SU465011A3 - The method of obtaining organic dispersions of vinyl polymers - Google Patents

Description

one

A method of producing organic dispersions of vinyl polymers is known by polymerizing the respective mosomers in an organic liquid that does not dissolve the polymer under the influence of free radical polymerization initiators.

However, the resulting organic dispersions of polymers are very unstable and not suitable for use as coating compositions.

The proposed method involves carrying out a polymerization process in the presence of a small amount of a compound containing a solvated organic polymer group with mol. at. 5000 and unsaturated groups capable of copolymerizing with the starting monomer, allows to obtain a stable organic dispersion of vinyl polymers.

The term “vinyl monomer also includes monomers that do not have a vinyl structure in the direct sense, but polymerizing like those. These include, for example, vinylidene and ethylene monomers, which polymerize like vinyl-structured monomers, and double-unsaturated butadiene-type monomers.

The proposed stabilizer used in the preparation of a dispersion of a synthetic polymer in an organic liquid is made by graft-copolymerization of a vinyl monomer with a compound containing a polymer group with mol. at. 500 and the unsaturated group from which the monomer is polymerized by the vinyl method to form a vinyl chain with a mol. at. 5000, and a polarity different from the polarity of the original polymeric group.

If the original polymeric group of the compound is a group derived from the polymerization of a vinyl type, then the resulting stabilizer will contain two kinds of polymeric groups obtained from the polymerization of a vinyl type. However, as stated above, these types of polymer groups should have

different polarity, in order for one of them to be solvated by an organic liquid, while the other could not and would be compatible with a synthetic polymer that is insoluble in the organic liquid.

This difference in polarity is also necessary in cases where the original polymer group is not a vinyl type group, for example, if a natural polymer or a polycondensation product is taken.

A stable dispersion of synthetic polymers in an organic liquid can be obtained by precipitating a polymer in an organic liquid in the presence of the proposed stabilizer, one polymer group of which is solvated by the organic liquid and the other is not and is compatible with this polymer.

In order to obtain an insoluble polymer, it is preferable to carry out the polymerization of the vinyl type in an organic liquid in the presence of said stabilizer.

Good results are obtained if the dispersion is carried out by polymerizing the vinyl monomer in an organic liquid in the presence of a compound containing a solvated polymeric group of mol. at. 5000, and an unsaturated group, with most of the monomer polymerizing into a polymer that is insoluble in the organic liquid, and forming dispersed particles in it that are stabilized with a graft copolymer formed by copolymerizing a vinyl type of a smaller portion of the monomer with an unsaturated group of this compound.

In this case, the polymer group of the graft copolymer, which should be compatible with the dispersed polymer, is indeed a group of the same type, being formed from the same vinyl monomer.

A compound containing a solvating polymeric group and an unsaturated group, the composition of which can be considered as a "precursor of the stabilizer, is best made on the basis of a condensation reaction that binds the indicated constituent and group.

Suitable condensation reactions for combining an unsaturated group with a solvating polymer group, resulting in a stabilizer precursor, are reactions that produce an ester, ether, amide, urethane, and other compounds. Such condensation reactions take place between the reactive group on the solvating chain and the corresponding group attached to the unsaturated group.

It would be desirable, having a very small amount of etherifying or other reactive groups in the polymer solvating group, to attach unsaturated groups to each of them, obtaining, on average, at least one unsaturated group in each stabilizer precursor for each solvating group. However, usually the esterification or some other reaction of the compound proceeds slowly in the final stage and any attempt to hasten the end of such a reaction can lead to the wearing of a significant number of unsaturated double bonds. Therefore, an improved process of making new and more

common precursors of stabilizers, in which an excess of esterifying or some other reactive groups is introduced into the unsaturated solvating group, which may enter into a condensation reaction in such a way that the unsaturated groups are combined in proportion to give the desired stabilizer precursor containing

average at least one unsaturated group per molecule.

The corresponding excess of reactive groups will depend on the absolute concentration of reactive groups in the mixture, in which

a condensation reaction proceeds. Taking into account that one of the two additional reactive groups will be attached to the polymer solvating group with mol. at. 5000-50000 or more, it is clear that the concentration of the reactive group in this mixture should be very small, namely, the highest will be a few percent, and the smallest - 0.1% or less. In order for the required number of groups to react at a certain time, the excess reactive groups used must respectively be 10% for a molecular weight of the solvating group of 5000, 100% for a molecular weight of the solvating group of 50,000, and 600% for molecules The actual weight of the solvating group is 500,000. The figures given are given with a rough approximation. The amount of excess may vary depending on the intensity of the reaction and on the amount of time it is required to bring the reaction to a certain stage.

The best way to introduce an excess of the respective reactive groups into the solvating group is to make the solvating group by the vinyl polymerization method of the monomer containing this reactive group. For example, a homopolymer made from such a monomer will have a large excess of these groups. On the other hand, if reactive groups are introduced into the solvating group by copolymerization, in which a smaller part of the monomer containing the reactive group is used, the number of reactive groups in each polymeric solvating group can be controlled, following the value of this smaller part. A polycondensation method is proposed for

making a precursor of a stabilizer containing solvating and unsaturated groups. For example, polymerization of higher alkylene oxides can produce polyethers with esterifying

the final hydroxyl groups to which the unsaturated groups are attached by a condensation reaction.

A method is also proposed in which a precursor solvating group

The stabilizer is a natural polymeric material or a derivative of the latter. For example, cellulose, being a relatively polar material, is solvated by polar organic liquids and already contains hydroxyl groups that participate in the condensation reaction, by means of which unsaturated groups are attached to them. Rubber is a relatively incomplete material and is solvated by organic liquids of the same polarity. If the rubber is reacted with maleic anhydride, entering, for example, an acid anhydride group, the result will be groups that take part. Stage in the condensation reaction. The molecular weight of such natural polymeric materials can be reduced by the degradation process.

Stabilizers for the dispersion of synthetic polymers in organic liquids can also be made by condensing a polymer compound with a mol. at. 5000, and containing a group that helps to carry out this reaction, in the amount of more than one per molecule with a compound containing additional reactive and unsaturated groups. In this case, a stabilizer precursor is obtained containing at least one unsaturated group per molecule, and it is then copolymerized with a vinyl monomer to form a vinyl chain with a polarity different from that of the original polymeric compound.

It is preferable to have an anticoagulant containing no more than two such vinyl chains per molecule.

It will be easier to achieve positive results; if the copolymerization constants of the vinyl monomer and the unsaturated group are equal, the precursor of the stabilizer, which is approximately one, i.e. If these constants differ from unity and are, for example, 10, then the stabilizer precursor will be spent at an earlier stage and it will be desirable to add it during the copolymerization, or a stabilizer precursor containing a larger number, for example, 20 or more unsaturated groups per molecule in order to increase the copolymerization rate of the precursor of the stabilizer.

These constants are close to unity when the unsaturated groups of the precursor stabilizer and the vinyl monomer are of the same chemical type.

According to the proposed method, one or more vinyl chains will be copolymerized with the stabilizer precursor through the unsaturated group of the latter, and although these

the chains are insoluble and precipitate in the organic liquid of the dispersion, the solvated group acts as a stabilizer and keeps the precipitated chain or chains in suspension.

It is possible to obtain a stabilizer in an organic solvent in which it is completely dissolved, and then add it in this form to a non-solvent organic l-liquid, in which the main polymer dispersion should occur and in which the vinyl chains of the stabilizer will precipitate. If a preformed vinyl polymer compatible with vinyl stabilizer chains is also added in dissolved vmde and precipitated together with them in the flat phase of disnersion, then dispersed particles will be obtained in pedyjibtat containing not only previously prepared polyshlr, but also vinyl depochki attached to solvated groups. They stabilize not only the vinyl chains to which they are directly attached, but also the whole particle into which these chains belong.

The polymer to be stabilized can be obtained in a non-solvent continuous phase, i.e. in this case, dispersed organic liquid is formed during the polymerization of the main vinyl monomer dissolved in it in the presence of a stabilizer containing solvated groups into which the vinyl chains have already polymerized, joint with this vinyl monomer.

The latter method can be improved if a part of the main vinyl monomer is co-polymerized with the precursor of the stabilizer in order to obtain vinyl chains attached to the solvated chains.

groups, and the remaining part of the main vinyl monomer in this case is converted to a polymer, which is stabilized as dispersed particles by introducing a stabilizer into the last vinyl chains, the latter being attached to the stabilizing solvated groups.

The main vinyl monomer may be a mixture of several monomers. Use separate stabilizers or

precursors of stabilizers, it is possible to obtain stable dispersions of vinyl polymers consisting of very small particles, even in the case when the content of solvated groups does not exceed 17 ° by weight

dispersed polymer. Best results are obtained when the amount of solvated groups is 3-10% by weight of the dispersed polymer. The nature of the solvating group largely depends on the nature of the organic liquid in which the main vinyl polymer is formed. If the organic liquid must have a polarity different from that of the main vinyl

polymer, in order not to dissolve it,

then the solvating group must have the same polarity in order for the organic liquid to solvate it.

If the organic liquid is mainly an aliphatic hydrocarbon, then the following groups that can be solvated by this liquid should be used:

polymers of esters with a long chain of acrylic or methacrylic acids, i.e., stearyl, lauric, octyl 2-ethylhexyl and hexyl esters of acrylic or methacrylic acid, polymer vinyl esters, polymers of ethylene, propylene, butadiene and isoprene.

If the organic liquid is a mainly aromatic hydrocarbon, then similar groups and analogs with a shorter chain are used, for example, polymers of ethoxyethyl methacrylate, methyl methacrylate and ethyl acrylate or ethyl cellulose. In this case, the following other groups can be used:

aromatic polyesters, for example, alkyd resins modified with vegetable oils;

aromatic polyethers (commercial name Epicotus);

aromatic polycarbonates and polymers of styrene and vinyl toluene.

If the organic liquid is polar, for example ethyl or methyl alcohol, the following groups are used:

acrylic or methacrylic acid polymers;

carboxymethyl cellulose; polyethylene or polypropylene glycols;

hydroxylated polymers, for example polyvinyl;

ethylene glycol alcohol or polymers of ethylene glycol monomethacrylate.

On the other hand, the dispersed stabilizing polymer must not dissolve in the organic liquid, i.e. it must have the opposite sex. For example, methyl methacrylate polymer should be dispersed: in an aliphatic hydrocarbon, polyacrylonitrile polymer in an aromatic hydrocarbon, and polystyrene in a polar organic liquid. Using these stabilizers, it is possible to carry out a dispersion of polymers of acrylic and methacrylic acids, esters, nitrols and amides of these acids, vinyl alcohol and such derivatives as chloride, acetate, chloroacetate and stearate, vinylidene chloride, styrene, and such derivatives as vinyl toluene, α-methyl styrene and divinyl benzene, allyl alcohol, and esters such as acetate and adipate, butadiene, etc. The polymer may be the product of a mixture of monomers, for example methyl methacrylate with a smaller portion of methacrylic acid.

It was established that the dispersed polymer should not swell significantly due to the organic liquid and that three main systems can be distinguished:

5 1) the polymer is insoluble, as it is polar with respect to the organic liquid;

2) the polymer is insoluble, since it is incomplete with respect to the organic liquid;

3) the polymer is insoluble in all ordinary or- ganic liquids because of its molecular structure and because of its polarity different from that of the organic liquid.

Typical systems for the first case are systems in which organic 15 liquid is incomplete. Most liquids of this type are aliphatic hydrocarbons, such as white spirit and isooctane. Somewhat more polar organic liquids, such as aromatic hydrocarbons, fatty esters, and ketones, are used for highly polar polymers. The organic liquid can be a mixture of several liquids, provided that the polarity of the mixture should be relative to the polarity of the polymer.

Polymers having suitable polarity for use in systems of the first type include esters of unsaturated acids with lower alcohols, for example, esters of acrylic, methacrylic and ethacrylic acids of methyl, ethyl and butyl alcohols. Of the homopolymers of such esters, butyl ether is the highest one that can be used, and is usually used as a comonomer with a more polar monomer. Higher alcohols can be used provided that they contain additional

0 polar group, needed to compensate for longer non-polar carbon chains. For example, glycol monoesters having a free hydroxyl group can be used here.

5 provides additional polar effect.

In addition, a hydroxyl group can be esterified (to form an ester) with a polar acid, for example, acetic or formic, or esterified (with

ether formation) polar

alcohol, for example ethanol, to form

p-ethoxyethylmethacrylate.

A similar result can be obtained by using incomplete esters of glycerol or its derivatives as the alcohol. It is also possible to use an alcohol containing, for example (in methanolamines or ethanolamines) amino groups, in glycidyl compounds -

0 oxane ring, and in hydroxyl acid - free carboxylic group (for example, in citric acid).

The esters of these hydroxyl materials of other unsaturated acids, such as maleic, fumaric, and itaconic, can be used; however, since these esters do not respond well to homopolymerization, it is best to use them in combination with another suitable polar monomer. A smaller portion of the comonomer can be added to the polymer to be dispersed, which in itself does not produce a sufficiently polar polymer. A similar type of polar monomer is obtained from the monomeric ester or ether of unsaturated lower alcohol, such as vinyl or allyl alcohol. You can use esters of lower acids, such as acetic acid, chloroacetic acid, lropionic acid and formic acid. If higher acids are used, then an additional polar group must also be present in order for a sufficiently polar polymer to be obtained, for example, a dicarboxylic acid, for example oxalic acid, in which the second carboxyl group remains free or is converted into the ester, can be used as the acid. alcohol, for example methyl or ethyl. Such an acid may have a hydroxyl group, such as lactic or citric acid, with the hydroxyl group remaining free or acetylated. You can also use an acid that contains an amino group, such as glycolic acid, in which case the amino group gives the necessary additional polarity. Similar principles apply to the ethers of unsaturated lower alcohols. The ester may be a simple ether of a lower alcohol, such as methyl or ethyl. The polarity is determined by the use of a di- or triatomic alcohol ether, in which one hydroxyl group remains free or is converted into an ester with a lower acid, such as acetic acid or formic, or into ether with methanol. As a simple ester, you can take the ester of a NuH-dimethyl ethanol amine, N, N-diethylethanolamine or a glypidyl compound. Another type of polar polymer is obtained by polymerization of acrylic or methacrylic acid or allyl alcohol. Polar derivatives such as acid chlorides, amides, methylolamides can also be polymerized. These monomers produce particularly insoluble polymers and are used for copolymerization with monomers that do not themselves form a sufficiently insoluble polymer. The systems of the second type use the following polar organic liquids: methanol, ethanol, acetone, glycol and, in extreme cases, dimethyl and methyl formamide. These polar organic liquids may contain less water. In this type of system, the polymer is relatively incomplete. Polymers of hydrocarbons are quite non-polar: styrene, vinyl toluene, divinyl benzene, diisopropene benzene, isoprene, butadiene, isobutylene, ethylene. The polymers of higher fatty esters of unsaturated acrylic, methacrylic and ethacrylic acids are non-polar. In these cases, the alcohol component of the ester contains the long carbon-carbon chain necessary to form a polymer of sufficient incompleteness. Typical is cetyl alcohol. Lauryl alcohol is the lowest alcohol that can be used in homopolymer esters, and the esters of this alcohol are used as comonomers with a more non-polar monomer. In addition, partial esters of a long chain polyol can be used, for example, distearate, glycerol diberatinate or dibeginate, where the residual hydroxyl group is esterified with unsaturated acid. Higher fatty esters or ethers of unsaturated alcohols such as vinyl and allyl can be used in the second type of systems. Suitable acidic components of such esters are stearic acid, behenic acid and dibasic monoesters such as cetyl or lauryl ester adipic or sebacic acid. Suitable ethers are cetyl alcohol or distearate, dilaurate or dibegine glycerol ethers. In systems of the second type, the dispersed polymer is insoluble, since it contains long carbon-carbon chains. In systems of the third type, the organic liquid may have any polarity, for example, an aliphatic hydrocarbon, benzyl or ethyl acetate. In this case, the polymer is insoluble regardless of its polarity. Such polymers include vinyl chloride, vinylidene chloride and acrylonitrile. It is clear that condensation reactions in which the required number of unsaturated groups is added to the solvating group, resulting in a preliminary anticoagulant, should not take place in the presence of free radicals or in a vinyl polymerization medium that can act on the unsaturated group. Preferably, the following methods are used: (f) ester linkages, especially those formed by interchanging them with either carboxyl / glycidyl or hydroxyl / acid chloride or hydroxyl / acid anhydride reactions; (it) ether bonds, especially formed by an addition reaction between alkylene oxides and hydroxyl; (iii) amide bonds, especially formed by the reaction of amide / acid chloride; (iii) urethane bonds, especially formed by the reaction of isocyanate with hydroxyl groups. Appropriate condensation bond, which is used for the joining of an unsaturated group and for the polymer solvate

The ruyus group containing esterifying fc on the azarization of complex ebers) or any reactive groups depends on the reactive group actually entering the polymer pep. Similarly, the appropriate conditions for this are determined by the type of communication to be obtained.

One or another member of the bond-forming pairs involved in the condensation reaction may be introduced into the solvating group. The number of suitable systems can be made very large by combining them, for example.

Copolymerized with a small amount

ol

fi-hydroxyethylmethacrylate

glycidyl methacrylate

methacrylic and acrylic acids

d.

methacrylic acid chloride, etc.

If the stabilizer precursor is used in dispersing polymers in polar fluids, then the following combinations are used. In the examples given, the solvating polymer components do not need a copolymer; each monomer contains a reactive group required for the condensation reaction.

Accordingly, the main component of the solvating group is scaled with

glycidium acrylic atom

acrylic acid chloride

The concentration of the polymer obtained by this method in the final polymer dispersion can be varied within wide limits, for example, from 5 to 65% of the dry residue. Preferably the dry residue of the dispersions is 25-50%. If it is required to increase the dry residue, this can be done by evaporation of a part of the liquid, maybe under reduced pressure.

The average size of dispersed particles is 0.05-2.0 microns. and the molecular weight of the dispersed NioKCT polymorphism is from 20,000 to 1,000,000 or more.

Dispersed polymers, have a mol. at. 50000-250000, can be used in coating compositions. In compositions for coatings subjected to air heating at 100–150 ° C, disperse solutions can be used.

using appropriate copolymerization with reactive groups, etherifying the ester with the formation of ethers and esters, etc. For example, in order to stabilize the stabilizer precursor with acridate or methacrylate monomer and result in a polymer of acrylate or methacrylate in a dispersed state, in an aromatic or aliphatic hydrocarbon, You can use the following combinations.

Respectively condensed with

methacrylic acid chloride

methacrylic acid glycidyl methacrylate

measures with mol. at. 100000-250000. In coating compositions, the drying of which occurs at

75-100 ° C. Dispersed polymers are used with mol. at. 60000-100000.

Acrylic or methacrylic acid or ester, amide or nitrile polymers are used in coating compositions.

of these acids, an aliphatic or a mixture of aliphatic and aromatic hydrocarbons is used as the organic liquid. Example I. A digester equipped with a stirrer and reflux condenser is filled with a mixture of 1000 wt. including white spirit, 1000 weight, including methyl ethyl ketone and 120 weight. including dinitrile of azo isobutyric acid, and the mixture is heated to boiling. During 2.5 hours the filling is uniform.

900 weight. including lauryl methacrylate and 100 wt. h

propylene glycol monomethacrylate and then

the mixture is heated for another hour, for

so that the reaction is finally over.

The reflux condenser is replaced by a direct,

add 1000 weight. including white spirit and distill the mixture until the temperature of the boiling liquid reaches 100 ° C. The precipitate in the boiler is filtered after cooling and a 25% polymer solution is obtained with the aperture of

viscosity 0.042 in benzene at 25 ° C.

Mix 3000 weight. including polymer solution, 300 weight. including methyl ethyl ketone and 167 weight. h, pyridine and weight immediately added with vigorous stirring. including methacrylic acid chloride. The white suspension is kept for 18 hours, and then a solution of caustic potassium in 400 wt. Is gradually added. including water and 400 wt. including ethanol with vigorous stirring. After separation of the liquid, the upper layer is drained, dried with anhydrous sodium sulfate and filtered. The resulting product is mixed with 5000 weight.h. ethanol to precipitate the compound, and allow the mixture to stand for 20 hours. The liquid is discharged, and the oily residue is dissolved in 1000 wt. including aliphatic hydrocarbon fraction boiling at 70-90 ° C. The resulting product is a 40% solution of the compound with a mol. at. 10000-15000, having 7-10 methacrylate groups per molecule, calculated from 90% of the reaction with the acid chloride. Example 2. In a digester equipped with a reflux condenser and a stirrer, 4,000 wt. including aliphatic hydrocarbon fraction, and then evenly add a mixture of 1960 weight. including lauryl methacrylate, 40 wt. including glycidyl methacrylate and 100 wt. including benzoyl peroxide paste (60% peroxide in dialkylphthalate). After further boiling over 40 minutes, 5 wt. lauryldimethylamine and the mixture was boiled for another hour. The polymer obtained is stirred for an hour with calcium oxide, drained and filtered to remove as much benzoic acid as possible. The reduced viscosity in benzene is 0.064 for a given field -1 -1.0 at 25 ° C. Add 30 wt. including methacrylic acid and 1 wt. of hydroquinone and the mixture is boiled under reflux in a nitrogen atmosphere until the acid concentration drops to 65-70% due to the esterification (with the formation of esters) of glycidyl groups. This process takes 18-20 hours. The result is a 33.7% solution of the polymer compound mol. at. up to 18,000 and 1.7 methacrylate groups per molecule. Example 3. The technique of manufacturing is the same as in Example 2. A mixture is taken that contains 1.940 wt. including lauryl methacrylate, 60 wt. including glycidyl methacrylate and 30 wt. including benzyl peroxide paste. In this case, it is no longer treated with calcium oxide, and the reduced viscosity of the obtained product is 0.109 in benzene at 25 ° C. Eternation is carried out (with the formation of ester) 30 wt. of methacrylic acid until the concentration of the acid falls by 25-26% of the initial value due to the esterification of the glycidyl groups (by acid number). A 28.9% solution of the polymeric compound is obtained with mol. at. 37000 and 2.0 methacrylate groups per molecule. Example 4. The technique of manufacturing is the same as in Example 1. 510 wt. including tert-butyl methacrylate, 2.5 wt. including propylene glycol monomethacrylate and 5 wt. including benzoyl peroxide paste is dissolved in 2000 wt. including hydrocarbon fraction boiling at 85 ° C and heated for 6 hours under reflux. The hydrocarbon fraction is then distilled off and replaced with an equal volume of the hydrocarbon 5 10 15 20 25 30 35 40 45 50 55 60 65 fraction boiling at 165 ° C. Prior to this, the entire mixture boils at 132 ° C, then 3 wt. maleic anhydride and the mixture is boiled for 4 hours. The resulting compound has a mol. c, 300,000 and 4 maleic unsaturated groups per molecule. Example 5 The manufacturing technique is the same as in Example 4, except that itaconic acid monomethyl ester is added instead of maleic anhydride. The resulting compound has a mol. at. 300,000 and 3.5 itaconate groups per molecule. Example 6. The manufacturing techniques are the same as in Example 1. 178 wt. including tertiary butyl methacrylate, 1.66 wt. including chlorohydrime methacrylic acid and 0.83 wt. h, dinitrile azoisobutyric acid is dissolved in 666.7 wt. ethyl acetate and refluxed for 5 hours. The ethyl acetate is distilled off in vacuo and replaced with white spirit, so that the final solution contains 25% polymer. 10 wt. allylamine and 25 wt. including lutidine, the mixture is vigorously stirred and left overnight. The product obtained is washed with several parts of water and then dried with 10 wt. Parts, anhydrous sodium sulfate and fn, dried. The resulting product is a 25% solution of the compound with a mol. at. 350000 p 3.5 al. Sawing groups per molecule with 50% allylation. Example 7. The manufacturing technique is the same as in Example 1. 104 wt. including tertiary butyl methacrylate, 0.5 weight. including monometacry, ethylene glycol stalemate and I weight. Part of benzoyl peroxide paste is dissolved in 400 wt. including hydrocarbon Lraction, boiling at 85 ° C, and refluxing for 5 hours. 200 weight. the solvent is then distilled off and replaced with 400 weight, white mineral spirits. The solution is dissolved in anhydrous sodium sulfate, filtered and heated to 40 wt. including allyl isocyanate in a nitrogen atmosphere at 60 ° C for 2 hours. Excess allyl isocyanate and white spirit are distilled until then. until you get 240 weight. h distille ta. The resulting product is a 21% solution of the compound with a mol. at. 260000 and 4 allyl groups n. one molecule. Example 8. The technique of manufacturing is the same as in Example 1. 208.5 wt. including tertiary butyl methacrylate, 2 wt. including methacrylic acid and 10 wt. including dinitrile azoisobulos acid is dissolved in 1,100 weight. including hydrocarbon fraction boiling at 100-120 ° C, and 100 weight. including butanol and heated under reflux for 4 hours. 600 weight. the solvent is distilled off. After this, 2 wt. h, lauryldimethylamine and 5 wt. of the allylglipidyl ether and the mixture obtained is heated to reflux until POR until the acid content drops by 25%.

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The resulting product is a 24% solution of the compound with a mol. at. 110,000 and 1.9 allyl groups per molecule.

Example 9. A mixture of 1,045 weight. including tertiary butyl methacrylate, 5 wt. including glycidyl methacrylate, 4000 wt. including distilled water, from which the air is removed, 12 wt. including potassium persulfate, 30 wt. including sodium lauryl sulfate and 0.5 weight. including primary octylmercanthan placed in the boiler, equipped with a stirrer and a thermometer, and maintained at 75 ° C for 5 hours. The fine particles formed are precipitated with excess ethanol dissolved in benzene, dried by shaking and with anhydrous sodium sulfate and filtered. After this, a partial precipitation of fractions having a mol. at. 50,000-200,000, as determined by measuring the reduced viscosity, and containing 9-35 glycidyl groups per molecule.

400 weight. including polymer fraction, 5 wt. including methacrylic acid and 0.05 wt. including dimethyllaurilamine dissolved in 800 weight. including hydrocarbon fraction boiling at 100-120 ° C. The mixture is refluxed under a nitrogen atmosphere until the acid concentration is such that 2 g of the acidic group is etherified per polymer molecule. This process is repeated for each fraction obtained by precipitating the polymer.

Example 10. A mixture of 870 weight. including ethyl acrylate, 3 wt. including hydroquinone and 375 parts of a block copolymer of propylene oxide and ethylene oxide of the type HO (C2H4O) a (CzNbO) (C2H4O) cH, containing 80% polyoxyethylene and 20% polyoxypropylene by weight, based on a polyoxypropylene block with mol. at. 1,500 and 1,800 are heated in a boiler equipped with a stirrer and a short packed distillation column leading to the refrigerator. Within 2 hours, water is removed as an azeotrope with ethyl acrylate, with a total of 100 weight gain. h distille ta. The mixture is cooled to 55 ° C and 0.3 weight% is added. including metallic sodium. A mixture of ethanol and ethyl acrylate is distilled off in 5 hours, and 200 weight is obtained. the distillate and the temperature of the boiling liquid are raised to 113 ° C.

Finally, over 3 hours, the excess ethyl acrylate is distilled off at a pressure of 70 mm Hg. the temperature rises from 50 to 160 ° C.

The compound obtained is a brown wax solid with a mol. at. 7000-9000 and 1.8 tertiary-acrylate groups per molecule in determining the amount of ester (by saponification numbers).

Example 11. 4000 weight. petroleum ether boiling at 100-120 ° C is boiled in a kettle equipped with a stirrer and reflux condenser. For 3 hours a mixture of 2000 wt. Is fed into this boiler. including 2-ethylhexyl acrylate, 60 wt. including glycidyl methacrylate and 12 wt. including dinitrile azoisobulos acid; Filtration of the mixture continues for

sixteen

2 hours After that serves 40 weight. including acrylic acid, 1 wt. including trade inhibitor Topanol A and 10 wt. including lauryldimethalamine, boiling continued for another 12 hours. A drop in the acid number indicates that 20-25% of the glycidyl rings are esterified. Example 12. The manufacturing technique is the same as in Example 11, except that 200 weight is added instead of 2-ethylhexyl acrylate. h cetidmethacrylate.

Example 13. In the boiler described in example 11, placed 1500 weight. including xylene, 1000 wt. petroleum ether boiling at 100-120 ° C and the whole mixture is boiled with reverse

a fridge. For 2.5 hours, a mixture of 1000 parts by weight of vinyltoluene, 43 wt. including vinyl acetate and 5 wt. including azodiisobutyronitrile. Boiling is then continued for 2 hours and the boiler is cooled. TO

a short packed fractionation column is attached to the boiler; 1000 weight. part of the ether and distilled off and add a mixture of 1200 weight. h of ethyl acrylate and 5 wt. including lauryldimethylamine. Within 4 hours distilled

a mixture of 100 weight. including ethyl acetate, ethyl acrylate and a smaller part of xylene. The final product has a dry residue of 35%, mol. at. 40,000 and contains 2--3 acrylic groups per molecule of compound.

Example 14. 2000 weight. including acetone is boiled in the boiler described in example 11, and for 7.5 hours a mixture of 1000 wt. including monomethacrylate in propylene glycol and 30 wt. including dinitrile azoisobulos acid, and then in

heated for 3 hours with a vertical fridge. After that, the mixture is cooled. The resulting solution was dried with freshly calcined anhydrous sodium sulfate. Then add 14 wt. including methacrylic acid chloride and 15 wt. including lutidine (2,6-dimethylpyridine) and the whole mixture stand in a closed boiler for 48 hours. Then lutidine hydrochloride is filtered off. The resulting compound has a mol. at. 15,000 and 2 double bonds per chain.

Example 15. In a boiler described in example 11, a mixture of 398 wt. including methyl methacrylate, 2 wt. including glycidyl methacrylate, 300 wt. including ethyl acetate and 1 wt. h. dinitrile

azo isobutyric acid for 6 hours. Then add 600 weight. including butyl acetate, and the solvent is distilled off until the dry residue reaches 37%. 650 weight. including this solution, 0.8 weight. including methacrylic acid,

0.2 weight. including hydroquinone and 2 wt. including lauryldimethylamine boil for 10 hours. At the end of this process, the acid number is equivalent to the esterification of 30% of all glycidyl groups. The resulting compound has a mol. at.

250,000 and contains about 2 methacrylate groups per chain.

Example 16. The manufacturing technique repeats the first part of Example 13, but after preparing a copolymer of vinyltoluoyl and vinyl acetate instead of adding ethyl acrylate

17

the acetate groups of this copolymer are hydrodated at boiling with 100 wt. including calcium hydroxide dissolved in 800 wt. h. alcohol. The copolymer slurry is completely precipitated by pouring the entire mixture in a thin stream into 10 liters of methyl alcohol. The solid copolymer is separated, washed with excess methanol, dried under vacuum, and dissolved in 2000 wt. hours of pure dry toluene. A 28% solution is obtained, which is heated to 100 ° C, and then 10 weight percent is added. h sodium wire, doing it slowly with vigorous stirring. After 2 hours, most of the sodium is dissolved, and the boiler is cooled. 1500 weight. This solution is placed in an autoclave, which is zirconium dry nitrogen, and then gaseous vinyl chloride. The temperature rises to 80 ° C and vinyl chloride is fed into the autoclave under high pressure until the pressure in the autoclave reaches 7.03 kg / cm. Supply takes place over 48 hours. At the end of this time, the autoclave is cooled, the excess vinyl chloride is released and the solution of the obtained compound is recovered. Add 10 wt. water and the mixture is vigorously stirred for 4 hours when the sodium chloride formed takes on a crude, crystalline form. Sodium chloride is filtered off, the resulting compound is mol. at. 40,000.

According to this manufacturing method, it is not possible to determine the exact number of vinyl bonds per compound molecule, it is about 1-5.

Example 17. A mixture consisting of 1493 wt. including lauryl methacrylate, 7 wt. including glycidyl methacrylate, 1500 wt. including petroleum ether boiling at 80-100 ° C, and 4 weight. including benzoyl peroxide paste. The mixture was boiled with stirring for 6 hours. Add 5 wt. including lauryldimethylamine, and heating is continued for 1.5 hours. Then add 800 weight. including the odorless lacquer and the solvent is distilled off until the boiler temperature reaches 110 ° C. After this, 4 wt. including methacrylic acid and 1 wt. of hydroquinone and the mixture is boiled for approximately 20 hours. After that, the acid number corresponds to 15-20% esterification of glycidyl groups. The molecular weight of the resulting compound is 450000, which corresponds to about 1.5 methacrylate groups per polymer chain.

The use of the compounds obtained.

Example 18. In a boiler equipped with a stirrer, a sampling pipe, a thermometer and a reflux condenser, a mixture of 63 wt. including a solution of the compound prepared in Example 1, 30 wt. including methyl methacrylate, 3.5 wt. including dinitrile isoisobutyric acid, 170 weight. including aliphatic hydrocarbon, boiling at 40-60 ° C, and 10 wt. including acetone. When boiling the mixture almost instantly turns white. After 30 minutes

18

5 wt. including 10% aqueous solution of n-octylmercaptan in white spirit and a mixture containing 475 weight. including methyl methacrylate, 2 wt. including n-octylmercaptan and 3 wt. including dinitrile of azo isobutyric acid, and this mixture is added evenly over 3 hours. The whole mixture is boiled for 30 minutes and then cooled. The result is a stabilized

latex consisting of very small particles, with a dry residue of 49%.

Example 19. The technique of manufacturing is the same as in Example 18. A mixture of 80 wt. including compounds made in example 2.16 weight. including methyl methacrylate, 18 wt. including ethyl acrylate, 1 wt. including methacrylic acid, 3 wt. including dinitrile azoisobulos acid, 125 weight. h. white spirit and 450 wt. including aliphatic hydrocarbon fraction boiling at 70-90 ° C. After 30 minutes a mixture containing 284 wt. is added uniformly over 3 hours to reflux. including methyl methacrylate, 315 weight. including ethyl acrylate, 32 wt. including methacrylic ki slots, 2.5 wt. h-octyl mercaptan and 5 wt. including dinitrile azoisobulos acid; The mixture is then boiled for 30 minutes, after which it is cooled and a thin, stabilized latex is obtained with particles of small size and 50% dry residue.

Example 20. The manufacturing technique is the same as in Example 18. A mixture of 264 wt. including compounds made in example 3, 300 weight. including methyl methacrylate,

4.8 weight. including methacrylic acid, 4 wt. including dinitrile azoisobulos acid, 295 weight. h. white spirit and 1340 weight. including aliphatic hydrocarbon fraction boiling at 70-90 ° C. After 20 minutes heating add 14 wt. h

10% aqueous solution of m-octylmercaptan in whitespirit, and then a mixture consisting of 1660 wt. Is added evenly over 2.5 hours. including methyl methacrylate, 34 wt. including methacrylic acid, 3 wt. including n-octyl mercaptan and

4 wt. including dinitrile azoisobulos acid; The liquid is boiled for 15 minutes and cooled. A low viscosity stabilized latex is obtained with small particles, the dry residue being 52%.

Example 21. The manufacturing technique is the same as in Example 20. Methacrylic acid is not used, 1700 wt. Is fed. including methyl methacrylate. A stabilized latex consisting of small particles is obtained, with a dry residue of 53.5%.

Example 22. The manufacturing technique is the same as in Example 21, but 120 wt. including methyl methacrylate, and 1880 wt. including methyl methacrylate. A stabilized latex is obtained with a dry residue of 53.5% and a particle size average between Examples 20 and 21. Example 23. The compound obtained in

Example 4, diluted to 25% solids in n-hexane. In a stainless steel autoclave equipped with a stirrer, a coil for temperature control, a thermometer and a means allowing the addition of reactive substances while the autoclave is under pressure, a mixture of 48 wt. including this 25% solution, 750 weight. including vipil chloride, 331 wt. including pure n-hexane and 1,125 weight. including diisopronyl peroxide carbonate. The temperature was raised to 50 ° C by passing hot water through a coil, and an additional 177 weight was added over 2 hours 40 minutes. including a 25% solution of the title compound. After 6 hours and 45 minutes, excess vinyl chloride is removed and the mixture is removed from the autoclave. The resulting product is a liquid dispersion with small particles of low viscosity and 57.9% dense particles, in which 93% of the monomer is converted to a polymer. The K-number of the polymer is 54. Example 24. 1 The manufacturing equipment is the same as in Example 23. The compound obtained in Example 5 was used. A latex with approximately the same properties was obtained. Example 25. Use the tools and method described in example 23. A mixture of 500 wt. including vinyl chloride, 440 weight. hours to-hexane, 0.75 weight. including diisopropyl peroxydicarbonate and 32 wt. including a 250% solution of the compound obtained in Example 5, is heated to 50 ° C. Then over 4 hours add 118 weight. including the solution of the indicated compound, the temperature was maintained at 50 ° C, and the unreacted vinyl chloride was removed after 6 hours. 15 minutes. The resulting product is a thixotropic dispersion with small particles, with a dry residue equal to 25.3%. The K-number of the polymer is 49. Example 26 The devices and method described in Example 23 are used. A mixture of 500 wt. including vinyl chloride, 147 weight. including n-hexane, 0.75 weight. including diisopropyl peroxydicarbonate and 32 wt. Part of the compound prepared in Example 8 (25% solution) was maintained at 50 ° C for 3 hours and an additional 118 wt. including the solution of said compound. Unreacted vinyl chloride is removed after 6 hours and 30 minutes. The resulting product is a slightly thick dispersion of small particles with a dry residue equal to 46%. The polymer has a K-number of 49. Example 27. The manufacturing technique is the same as in Example 23. The compound obtained in Example 6 was used. latex with the same properties. Example 28. The technique of manufacturing is the same as in Example 25. The compound obtained in Example 7 is used. A latex with similar properties is obtained. Example 29. A mixture of 25 wt. including vinylidene chloride, 2.75 weight. including methyl acrylate, 19 wt. h n-hexap, 0.26 weight. including diisonroiyl peroxydicarbonate and 1 wt. The compounds obtained in Example 4 were placed in a stainless steel vessel, which was sealed and subjected to thermostat for 5 hours at 50 ° C. Get latex with particles of small size and a dry residue equal to 49%. Example 30. A mixture of 50 wt. including viil acetate, 90 wt. including petroleum ether, boiling at 73 ° C, 1 wt. including dinitrile azoisobulos acid and 3 weight. Part of the compound obtained in Example 4 is heated to boiling for 4 hours in a boiler equipped with a stirrer and reflux condenser. A dispersion with small particles is obtained. The dry residue is 34.3%. Example 31. The manufacturing technique is the same as in Example 30, but vinyl chloride is used instead of vinyl acetate. After 5 o'clock boils get 33% latex in small dispersed particles. Example 32. The compound obtained in Example 10 was dissolved in ethanol to obtain a 20% solution. A mixture of 10 wt. including such a solution and 10 wt. including styrene, 31 wt. including ethanol, 47 wt. including ethylene glycol and 2 wt. including dinitrile, azo-butyric acid is heated to boiling in a boiler equipped with a stirrer and reflux condenser. After 35 minutes heating through the refrigerator is evenly served for 1 hour 45 minutes out of 10 weight. including a 20% solution of this compound, 60 wt. including styrene, 4 wt. including dinitrile azoisobulos acid; After boiling for an hour and cooled to room temperature, a somewhat thick latex is obtained with particles of small size and a dry residue equal to 39%. Example 33. The manufacturing technique is the same as in example 32. At 10 wt. including the feed solution of this compound is replaced by 8 wt. including ethanol. A thinner latex is obtained with a dry residue of 40%. Example 34. The manufacturing technique is the same as in Example 33. Styrene is replaced by a mixture of styrene, ethyl acrylate and acrylonitrile in a ratio of 65: 25: 10 by weight. Get latex thin, somewhat coarse, with a dry residue equal to 36%. Example 35. A mixture of 266 wt. including the solution of the compound obtained in Example 11, 300 wt. including methyl methacrylate, 4.8 weight. including methacrylic acid, 3.8 weight. including dinitrile azoisobulos acid, 300 weight. h. odorless lacquer gasoline and 1335 weight. The petroleum ether fractions boiling at 70-90 ° C are refluxed for 20 minutes. Then add 15 wt. including 10% aqueous solution of n-nonylmercaptan and white spirit, and a mixture of 1660 weight. including methyl methacrylate, 34 wt. including dinitrile azoisobutyric acid, which is uniformly pumped into the reflux pump for 3 hours. The mixture is then heated for another 15 minutes and cooled. The resulting product is a low viscosity stabilized latex with fine dispersing particles. Example 36. The manufacturing technique is the same as in Example 35. In the initial charge, 125 weight is taken. including methyl methacrylate and 5 250 weight. including the solution of the compound made in Example 12. A sufficiently stabilized latex with small particles is obtained. Example 37. A mixture of 730 wt. including oil fraction boiling at 60-90 ° С, 250 wt. hours of pure toluene, 10 wt. including methacrylic acid, 90 wt. including methyl methacrylate, 35 wt. including a solution of the compound prepared in example 13, and 2 wt. part of dinitol-15oryl azoisobutyric acid is boiled with a condenser for 30 minutes. At this time, a low particle size latex is obtained. For 2.5 hours, a mixture of 20 wt. including 20 methacrylic acid, 280 weight. including methyl methacrylate and 2 wt. including dinitrile azoisobulos acid; The mixture is boiled for another 20 minutes and cooled. Get latex with small particles and a dry residue equal to 40%. Example 38. The manufacturing techniques are the same as in Example 37, but xylene is used instead of toluene, and the solution of the compound obtained in Example 13 is replaced with a solution of the compound obtained in Example 16. About the same result is obtained. Example 39. A mixture of 100 wt. Part of the product of example 15,850 weight. including ethyl acetate, 1 weight. including dinitrile azoisobulos acid and 50 weight. 35 h. Acrylonitrile is refluxed for one hour. Then a mixture of 400 wt. Is injected into the boiler for 3 hours. including acrylonitrile and 3 wt. including dinitrile azoisobulos acid; The result is a latex with 40 small particles. Example 40. In a boiler equipped with a reflux condenser and a stirrer, a mixture of 1700 wt. including ethyl acetate and 220 wt. including the solution prepared in Example 15. This 45 mixture was boiled under reflux and a mixture of 110 wt. including acrylic acid and 2 wt. including dinitrile isoisobutyric acid. Boiling is continued for 30 minutes, and then 800 weight is added over a period of 2.5 hours 50. including acrylic acid, which dissolved 5 wt. including dinitrile azoisobulos acid; The result is a stabilized latex with small particles. Example 41. A mixture of 142 wt. including the solution prepared in example 17, 61 wt. including methacrylic acid, 92 wt. including methyl methacrylate, 280 weight. including oil fraction. boiling at 70-90 ° C, 120 wt. h. white spirit-60 ta and 1 wt. The isoisobutyric acid dinitrile is refluxed for 20 minutes. Then add 0.3 weight. including primary octylmercaptan and then a mixture of 210 wt. including methyl methacrylate, 65 25 55 140 weight. including methacrylic acid, 1 wt. including primary octyl mercaptan and 1 wt. including dinitrile isoisobutyric acid, which is fed uniformly for 2.5 hours. Latex is obtained with very fine particles, its viscosity increases with the course of the reaction, and the final product is a viscous syrup. Example 42. A mixture of 80 wt. including a solution of the compound obtained in example 12, 18 wt. including methyl methacrylate, 16 wt. h r-ethoxyethyl acrylate, 1 wt. including methacrylic acid, 3 wt. including dinitrile azoisobulos acid; 125 weight. h. odorless lacquer gasoline, 450 wt. The aliphatic hydrocarbon fraction boiling at 70-90 ° C is refluxed for 30 minutes. Then, a mixture of 280 wt. Is uniformly fed to the sprayed mixture for 3 hours. including methyl methacrylate, 300 weight. h r-ethoxyethyl methacrylate, 33 wt. including acrylic acid, 2.5 wt. including n-octylmercaptan, 5 wt. including dinitrile azoisobulos acid; The vessel is heated for another 25 minutes and cooled. A stabilized latex with small particles is obtained. Example 43. A mixture of 10 wt. including a solution of the compound obtained in example 14.4 wt. h. vinyl stearate, 4 wt. including acrylonitrile, 2 wt. including acrylamide, 40 wt. including methanol, 40 wt. h ztylenglykol, 2 wt. azoisobutyric acid dinitrile is heated to reflux. After 30 minutes, a uniform mixture of 28 wt. h. vinyl stearate, 30 wt. h. Acrylonitryla, 2 wt. including acrylamide and 2 wt. including dinitrile azoisomas yu acid. Boiling lasts another 1.5 hours. Stable latex with small particles is obtained. Example 44. A mixture of 1000 wt. including petroleum ether, boiling at 40-60 ° C, 150 weight. including the solution of the compound obtained in Example 17, 50 wt. including styrene, 150 wt. including acrylonitrile, 10 wt. including dinitrile azoisobulos acid and 0.3 weight. including tertiary amylmercaptan, is refluxed for 1.5 hours. Some thick latex is obtained with rather large individuals. Example 45. The manufacturing technique is the same as in Example 4, but the precursor: stabilizer used in Example 4 is used. A latex is obtained with particles of small size and a dry residue equal to 58%. Example 46. A stabilizer precursor is prepared by placing a mixture of 190 wt. including butyl acetate and 10 wt. including ethyl acetate and boil (120 ° C) under reflux. Then over 5 hours served a mixture of 76 wt. including lauryl methacrylate. 19 wt. octyl methacrylate, 5 wt. including glycidyl methacrylate and 1 wt. including paste benzoyl peroxide (60% peroxide). Add 0.5 wt. including complex alkylamine "Army DMDS, which acts as a catalyst in the stage of esterification; heating pro23

continue for another hour to destroy the residual peroxide initiator. The molecular weight determined by viscosity is 75,000. Add 2.5 wt. including acrylic acid together with a small amount (about 1/10 of the hydrochloric acid), and the mixture is heated under reflux. After 6 hours, the acid number of the reaction mixture decreases from 3.1 to 3.3 mn KOH / g, which corresponds approximately to the addition of three acrylic radicals in each molecule. The resulting product is pure golden brown syrup with a dry residue of 32%.

A synthetic dispersion agent is prepared in the form of a graft copolymer by placing 200 wt. including ethyl acetate, 300 weight. including the above predecessor stabilizer, 97 weight. including methyl methacrylate, 3 wt. including methacrylic acid and 1 wt. including dinitrile azoisobulos acid as an initiator, raise the temperature to 85 ° C and hold it for 2 hours. Then another 1 part of initiator is added, and the mixture is boiled for 2 hours. The molecular weight of the grafted chains is 30,000, the dry residue is 31%. The resulting product is an opalescent yellow syrup,

415 weight. including low-boiling oil fraction (70-90 ° С) is placed in the boiler. Then, a mixture of 80 wt. including methyl methacrylate, 2 wt. including methacrylic acid, 15 wt. including a dispersion solution prepared as described above, and 1.5 wt. including dinitrile azoisobulos acid; The mixture is then boiled.

24

under reflux (75 ° C) and incubated for 3 hours before cooling. The resulting product is a stable white latex.

Example 47. A mixture of 340 wt. including low-boiling oil fraction (70-90 ° С), 100 wt. h. white spirit, 1 wt. including dinitrile azoisobulos acid and 1 weight. including primary octyl mercaptan, which is a 10% solution of it in white spirit. The mixture was boiled (75 ° C), and then a mixture of 150 wt. including a solution of the dispersion agent, manufactured according to example 46, 400 weight. including methyl methacrylate. Shvee.ch.

methacrylic acid, 1 wt. including dinitrile azoisobulos acid and 10 wt. including 10% aqueous solution of primary actilomercaptan in white spirit. The resulting product is a stable white latex with a dry

balance equal to 50%.

Subject invention

A method of producing organic dispersions of vinyl polymers by polymerizing the corresponding monomers in an organic liquid medium that does not dissolve the polymer under the influence of free radical polymerization initiators, characterized in that, in order to increase the stability of the dispersion, the polymerization process is carried out in the presence of a small amount of compound containing a solvated polymeric group with a molecular weight of at least 5,000 and unsaturated groups capable of copolymerizing with the starting monomer.