CN1163279A - Preparation for non-soluble polymer - Google Patents

Preparation for non-soluble polymer Download PDF

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CN1163279A
CN1163279A CN 97102105 CN97102105A CN1163279A CN 1163279 A CN1163279 A CN 1163279A CN 97102105 CN97102105 CN 97102105 CN 97102105 A CN97102105 A CN 97102105A CN 1163279 A CN1163279 A CN 1163279A
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weight
acid
polymkeric substance
monomer
gel formation
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C·谢德
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BASF SE
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BASF SE
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Abstract

The invention relates to a method for preparing non-water insoluble polymer by polymerization of alkylene unsaturated monomer, wherein polymerization is carried on in hydrogel whose viscosity is at least 800 mPa.s, and average molecular weight of gelatine formation is more than 20,000. Obtained dispersion has long storage life and the polymer can easily deposit.

Description

The preparation of non-soluble polymer
The present invention relates to prepare the method for non-soluble polymer with the radical polymerization of alkylene unsaturated monomer.
Aqueous polymeric dispersions or non-soluble polymer are used now very widely.They are usually with free radical emulsion or suspension polymerization.Carry out the necessary dispersion agent that adds as protective colloid or emulsifying agent and so on smoothly for making polymerization.These dispersion agents influence the interface of monomers/water and polymkeric substance/water; determine final coating of particles and size in certain limit; with by around polymer beads, forming the gelling that protective layer prevents polymkeric substance, this protective layer prevents that particle is close to mutually and can take place in the agglomerative distance.
But according to predetermined purposes, dispersion agent remains in the polymeric dispersions, therefore also causes sizable shortcoming.They are to the surface property of the film of polymer formation and cohesiveness produces negatively influencing and it is more difficult that polymkeric substance is isolated from dispersion.Do a large amount of trials and utilized the less dispersion agent of shortcoming.Be intended to avoid using low-molecular-weight emulsifying agent especially.
US-A-4,151,143 have described the polymkeric substance with the emulsifier-free of two stage emulsion polymerization prepared.Fs prepares common carboxylic polymkeric substance with solution or block polymerization.Polymkeric substance is by with organic amine or alkali neutralization partially or completely then, or utilizes strong shearing action and be dispersed in the water.In subordinate phase, some are water miscible and some are that non-water-soluble monomeric mixture adds in the dispersion with initiator.After initiation, in dispersion, produced monomeric polymerization, its mode is to produce grafting and form a kind of stable emulsion that does not have emulsifying agent.
EP-A-597567 has described the sphere that obtains by letex polymerization or the big polymer beads of round bar shape.Having under the situation of stabiliser system, at least a alkylene unsaturated monomer of polymerization carries out letex polymerization.Stabiliser system is a kind of stablizer of polymeric amphiphilic, and it comprises hydrophobic and hydrophilic segment.Polymer stabilizer usefulness monomer such as vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE, methacrylic acid N, N dimethylamine base ethyl ester, vinylformic acid N, N dimethylamine base ethyl ester etc. is prepared.The molecular weight of polymer stabilizer from 1000 to 1500 should point out that the high-molecular weight stablizer is disadvantageous, because they cause too high viscosity and no longer fully are dissolved in the water during neutralizing.But, have been found that the method for avoiding adding emulsifying agent of being advised so far in the prior art is unsatisfied, especially the storage life of final polymeric dispersions and polymkeric substance be easy to isolating aspect.
The purpose of this invention is to provide and a kind ofly prepare the method for non-soluble polymer by free-radical emulsion polymerization, this method can not add emulsifying agent carries out, and makes polymeric dispersions that long storage life be arranged.In addition, the polymkeric substance that obtains should be segregative.
The discovery that we are taken aback is carried out polymerization at the hydrogel of thickening in mutually and just can be realized purpose of the present invention.
Therefore, the present invention relates to prepare the method for non-soluble polymer with radical polymerization, the letex polymerization by the alkylene unsaturated monomer more specifically, wherein polyreaction is carried out in mutually at a kind of hydrogel that viscosity is at least 800mPa.s, the molecular-weight average of gel formation thing is greater than 20,000.
The invention still further relates to the polymeric dispersions that obtains with present method.
Gel phase
The gel formation thing can be natural or the synthetic polymkeric substance.Preferred natural gel formation thing is alginate, pectin, guar gum, carragenates, Mierocrystalline cellulose and derivatived cellulose, as carboxymethyl cellulose and Natvosol, starch and starch derivative such as Sumstar 190 carboxymethyl starch and hydroxyethylamyle.
But preferably use the polymkeric substance of synthetic band carboxyl.These polymkeric substance or multipolymer obtain by radical polymerization, and preferably comprise: a) monomer of at least a band carboxyl, b) if desired, at least a (methyl) vinylformic acid C 1-C 30-alkyl ester, c) if desired, at least a linking agent, d) if desired, at least another kind of monoene unsaturated monomer, and e) if desired, at least a monoene unsaturated monomer, this monomer 25 ℃ down with the water miscibility at least 1% weight with have at least one 12 carbon or the more alkyl group of carbon atom.
Monomer is C preferably a) 3-C 8The monoene unsaturated aliphatic carboxylic acid, the mixture of their acid anhydrides or carboxylic acid and acid anhydrides.The example of suitable carboxylic acid is vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE, methylene-succinic acid and butenoic acid.The example of suitable acid anhydrides is methacrylic anhydride and MALEIC ANHYDRIDE.Preferred monomer is vinylformic acid, methacrylic acid, maleic acid and/or MALEIC ANHYDRIDE a).
Monomer a) is present in amount in the polymkeric substance that forms gel normally based on from 20 to 100% weight of total polymer weight, preferably from 35 to 99.95% weight, particularly preferably from 85 to 99.95% weight.If monomer is a MALEIC ANHYDRIDE a), preferred amount from 50 to 65% weight.
Monomer a) can be with free acid, acid anhydride or salt binding in the polymkeric substance that forms gel.
Monomer b) be acrylic or methacrylic acid and saturated, linearity or side chain C 1-C 30The ester of alcohol.The example of ester is methyl, ethyl, n-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base, n-docosane base, n-tetracosane base, 2-ethylhexyl or the cyclohexyl ester of acrylic or methacrylic acid.Above-mentioned monomeric mixture also can be used.
Preferably use the C of acrylic or methacrylic acid 1, C 2, C 3And/or C 12-C 22Alkyl ester.
Monomer c) amount in the polymkeric substance that forms gel is from 0.1% to 80% weight.Acrylic or methacrylic acid C 12-C 22It is 0.1% to 10% that alkyl ester is preferably measured, and particularly preferably is 0.5 to 5% weight.The C of acrylic or methacrylic acid 1, C 2Or the amount of C4-alkyl ester is preferably 30 to 65% weight.
Linking agent c) in molecule, contains two monoene unsaturated double-bonds at least.
Such suitable crosslinking agent is for example to be acrylate, methacrylic ester, allyl ethers or the vinyl ethers of dibasic alcohol at least.In the original alcohol some or all OH groups can etherificate or esterification, but linking agent contains at least two alkylene unsaturated groups.The example of original alcohol is a dibasic alcohol, as 1,1, the 2-propylene glycol, 1, ammediol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 2, the 3-butyleneglycol, 1, the 4-butyleneglycol, but-2-ene-1, the 4-glycol, 1, the 2-pentanediol, 1, the 5-pentanediol, 1, the 2-hexylene glycol, 1, the 6-hexylene glycol, decamethylene-glycol, 1, the 2-lauryl alcohol, 1, the 12-lauryl alcohol, neopentyl glycol, 3-methylpentane-1, the 5-glycol, 2,5-dimethyl-1, the 3-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol, 1, the 2-cyclohexanediol, 1,4 cyclohexanediols, 1,4-two (methylol) hexanaphthene, the single DOPCP of hydroxy new pentane acid, 2,2-two (4-hydroxyphenyl) propane, 2,2-two [4-(2-hydroxypropyl) phenyl] propane, 2,2 two [4-(2 hydroxyls-propyl group) phenyl] propane, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, three four propylene glycol that contract, 3-sulfo-pentane-1,5 two pure and mild polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran, every kind molecular weight from 200 to 10,000.Except the homopolymer of oxyethane or propylene oxide, the also multipolymer of the segmented copolymer of epoxy available ethane or propylene oxide or coupling collar oxidative ethane or propylene oxide group.The example that has more than the original alcohol of two oh groups is trihydroxymethyl propane, glycerol, tetramethylolmethane, 1,2,5-penta triol, 1,2, and 6-hexanetriol, trihydroxyethyl tricyanic acid, sorbitan and sugar are as sucrose, glucose, seminose.With oxyethane or propylene oxide reaction after polyvalent alcohol also can be used as corresponding ethoxylate and propoxylated glycerine.
Suitable crosslinking agent is vinyl ester or monohydroxy unsaturated alcohol and the unsaturated C of alkylene in addition 3-C 6The ester of carboxylic acid reaction gained, carboxylic acid be vinylformic acid, methacrylic acid, methylene-succinic acid, maleic acid or FUMARIC ACID TECH GRADE for example.The example of this class alcohol is allyl alcohol, 1-butylene-3-alcohol, 5-hexen-1-ol, 1-octen-1-ol, 9-decylene-1 alcohol, dicyclopentenyl alcohol, 10-hendecene-1-alcohol, styryl carbinol, geraniol, crotyl alcohol, suitable-the 9-octadecene-1-ol.Yet, the monohydroxy unsaturated alcohol also can with polycarboxylic acid, for example propanedioic acid, tartrate, trimellitic acid, phthalic acid, terephthalic acid, citric acid or Succinic Acid esterification.
Other suitable crosslinking agent is a unsaturated carboxylic acid, for example the ester of oleic acid, Ba Dousuan, styracin or 10-undeeanoic acid and above-mentioned polyvalent alcohol.
In addition, (this pair key in aliphatic hydrocarbon not by conjugated), the straight or branched, linearity or ring-type, fat or the aromatic hydrocarbon that have two two keys at least, for example Vinylstyrene, divinyl toluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-tetrahydrobenzene, trivinyl hexanaphthene or molecular weight 200-20,000 polyhutadiene also is suitable.Other suitable crosslinking agent are acrylamide or the Methacrylamides that have diamine functional group at least.These amine are for example 1,2-diamino methane, 1,1,3-diaminopropanes, 1,4-diaminobutane, 1,1,12-two decane diamines, piperazine, diethylenetriamine and isophorone diamine.Allyl amine and unsaturated carboxylic acid such as vinylformic acid, methacrylic acid, methylene-succinic acid, maleic acid.Or the acid amides of above-mentioned di-carboxylic acid at least also is fit to.
Urea derivatives, the N-vinyl compound of acid amides, cyanurate or the urethanum of bifunctional at least, for example the N-vinyl compound of urea, ethylidene-urea, propylidene urea or tartrate acid amides also is fit to.
Other suitable crosslinking agent is divinyl Er Yang oxane, diallyl phosphoric acid ester, triallyl phosphoric acid ester, triallyl triazene triketone, diallyl amine, triallylamine, tetraallyl silane, tetrem thiazolinyl silane, six allyl group trimethylene sulfones, divinyl and isoprene.
Most preferred linking agent is C 2-C 6(methyl) acrylate of glycol, polyvalent alcohol be the allyl ethers of TriMethylolPropane(TMP), five tetrahydroxybutanes, sucrose or Sorbitol Powder (having in molecule more than an allyl ethers functional group), unsaturated C for example 3-C 22Methacrylic ester, trivinyl hexanaphthene and/or the non-conjugated C of alcohol 6-C 14Alkyl diene and divinyl glycol.The consumption of linking agent is 0.05 to 10, preferably from 0.05 to 5, and most preferably be from 0.1 to 3% weight.
Monoene unsaturated monomer (d) is following compounds preferably:
A) the N-vinyl compound of following molecular formula is arranged: R in the formula 1Be hydrogen or C 1-C 12Alkyl and m are 1,2 or 3.
The example of these compounds is N-vinyl pyrrolidone and N-caprolactam.
B) available C 1-C 12The N-vinyl imidazole that-alkyl replaces and the 1-vinyl-3-alkyl imidazole salt of 1-30 carbon atom is arranged in alkyl chain.
C) compound that following molecular formula arranged with and quaternary ammonium salt:
R in the formula 2Be H or CH 3,R 3Be OR 4NR 5R 6, NHR 4NR 5R 6Or NR 5R 6, R 4Be C 2-C 12Alkylidene group and R 5Or R 6Can be identical or different, be hydrogen or C 1-C 12Alkyl.
These examples for compounds are (methyl) acryloyl diethyllaminoethyl amine, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) acryloyl dimethylaminoethyl amine, (methyl) dimethylaminoethyl acrylate, acrylamide, Methacrylamide, N,N-DMAA, N-tertiary butyl acrylamide, the special octyl acrylamide of N-, N-dodecyl acrylamide and N-methyl undecyl acrylamide;
D) saturated C 1-C 30Vinyl carboxylates is as vinyl-acetic ester, propionate, new n-nonanoic acid vinyl acetate, vinyl neodecanoate or vinyl laurate;
E) hydroxyalkyl list (methyl) acrylate, wherein alkylidene group is that 2 to 6 carbon atoms are arranged.As hydroxyethyl monomethacrylates and mono acrylic ester;
F) C that had reacted with the 2-50 ethylene oxide unit 1-C 22(methyl) acrylate of alcohol;
G) C 1-C 22Alkyl vinyl ether is as vinyl methyl ether or EVE;
H) acrylamido propane sulfonic acid, styrene sulfonic acid, methacrylic acid sulfo group-ethyl ester or their salt.
I) C of terminal double bond is arranged 4-C 30-alkene;
Mixture with vinylbenzene, vinyl cyanide, methyl vinyl ketone, vinylchlorid, 1,2-dichloroethene or above-mentioned monomeric any requirement.
Preferably acrylamide, N-vinyl pyrrolidone, vinyl acetate, methoxy ethylene, ethyl vinyl ether, iso-butylene, diisobutylene, C 12-C 22Alkene, as 1-octadecylene, 1-hexadecylene and 1-laurylene.The particularly preferred monomer d that contains) be acrylamide, N-vinyl pyrrole ketone and vinyl methyl ether.
Monomer d) consumption can be high to 70%, is preferably height to 10%, is preferably high to 5% weight especially.The amount that methoxy ethylene, ethyl vinyl ether, iso-butylene or diisobutylene especially preferably exist is from 25 to 50% weight.The amount that acrylamide and N-vinyl pyrrolidone preferably exist is 15 to 60% weight.
The unsaturated monomer e of monoeneization) compound of following molecular formula preferably: R in the formula 7Be H or CH 3,
X is-O-,-COO-,-CONH-or-CH 2-,
R 8Be C 12-C 30Alkyl,
N be 1 to 100 and
The 0th, 0-100.
Particularly preferably be the monomer of above-mentioned molecular formula, in the formula
R 7Be H or CH 3,
X is-O-,-COO-,-CONH-or-CH 2-,
R 8Be C 12-C 22Alkyl,
N be 1 to 100 and
O is 0.
Other suitable monomers (e) is described among EP-A-296436, US-A-4514552, US-A-4916183, US-A-5013787, EP-A-335624, EP-A-413953, EP-A-446621, US-A-4421902, EP-A-192724, EP-A-216479, EP-A-170025 and the EP-A-172723 at EP-A-632-063.The content of these publications is incorporated conduct here into reference to data.
The consumption of monomer (e) in forming the polymkeric substance of gel preferably 0.1 to 25 is 0.5 to 15 more preferably, particularly preferably is 2 to 10% weight.
According to a following preferred embodiment, the polymkeric substance that forms gel preferably has following ingredients.Said in each case amount is a weight percent:
The monomer of (1) 20% to 80% at least a band carboxyl (a);
20% to 80% at least a monomer (b);
0% linking agent;
0 to 30% at least a monomer (d); With
0.1 to 15% at least a monomer (e).
(2) 30 to 100% at least a monomer (a);
0 to 20% at least a monomer (b);
0 to 10% at least a linking agent;
0 to 70% at least a monomer (d); With
0% monomer (e).(3) 20 to 80% vinylformic acid, methacrylic acid, methylene-succinic acid and/or maleic acid; 20 to 30% (methyl) vinylformic acid C 1-C 8The alkane ester; 0 to 10% at least a linking agent; 0 to 30% at least a monomer (b) and; 0.1 monomer to 15% a kind of following molecular formula:
Figure A9710210500131
In the formula
R 7Be H or CH 3
X is-O-,-COO-or-CH 2-;
R 8Be C 12-C 22Alkyl; With
N is 1 to 100.
(4) 80% to 99% vinylformic acid, methacrylic acid and/or MALEIC ANHYDRIDE;
0.05 to 10% at least a (methyl) vinylformic acid C 8-C 22Alkyl ester;
0.05 to 5% at least a linking agent; With
0 to 10% at least a other monomer (d).
(5) 90 to 99.4% vinylformic acid, methacrylic acid and/or MALEIC ANHYDRIDE;
0.5 to 5% at least a (methyl) vinylformic acid C 8-C 22Alkyl ester;
0.1 to 5% at least a linking agent; With
0 to 5% at least a monomer (b).
(6) 95 to 99.95% vinylformic acid, methacrylic acid and/or MALEIC ANHYDRIDE and
0.05 to 5% at least a linking agent.
(7) 40 to 65 MALEIC ANHYDRIDE;
35 to 60% at least a C 1-C 22Alkyl vinyl ether and/or a kind of C 6-C 30Alkane-1-alkene and/or iso-butylene;
0 to 5% at least a linking agent and
0 to 10% at least a monomer (d).
(8) 40 to 85% (methyl) vinylformic acid;
15 to 60% at least a N-vinyl lactam and/or a kind of acrylamides;
0 to 5% at least a linking agent; With
0 to 10% other monomer (d).
Usually the molecular weight of gel formation thing is preferably more than 50,000 greater than 20,000, particularly preferably is greater than 100,000.
The polymkeric substance that forms gel can prepare by enough different methods, as precipitation polymerization, solution polymerization, emulsion polymerization, inverted emulsion polymerization.They also can use the reaction similar to polymerization to obtain from other polymkeric substance.Polymkeric substance is preferably at organic solvent, solvent mixture or supercritical CO 2In with precipitation polymerization or in water with emulsion copolymerization or in the mixtures of liquids of Shui Heshui-immiscibility with inverted emulsion or suspension polymerization.
The polymkeric substance of the formation gel that is fit to is to obtain from commerce, as Carbopol  Synthalen , Stabylen , Aqupec , Stabyleze , Hivis , Pemulen , Lutexal , Sterocoll , Latecoll , Rohagit , Sanwet , Salcare , Antil  or Acrysol .The alkylene unsaturated monomer
Treat that in gel phase polymeric alkylene unsaturated monomer is that those are used in the monomer in emulsion and the suspension polymerization usually.Therefore they are water-fast monomer substantially.They can utilize separately or mix use with other monomer.The major portion of mixture comprises non-basically water-soluble monomer.More a spot of non-water-soluble comonomer also can exist.
Suitable water-insolube substantially monomer is the unsaturated monomer of monoeneization specifically, as alkene such as ethene, vinyl aromatic monomer such as vinylbenzene, alpha-methyl styrene, chloro styrene or Vinyl toluene, the ester such as the vinyl acetate of the mono carboxylic acid of vinyl alcohol and 1 to 22 carbon atom, propionate, vinyl propionate, vinyl laurate, stearic acid vinyl ester, α, the unsaturated list of the 3-6 of a β monoeneization carbon atom and two carboxylic acid, as vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE and methylene-succinic acid and common 1 to 30, preferred 1-18, the ester of the alkane chain alcohol of 1-12 carbon atom especially, it is the methyl of vinylformic acid and methacrylic acid, ethyl, normal-butyl, isobutyl-, with the 2-(ethyl hexyl) ester, the maleic acid dimethyl esters, or maleic acid di-n-butyl ester, α, the nitrile compound of the unsaturated carboxylic acid of β monoeneization such as vinyl cyanide, C 4-C 8The chlorination of conjugated diolefine such as 1,3-butadiene, 1 to 6 carbon atom or fluorizated alkane alkene chain be vinylchlorid or 1,2-dichloroethene and N-C for example 4-C 30Alkyl (methyl) acrylic acid amides such as N-normal-butyl acrylamide etc.
Water-soluble comonomer is α particularly, the unsaturated carboxylic acid of the 3-6 of a β monoeneization carbon atom such as vinylformic acid, methacrylic acid, butenoic acid or maleic acid, (methyl) acrylic acid hydroxy alkyl ester are as (methyl) hydroxyethyl acrylate, and (methyl) vinylformic acid dialkylamino alkyl ester is as (methyl) vinylformic acid diformazan aminoethyl ester, vinyl pyrrolidone, caprolactam, vinyl imidazole etc.
If desired, linking agent also can utilize, suitable crosslinking agent such as above-mentioned.Carry out polymerization
By utilizing hydrogel that above-mentioned gel formation thing forms to carry out polymerization in mutually.Process is preferably at least 1000 there being viscosity to be at least 800, more preferably is at least 1500, particularly preferably carries out for the gel phase at 2000mPa.s (25 ℃ measure with the manual viscometer of Haake VT-02) at least.In most of the cases, viscosity is at least 5000, even at least 10,000 or 25,000mPa.s can use.
The common consumption of gel formation thing is 0.05 to 10, is preferably 0.1 to 5, particularly preferably is 0.1 to 2% weight, and it is basic calculation and based on the water gross weight that this weight percent forms thing with nonionic hydrogel.
Usually the gel formation thing exists in the form of water with salt, and the form of salt can exist, and also can add alkali to water and produce.Add to water the suitable alkali that is used to form salt that adds before or after the gel formation thing be for example mineral alkali such as lithium hydroxide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonium, pyridine compounds, amidine compound, organic amine, as monoethanolamine, diethanolamine, trolamine, dimethylethanolamine, methyldiethanolamine, triethylamine, 2-amino-2-methyl-1-propanol etc.
Gel phase also can contain other conventional additives, as emulsifying agent, colloid protective agent, suds-stabilizing agent, anti-aging agent, organic solvent or inorganic solvent.But preferably gel phase does not contain emulsifying agent or colloid protective agent.
Polyreaction is undertaken by the free radical method and is caused by initiator with usual way, and these initiators can cause free radical aqueous polymerization, particularly letex polymerization.These initiators can be superoxide, as alkali-metal peroxidation dithionate or ozonide.Suitable in addition is redox initiator, just comprise for example t-butyl hydrogen peroxide of a kind of superoxide and/or hydrogen peroxide at least, the associating system of hydroxyl methyl-sulfinic acid sodium salt or hydrogen peroxide and xitix, preferred system is the metallic compound in the polymeric media of can being dissolved in that also contains in a small amount, multiple valence state can take place in the metal component of this metallic compound, xitix/ferric sulfate (II) salt/hydrogen peroxide just, hydroxyl methyl-sulfinic acid sodium salt, S-WAT, sodium bisulfite, or sodium sulfite also can be used to replace xitix, t-butyl hydrogen peroxide or alkali-metal peroxide dithionate and/or peroxidation two ammonium sulfate replacement hydrogen peroxide.Light-initiated also is suitable.In addition, also available ionizing radiation of polymerization and electrochemical initiation.The amount of initiator is generally 0.1 to 5% weight, is base with the gross weight of wanting the polymeric polymkeric substance.
If desired, the molecular weight of polymkeric substance can reduce to the usual way in the polyblend by adding conditioning agent.Suitable adjusting base for example is a mercaptan.
Polyreaction is carried out in rare gas element usually.For example can be by at first the whole components that exist between polymerization period being added in the aggregation container, initiation reaction, if desired, reaction mixture is so that the temperature of controlled polymerization reaction.In the possible program of another kind, the part of single component or component is only put in beginning, initiated polymerization, the resistates of component separately or together, continuously or by stages, if needs are arranged, also will be with different interval metering supplies.Also monomer available and polymerization starter are separately supplied with, segmentation or introduce program in the polymer container continuously.Different monomers and monomer mixture also can join in the reaction mixture continuously.
Temperature during the polyreaction is generally 40 to 160 ℃, is preferably 50 to 120 ℃.It during reaction can change.Polyreaction is preferably under atmospheric pressure carried out, but also can carry out under low pressure and superpressure.If the temperature of polyreaction is higher than the boiling point of component, polyreaction is carried out in the pressure vessel of height to 20 crust.
The particulate size of formed polymkeric substance is generally 50nm to 20 μ m.Some particles are very breakable loose connection things.But thin part accounts in a large number usually.
The operating method that can be by design and used agitating unit and the additive of adding and impact polymer particulate size.When utilizing stirring commonly used and mixed system, particle size is usually in above-mentioned scope.
After polymerization process, polymkeric substance is subjected to the aftertreatment of physics and chemistry, particularly removes volatiles such as remaining monomer.These class methods such as steam distillation, with steam and/or nitrogen remove, concentrate, oxide treatment or add polymerization starter.
The polymer dispersed physical efficiency of gained is utilized after this manner.Found that they have very long storage life.
Resulting polymkeric substance also can be by separating as spraying drying and drum-type are dry.A special advantage is that polymkeric substance can be precipitated out from dispersion with the simple mode that reduces viscosity.Also can cause precipitation with adding small amount of electrolyte or water miscibles organic solvent or dilute with water.Separate selected polymkeric substance then, in case of necessity, carry out drying and other processing.To the inorganic salt of precipitation suitable electrolyte such as sodium potassium, preferably sodium-chlor and sodium sulfate.Magnesium salts or calcium salt such as sal epsom or calcium formiate also are fit to.The miscible organic solvent of suitable water is C preferably 1-C 4Alcohol, glycol, water miscible carboxylic acid and acetone.
Dispersion according to resulting polymkeric substance of the present invention and polymkeric substance has use widely.Can be used as tackiness agent as them, as the auxiliary agent (adding in the cement) of building industry, as top coat or the material of binding agent as making the coating leather goods, as the impact activator in engineering polymers, or as the auxiliary agent of paper.
Following embodiment for example understands the present invention rather than to its restriction.Be the polymkeric substance of used formation gel below:
Polymkeric substance 1: vinylformic acid (＞95%), the multipolymer of methacrylic acid octadecane ester and pentaerythritol triallyl ether.It is sold with trade names Pemulen TR1  by B.F.Goodrich company.
Polymkeric substance 2: vinylformic acid (＞94%), the multipolymer of methacrylic acid octadecane ester and pentaerythritol triallyl ether.It is sold with trade names Pemulen TR2  by B.F.Goodrich company.
Polymkeric substance 3: crosslinked a little polyacrylic acid, it is sold with trade names Carbopol  940 by B.F.Goodrich company.
Polymkeric substance 4: the multipolymer of the methacrylic ester that ethyl propenoate, methacrylic acid and stearyl alcohol and 25 ethylene oxide unit(s)s reacted, weight ratio is 55/40/5, the k value is 95 (0.1% concentration is in THF).
Polymkeric substance 5: crosslinked a little polyacrylic acid sodium salt, sell with trade names Lutexal  P by BASF AG company.
Polymkeric substance 6: MALEIC ANHYDRIDE and methylvinylether (weight ratio about 60/40) and 1, the tripolymer of 9-decadiene is sold with trade names Stabileze 06 by ISP company.
Viscosity is down with Haake VT 02 manual viscometer determining at 25 ℃.Embodiment 1
By 600ml water, 1.8g polymkeric substance 1 and 0.8g sodium hydroxide form gel in the 2l agitator.Aqueous viscosity is 3200mPa.s.After adding the 0.3g Sodium persulfate, mixture is heated to 80 ℃ under nitrogen atmosphere, and stirs the mixture with 200 rev/mins with anchor type agitator.Under this temperature, 142.5g ethyl propenoate and 7.5g methacrylic acid mix more than 3 hours.Mixture kept under this temperature 3 hours again.Obtain a kind of polymeric dispersions that the white of solids content 19.5% is arranged.The viscosity of dispersion is 7Pa.s.Even after 9 months, the phenomenon that also is not separated.After the solution of 0.5gNaCl in 50ml water was joined the 50ml dispersion, the latter was condensed into thin flocks and is easy to separate.
After being stirred in the 10ml dispersion in the 100ml water, polymkeric substance precipitates lentamente with trickle dispersive throw out.Embodiment 2
Replace polymkeric substance 1 to carry out identical reaction with 1.8g polymkeric substance 2.The viscosity of water is 1400mPa.s.Obtaining viscosity is the white dispersion that 7Pa.s has solids content 19.7%.Even the tendency that is not separated after 9 months.Embodiment 3
Replace polymkeric substance 1 to carry out identical reaction with 1.8g polymkeric substance 3. the viscosity of water is 13,000mPa..s.Obtaining viscosity is the white dispersion that 1.7Pa.s has solids content 19.9%.Even the tendency that is not separated after 9 months.Embodiment 4
Replace polymkeric substance 1 to carry out identical reaction with 4g polymkeric substance 4.The viscosity of water is 1.700mPa.s.Obtaining viscosity is the white dispersion that 1.7Pa.s has solids content 19.6%.Even the tendency that is not separated after 9 months.
After joining 10ml ethanol in the 50ml dispersion, polymkeric substance precipitates slowly with the form of fine particle.Embodiment 5
Replace polymkeric substance 1 to carry out identical reaction with 3g polymkeric substance 5.The viscosity of water is 11, and 000mPa.s does not add other alkali (NaOH).Obtained solids content 19.6%, viscosity is the white dispersion of 1.7Pa.s.Even the tendency that is not separated after 9 months..Embodiment 6
Replace polymkeric substance 1 to carry out identical reaction with 1.8g polymkeric substance 6.The viscosity of water is 17,000mPa.s.Obtained solids content 20.1%, viscosity is the white dispersion of 8Pa.s.Even the tendency that is not separated after long-term the placement.Embodiment 7
Replace embodiment 1 used monomer to carry out identical reaction with the 150g ethyl propenoate.Obtained solids content 20.3%, viscosity is the white dispersion of 9.5Pa.s.Even the tendency that is separated arranged after 9 months.Embodiment 8
Carry out identical reaction with used monomer among the 150g methyl methacrylate replacement embodiment 1.Obtained solids content 21.0%, viscosity is the white dispersion of 25Pa.s.Even the tendency that is not separated after 9 months.Embodiment 9
Carry out identical reaction with used monomer among the 150g vinylbenzene replacement embodiment 1.Monomer was added in the reaction mixture in 6 hours.Obtained solids content 19.8%, viscosity is the white dispersion of 6pa.s.Embodiment 10
Replace used monomer among the embodiment 1 with the positive n-butyl acrylate of 150g, carry out identical reaction.Obtained solids content 20.2%, viscosity is the stable white dispersion of 4Pa.s.

Claims (18)

1. the unsaturated monomer by alkylene prepares the method for non-water-soluble polymkeric substance with radical polymerization, and wherein polyreaction is carried out in viscosity is at least the hydrogel of 800mPa.s, and the molecular-weight average of gel formation thing is greater than 20,000.
2. according to the process of claim 1 wherein that used gel formation thing is a kind of polymkeric substance of synthetic band carboxyl.
3. according to the method for claim 2, wherein used gel formation thing is a kind of polymkeric substance with carboxyl, and it comprises from the unsaturated fatty C of monoeneization 3To C 8The unit of selecting in the group that the mixture of carboxylic acid and their acid anhydride and carboxylic acid and acid anhydride is formed.
4. according to the method for claim 3, wherein used gel formation thing be a kind of polymkeric substance with carboxyl it comprise the unit of selecting from vinylformic acid, methacrylic acid, maleic acid, FUMARIC ACID TECH GRADE, methylene-succinic acid, butenoic acid, methacrylic anhydride and MALEIC ANHYDRIDE.
5. according to each the method in the claim 2 to 4, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) monomer of at least a band carboxyl of 20 to 100% weight;
B) at least a (methyl) vinylformic acid C of 0 to 80% weight 1-C 30Alkyl ester;
C) at least a linking agent of 0 to 10% weight;
D) at least a other the undersaturated monomer of monoeneization of 0 to 70% weight;
E) at least a monoene unsaturated monomer of 0 to 25% weight, this monomer has the water miscibility of 1% weight at least under 25 ℃, the alkyl of at least one 12 or more carbon atom.
6. according to the method for claim 5, wherein the polymkeric substance with carboxyl comprises following ingredients:
A) monomer of at least a band carboxyl of 20 to 80% weight;
B) at least a (methyl) vinylformic acid C of 20-80% weight 1-C 30The alkane ester;
C) at least a linking agent of 0-1% weight;
D) at least a other the unsaturated monomer of monoeneization of 0-30% weight;
E) at least a monoene unsaturated monomer of 0.5-15% weight, this monomer have the alkyl of the water-soluble of 1% weight and at least one 12 or more carbon atom at least under 25 ℃.
7. according to the method for claim 6, wherein have the compound of following molecular formula to be used as monoene unsaturated monomer (e): In the formula: R 7Be H or CH 3, X is-O-,-COO-,-CONH-or CH 2-, R 8Be C 12-C 22Alkyl, n are 1 to 100.
8. according to the method for claim 5, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) monomer of at least a band carboxyl of 30 to 100% weight;
B) at least a (methyl) vinylformic acid C of 0 to 20% weight 1-C 30Alkyl ester;
C) at least a linking agent of 0-10% weight;
D) at least a other the unsaturated monomer of monoeneization of 0-70% weight;
9. according to the method for claim 8, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) vinylformic acid of 80 to 99.9% weight, methacrylic acid.MALEIC ANHYDRIDE;
B) at least a (methyl) vinylformic acid C of 0.05 to 10% weight 8-C 22The alkane ester;
C) at least a linking agent of 0.05-5% weight;
D) unsaturated monomer of at least a other monoeneization of 0-10% weight.
10. according to the method for claim 9, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) vinylformic acid of 90 to 99.4% weight, methacrylic acid, MALEIC ANHYDRIDE;
B) a kind of (methyl) vinylformic acid C of 0.5 to 5% weight 8-C 22-alkane ester;
C) at least a linking agent of 0.1-5% weight;
D) at least a other the unsaturated monomer of monoeneization of 0-5% weight.
11. according to the method for claim 5, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) vinylformic acid of 95 to 99.95% weight, methacrylic acid or MALEIC ANHYDRIDE; With
B) at least a linking agent of 0.05 to 5% weight;
12. according to the method for claim 5, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) MALEIC ANHYDRIDE of 40 to 65% weight;
B) at least a C of 35 to 60% weight 1-C 22-alkyl vinyl ether or C 6-C 30-alkane-1-alkene or iso-butylene;
C) at least a linking agent of 0 to 5% weight;
D) at least a other the unsaturated monomer of monoeneization of 0-10% weight.
13. according to the method for claim 5, wherein used gel formation thing is the polymkeric substance of band carboxyl, comprises following ingredients:
A) (methyl) vinylformic acid of 40 to 85% weight;
B) at least a N-vinyl lactam or the acrylamide of 15 to 60% weight;
C) at least a linking agent of 0-5% weight;
D) at least a other the unsaturated monomer of monoeneization of 0-10% weight.
14. according to each method in the claim 1 to 13, wherein use the polymkeric substance of band carboxyl, some of them or whole carboxyls occur with the carboxylate group.
15. each method in requiring according to aforesaid right, the consumption of wherein used gel formation thing is 0.05 to 10, preferably 0.1 to 5%, and particularly preferred is 0.1 to 2% weight, this weight percent is based on the gross weight of gel phase.
16. each method in requiring according to aforesaid right, wherein the viscosity of gel phase is 1500 at least, preferably at least at 1000mPa.s
17. each method in requiring according to aforesaid right, wherein the polymkeric substance of gained is by adding entry or water-miscible solvent or a kind of ionogen precipitates.
18. one kind with each the available polymeric dispersions of method in requiring according to aforesaid right.
CN 97102105 1996-01-08 1997-01-07 Preparation for non-soluble polymer Pending CN1163279A (en)

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DEP19600405.5 1996-01-08
CN 97102105 CN1163279A (en) 1996-01-08 1997-01-07 Preparation for non-soluble polymer

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012483A (en) * 2018-06-05 2018-12-18 中化化工科学技术研究总院有限公司 A kind of macromolecule emulsifier and preparation method thereof
EP3781622B1 (en) * 2018-04-20 2022-10-12 Basf Se Adhesive compositions with a gelcontent from crosslinking of keto- or aldehyde groups

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3781622B1 (en) * 2018-04-20 2022-10-12 Basf Se Adhesive compositions with a gelcontent from crosslinking of keto- or aldehyde groups
CN109012483A (en) * 2018-06-05 2018-12-18 中化化工科学技术研究总院有限公司 A kind of macromolecule emulsifier and preparation method thereof

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