMA Methyl ethacrylate
  • n-BA n-butyl acrylate
  • VDL 2-vinyl-1,3-dioxolane
  • Example 2 Analogously to that described in Example 1, 500 g of demineralized water and 3.0 g of sodium dioctyl sulfosuccinate are placed in a laboratory reactor and heated to 80 ° C. ⁇ 1 ° C. at a stirring speed of 200 rpm. Shortly before metering in the pre-emulsion, 0.042 g of ammonium peroxodisulfate and 0.024 g of sodium bisulfite are added and the pre-emulsion is metered in over 4 h at 80 ° C. ⁇ 1 ° C.
  • Example 7-10 The emulsions of Examples 7-10 are prepared analogously to the procedure of Example 6.
  • the feed material ratios and the analytical data of the emulsions can be found in Tables 1 and 2.
  • Example 1 46 ⁇ 0.5 787 80 - -
  • Example 6 200 ⁇ 0.5 - - 42 50
  • the residual monomer content was determined using headspace GC.
  • the detection limit of Ac is 0.5 ppm.
  • the aldehyde content was determined after dissolving the emulsion in THF using oxime titration, taking into account the blank values (from Examples 5 and 10).
  • Examples 1, 2, 6 and 7 clearly demonstrate that acrolein released during the reaction from an acrolein depot in the form of the cyclic acetal of acrolein with ethylene glycol is incorporated into the polymer.
  • This procedure of a constant release and copolymerization of acrolein from the acetal, whereby the equilibrium is constantly shifted towards the cleavage products acrolein and ethylene glycol obviously also has an additional advantage that the content of the aldehyde groups incorporated into the polymer is higher than when using free acrolein, as a comparison of Examples 1 and 2 with 3 and 4 or 6 and 7 with 8 and 9 shows.
  • the other physical properties of the emulsion polymer are not influenced by the change from Ac to VDL, as a comparison without Ac / VDL (Examples 5 and 10) shows.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des unités structurales de la formule (I), dans laquelle R représente H ou un alkyle C1-C4 à chaîne droite ou ramifiée, produites selon un procédé de polymérisation en émulsion ou en suspension par addition d'acétals vinyliquement non saturés de la formule (II), dans laquelle R correspond à la définition donnée ci-dessus et R1 et R2 correspondent à la définition donnée dans la description. Cela évite les dangers que l'on connaît lorsque l'on doit travailler avec des aldéhydes α,β-insaturés, les aldéhydes ne sont pas libérés de leurs formes de stockage avant la polymérisation, et dans les copolymères est incorporée une proportion de groupes aldéhyde plus grande que celle obtenue lorsque l'on utilise des aldéhydes libres. L'invention concerne également l'utilisation des polymérisats produits selon le procédé de polymérisation en émulsion ou en suspension comme vernis pour cuirs modifiés par acroléine.
PCT/EP1995/005080 1995-01-09 1995-12-21 Procede de production de copolymeres contenant des groupes aldehyde WO1996021687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19500386.1 1995-01-09
DE1995100386 DE19500386A1 (de) 1995-01-09 1995-01-09 Verfahren zur Herstellung von seitenständige Aldehydgruppen tragenden Copolymeren

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WO1996021687A1 true WO1996021687A1 (fr) 1996-07-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2357509A (en) * 1999-12-23 2001-06-27 Hyundai Electronics Ind Polyacetal

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100533379B1 (ko) * 1999-09-07 2005-12-06 주식회사 하이닉스반도체 유기 난반사 방지막용 조성물과 이의 제조방법
KR100549574B1 (ko) * 1999-12-30 2006-02-08 주식회사 하이닉스반도체 유기 반사 방지막용 중합체 및 그의 제조방법

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290894A (en) * 1986-12-23 1994-03-01 Biopolymers Limited Biostatic and biocidal compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU560425A1 (ru) * 1976-03-15 1977-12-25 Институт Высокомолекулярных Соединений Ан Ссср Способ получени водорастворимых полимеров, содержащих альдегидные группы
US4851583A (en) * 1988-01-04 1989-07-25 Betz Laboratories, Inc. Method of generating acrolein

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290894A (en) * 1986-12-23 1994-03-01 Biopolymers Limited Biostatic and biocidal compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2357509A (en) * 1999-12-23 2001-06-27 Hyundai Electronics Ind Polyacetal
GB2357509B (en) * 1999-12-23 2004-04-14 Hyundai Electronics Ind Organic anti-reflective coating polymer and preparation thereof

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