JPS6036521A - Manufacture of granular polymer - Google Patents

Abstract

PURPOSE:To obtain at low cost a highly heat-resistant granular polymer useful for adhesives, etc., by the reaction between polyisocyanate and polycarboxylic acid in the presence of each specific first non-aqueous organic liquid, second one and dispersion stabilizer to effect a dispersed state in the first organic liquid. CONSTITUTION:The objective polymer can be obtained by the reaction between a polyisocyanate and an acid anhydride group-contg. polycarboxylic acid and/or the original polycarboxylic acid in the presence of (A) a first non-aqueous organic liquid insoluble to the final polymer (e.g., n-hexane), (B) a dispersion stabilizer soluble to the liquid (A), and (C) a second non-aqueous organic liquid soluble or swellable to the final polymer and immiscible with the liquid (A) (e.g., N-methylpyrrolidone). Said stabilizer (B) is an epoxy group-contg. vinyl polymer with an average molecular weight >=6,000 preparad by the reaction between (D) an ethylenic unsaturated monomer having >=6C hydrocarbon side chain and (E) an epoxy group-contg. ethylenic unsaturated monomer in a molar ratio (D)/(E) of 1/1-6/1. The stabilizer (B) will be used in such an amount as to be >=1.5wt% based on the liquid (C).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a particulate polymer, and more specifically, mainly to a 7-t, a molded product, and an adhesive.

We will discuss how to use particulate polymers with excellent heat resistance that can be applied to paints, composite materials, etc.

A polymer in which imide groups are engineered by reacting polyisocyanate with polycarboxylic m having an acid anhydride group in solution in an expensive solvent such as N-methylpyrrolidone, dimethylformamide, or dimethylacetamide. It is known to obtain solutions 9, such as polyamide-imide solutions, polyimide solutions, etc. However, in order to obtain solid polymer gold from such a polymer solution, it is necessary to remove or recover the solvent by an extremely uneconomical process, which poses a major cost problem in industrial scale production. One promising method for obtaining solid polymers is a bulk polymerization method that does not require a solvent. However, polymers having imide groups generally have a rigid and highly polar molecular structure, and are characterized by a high glass transition temperature. Therefore, when applying the bulk polymerization method, it is generally necessary to proceed with the reaction under harsh conditions of high temperature and high pressure.
However, it is difficult to suppress side reactions, and no rule of 70 has been successfully put into practical use yet.

Furthermore, among polyamide resins, aromatic polyamides are known to have very good heat resistance, but generally the reactivity between aromatic dicarboxylic acids and aromatic diamines is not sufficient.

6. Polymer L1 such as 6-nylon and 6-nylon:
In order to obtain the polymer, a polymerization reaction of an aromatic dicarboxylic acid earth chloride and an aromatic diamine, which is more reactive than a free carboxyl group, is used. but.

In the reaction of aromatic diamine and aromatic dicarboxylic acid dichloride, hydrochloric acid is produced as a by-product, and side reactions such as formation of undesirable amine hydrochloride occur, so it is necessary to remove hydrochloric acid.
Problems remain in industrial scale manufacturing.

As a result of research into an inexpensive method for producing a particulate polymer with excellent heat resistance, the present inventor has completed a method for producing a particulate polymer dispersed in a non-aqueous organic liquid. .

The present invention provides a first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a dispersion stabilizer that is soluble or insoluble in the particulate polymer to be produced. In the presence of a second non-aqueous organic liquid that is swellable and essentially immiscible with the first non-aqueous organic liquid, polyisocyanate (I) and a polycarboxylic acid having acid anhydride groups ( II) and/or a polycarboxylic acid (full) to form a particulate polymer dispersed in a first non-aqueous organic liquid, the dispersion stabilizer has a carbon number The ethylenically unsaturated monomer (3) having a side chain consisting of 6 or more hydrocarbon groups and the ethylenically unsaturated monomer (B) having an epoxy group in a molar ratio of (A)/(I31 to 1 /
An epoxy group-containing vinyl polymer having a number average molecular weight of H6 o o or more, which is obtained by reacting in a range of 1 to 6/1, is used as a second non-aqueous organic liquid, polyisocyanate.

The present invention relates to a method for producing a particulate polymer, characterized in that it is used in an amount of 0.5 MM% or more based on polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group.

According to the production method of the present invention, the one-particulate polymer is obtained as a dispersion of relatively small particles in the non-aqueous organic liquid of ε-i3-, and therefore can be easily recovered from the dispersion by a filtration operation. In addition, especially in the production method of the present invention, an inexpensive general-purpose solvent that is insoluble in the particulate polymer to be produced can be used as the first non-aqueous organic liquid. Unlike the solution polymerization method, which has a limit in solidification due to the insolubility of the polymer in the solvent, the present invention makes it possible to obtain a high solids content of 50% or more in a non-aqueous organic liquid.

Amata 1 In the present invention, the conversion rate of monomers into particulate polymers can be sufficiently increased in the direct reaction region of the solution polymerization method, and the reaction can be completed under relatively mild conditions, so side reactions etc. There is no decrease in purity due to

As the first non-aqueous organic liquid in Genmei Ippon.

It is insoluble in the particulate polymer that is produced.

li @ A non-aqueous organic liquid having inert properties that does not inhibit the reaction is used.

For example, n-hexane, octane, dodecane, liquid paraffin, ■≦OPA-E, l80PAR-H.

l5OI) Aliphatic or alicyclic hydrocarbons such as A-K (trade name manufactured by Esso Standard Oil Co., Ltd.; a petroleum-based saturated aliphatic or alicyclic hydrocarbon with a boiling point range of about 40 to 300°C) etc. are used. In consideration of reaction preservation, those having a boiling point of 80° C. or higher are preferable. These can be used alone or in combination of two or more.

In the present invention, the second non-aqueous organic liquid that is essentially immiscible with the first non-aqueous organic liquid is a non-aqueous organic liquid that has inert properties that do not inhibit the double polymerization reaction, and is a non-aqueous organic liquid that has an inert property that does not inhibit the double polymerization reaction. -C9 which is soluble or swellable with at least one of (11, (n) and/or (■)) and contacts the reaction between the terminal groups in the polymerization reaction process.

A solvent is used that acts as a solvent to increase the molecular weight of the resulting polymer. Here, what does it mean to be essentially immiscible with the first non-aqueous organic liquid?

In addition to those that are completely insoluble in the first non-aqueous organic liquid, it also includes non-aqueous organic liquids that are not completely insoluble but immiscible to the extent that the two liquids phase separate at a certain mixing ratio. That is what it means. The second non-aqueous organic liquid is preferably a polar liquid that has a greater affinity for the resulting polymer or reactant contained in the dispersed phase than the first non-aqueous organic liquid. Examples of such a second non-aqueous organic liquid include N-methylpyrrolidone, N-vinylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, and phenol.

Cresol etc. are used. These may be used alone or in combination of two or more. Preferably, a combination of an aliphatic or alicyclic hydrocarbon and N-methylpyrrolidone is used as the first non-aqueous organic liquid.

Carbon number 6 used in the production of the dispersion stabilizer in the present invention
Ethylenically unsaturated monomers containing side chains consisting of the above hydrocarbon groups include 2, for example, 1-octene, 1- or 2
- nonene, 1- or 2-decene, 1- or 2-dodecene, 1- or 2-hexadece/, 1- or 2-hegetadecene, 2-methyl-1-nonene, 2-methyl-1-decene, Vinyl such as 2-methyl-1-dodecene, 2-methyl-1-hexadecene, 2-methyl-1-heptadecene,
Propenyl or vain propenyl group-containing aliphatic straight-chain unsaturated hydrocarbon, acrylic acid and/or methacrylic acid and 2
-Ethylhexyl alcohol.

Esters with aliphatic alcohols having 6 or more carbon atoms such as hexyl alcohol or alicyclic alcohols having 6 or more carbon atoms such as cyclohexanol, norbonanol, and adamantanol are used.

The ethylenically unsaturated monomer having an epoxy group used in the present invention is not particularly limited, and examples include 1,3-butadiene monoepoxide, 2-methyl-1,3-butadiene monoepoxide, 1,3-pentadiene monoepoxide, 1,5-henolidiene monoepoxide,
1. Epoxy group-containing aliphatic unsaturated hydrocarbons such as 8-nonane diene monoepoxide, and epoxy-containing ether-bonded aliphatic unsaturated hydrocarbons such as glycidyl allyl ether.

Vinyl sulfone or epoxy group-containing nitrogen-bonded aliphatic unsaturated hydrocarbons such as methacrylic acid and/or glycidyl acrylate, cyclohexene oxide, dicyclopentadiene monooxide, methacrylic acid or acrylic acid and cyclohexanol oxide or An epoxy group such as an ester of water-oxidized dicyclobentadicone monooxide, or an alicyclic unsaturated hydrocarbon can be used.

These ethylenically unsaturated monomers having side chains consisting of hydrocarbon groups having 6 or more carbon atoms and ethylenically unsaturated monomers having epoxy groups are random copolymers, block copolymers, or graft copolymers. It functions as a dispersion stabilizer. The copolymer is preferably a random copolymer of lauryl methacrylate, stearyl methacrylate, lauryl acrylate or stearyl methacrylate and glycidyl acrylate or glycidyl methacrylate. There are no particular restrictions on the polymerization method for obtaining the dispersion stabilizer1.
For example, a conventional polymerization method of ethylenic monomers using a radical initiator as a reaction initiator can be used.

That is, the side chain portion of the dispersion stabilizer consisting of a hydrocarbon group having 6 or more carbon atoms is a portion that is soluble in the first non-aqueous organic liquid,
Retaining solubility of the copolymer in the first non-aqueous organic liquid.

Furthermore, this portion forms a repellent layer covering the surface of the dispersed particles to prevent fusion of the dispersed particles.

Also, the epoxy group is essentially insoluble in the first non-aqueous organic liquid, but rather soluble in the second non-aqueous organic liquid.

Furthermore, the components constituting the particulate polymer and the epoxy group chemically bond to each other, thereby fixing the dispersing agent to the surface of the dispersed particles and forming a stable repellent layer on each dispersed particle.

Therefore, the balance between two different functions of 9 or more determines the effectiveness of the dispersion stabilizer. Molar ratio (A)/(B) of the ethylenically unsaturated monomer (A) containing a side chain consisting of a hydrocarbon group having 6 or more carbon atoms and the ethylenically unsaturated monomer (B) having an epoxy group When the ratio exceeds 6/1, the solubility in the first non-aqueous organic liquid is greater than the affinity for the dispersed particles, and the effect of the dispersion stabilizer 9 is not exhibited. If it is less than 1/1, the solubility in the first non-aqueous organic liquid will be so low that it will not be effective as a dispersion stabilizer.

On the other hand, in order to form a repellent layer covering the surface of the dispersed particles and prevent fusion of the dispersed particles, that is, to exhibit the effect as a dispersion stabilizer, the number average molecular weight of the copolymer must be 6000 or more. . If the number average molecular weight is less than 6,000, the formation of a repellent layer is insufficient and the proportion of 9-dispersed particles fused together increases.

It becomes difficult to synthesize a stable particulate polymer in which the dispersed particles do not aggregate easily. There are no particular restrictions on the use of a copolymer with a large number average molecular weight obtained by a conventional polymerization method as a dispersion stabilizer. Furthermore, when a particulate polymer is synthesized under certain conditions, there is a relationship between the particle size obtained and the number average molecular weight of the copolymer. For example, when a copolymer with a number average molecular size of z6ooo was used as a dispersion stabilizer, the main particle size was 50 to 500μ.

In a copolymer with a number average molecular weight of 60,000, the main particle size is 20
~40μ, and at a number average molecular weight of 300.000, the main particle size was 5 to 20μ. This is an industrially effective technology that allows particle size adjustment of particulate polymers obtained simply by using copolymers with different number average molecular weights as dispersion stabilizers without using special production equipment. It shows.

However, the number average molecular weight was 300. Naturally, if you make it larger than OOO, the viscosity will increase and it will become difficult to handle.

For the purpose of obtaining even finer particles, it is more advantageous to improve the synthesis equipment, such as by using an emulsifier (homo mixer), than to use a dispersant with a large number average molecular weight.

From the above, the number average molecular weight of the copolymer for C as a dispersion stabilizer must be 6,000 or more, and the number average molecular weight is from 6,000 to 300. It is said that a range of OOQ is more preferable. The number average molecular weight can be measured by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve. The number average molecular weight of the dispersion stabilizer is controlled by the reaction temperature and catalyst amount during its production.

The amount of dispersion stabilizer used is 0.5 based on the weight of the dispersed particles (non-aqueous organic liquid, polyincyanate, polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group).
Heavy! -4 or higher.

Considering heat resistance and economic efficiency, the amount of dispersion stabilizer used is 2.
A N range of ~20% by weight is preferred.

The dispersion stabilizer is usually produced and used in the form of a solution, and the amount used is calculated, for example, by the weight of nonvolatile matter in the solution after drying at 170° C. for 2 hours.

Examples of the polyyn7anate used in the present invention include trilene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate, 4,4'-
Aromatic diisocyanates such as diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate.

Aliphatic diisocyanates such as 1.12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate,
cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate, isophorone diisocyanate, triphenylmethane-4,4,'4''-triisocyanate, polyphenylmethyl polyisocyanate, e.g. Polyisocyanates such as phosgenated condensates and incyanurate ring-containing polyisocyanates obtained by trimerization of these polyisocyanates are used.

Considering heat resistance, cost, etc., tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, triphenylmethane-4,4,'4''-triincyanate, etc. are preferably used. It is preferable to use aromatic polyisocyanates and, among these, polyisocyanates having incyanurate i obtained by trimerization reaction of aromatic diisocyanates.A suitable method for producing isocyanurate ring-containing polyisocyanates is described in Japanese Patent Publication No. 56-34209. The polyisocyanate containing isocyanurate f Difunctional polyisocyanates are used in the synthesis of certain particulate polymers. Trifunctional or higher functional polyisocyanates are used in the synthesis of mono-branched thermosetting particulate polymers. Isocyanates may be used alone or in combination of two or more depending on the purpose.

Polyincyanate is used to control the reaction rate during the polycondensation reaction process and to obtain a stable particulate polymer.
-Butanol, benzyl alcohol.

It is also possible to use a suitable blocking agent having one active hydrogen in the molecule, such as 6-caprolactam, methyl ethyl ketone oxime, phenol, or cresol, which is partially or completely stabilized.

As a polycarboxylic acid having an acid anhydride group.

For example, tricarboxylic anhydrides such as trimellitic anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, 3,4,4'-benzophenonetricarboxylic acid-3,4'-anhydride, 1 , 2,3.4-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-C2,2,2]-]octo7
)-ene-2:3,5:6-tetracarboxylic acid and other aliphatic and alicyclic tetrabasic acids, pyromellitic acid, 3.
3: 4.4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 2,3
, 6.7-naphthalenetetracarboxylic acid, 1,2,5.
6-naphthalenetetracarboxylic acid, ethylene glycol bistrimelitate, 2,2'-his(3,4-biscarboxyphenyl)furopane.

2, 3.3'-, or 3. a, '4.4'-biphenyltetracarboxylic acid, perylene-3,4,9,1
0-Tetracarboxylic acid, bis3,4-dicarboxyphenylsulfone.

2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane, 2.2-bis[4-(2,3-
dicarboxyphenoxy)phenyl]furopane.

4-(2,3-dicarboxyphenoquine)-4'-(3
,4-dicarboxyphenoxy)-diphenyl-2,2
- Aromatic tetrabasic acids such as propane, diophene-2,3,
Examples include tetrabasic acid dianhydrides or -anhydrides such as heterocyclic tetrabasic acids such as 4,5-tetracarboxylic acid and virazine tet>carboxylic acid.

A polyamide-imide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxyl group, such as tricarboxylic anhydride, and a polyinocyanate. Further, a polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group such as tetracarboxylic dianhydride and a polyincyanate. Generally, considering heat resistance, cost, etc., trimellitic anhydride and 2.2-bis(4-(3,4-dicarboxyphenoxy)phenyl) are recommended.
Two meters of propane water, 3. a; 4.4'-Benzophenonetetracarboxylic dianhydride or pyromellitic dianhydride is preferred.

Examples of polycarboxylic acids include terephthalic acid.

Isophthalic acid, 2. (i-7,2,5- or 3,6-dicarboxy7toluene, 2,6-dicarboxynaphthalene.

3.3'- or 4.4'-dicarbogysibiphenyl, bis(3-4id4-carboxyphenyl) ether.

Bis(3- or 4-carboxyphenyl)ketone.

Bis(3-father+i4-:tyrpoxophenyl)sulfo7, H,:t, (3-also B4-carboxymphenyl)methane, his(3-4 is 4-carboxymphenyl)dimethylmethane, trimectsu l-1fi, trimenic acid;

Pyromellitic acid, tris(2-carboxyethyl)isocyanurate, tricarpallic acid, nitrilotriacetic acid, nitrilotripropionic acid, adipic acid, sebacic acid,
Dodecanedicarboxylic acid and the like are used. Considering heat resistance, isophthalic acid, hachiphthalic acid, trimesic acid, tris(2-carboxyethyl)incyanuride-1
-Or nitrilotriacetic acid is preferred.

What is the amount of polyisocyanate and polycarboxylic acid and/or polycarboxylic acid that has one acid anhydride group?

The equivalent ratio of the total carboxyl groups of the polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group to the total incyanate groups of the polyisocyanate (total carbonasyl groups/total incyanate groups) is 0.5 to 2. It is preferable to set it within the range of .0. Here, 1 equivalent of acid anhydride group is treated as 1 equivalent of carboxyl group. Sufficiently high molecular weight and highly 1iIlt thermal properties.

When a particulate polymer with resilience is required,
The equivalent ratio of carboxyl group to insia-un-1- group is preferably 0.85 to 1.15. More preferably, the amounts are adjusted to be substantially equivalent.

According to the present invention, gelled particulate polymers can also be obtained. In order to obtain a gelled particulate polymer, a resin composition containing a trifunctional or higher crosslinking component sufficient for gelation is reacted with a resin composition.
It's best to proceed in a trench that turns into a gel.

Among the above-mentioned polyincyanates, compounds that can be trifunctional or higher-functional crosslinking components include compounds obtained by converting diincyanates into three compounds, such as tolylene diyinanate, xylylene diisocyanate-1-,4,4'-diphenyl ether Diisocyanate, trimers of aromatic diisocyanates such as naphthalene-1,5-diincyanate and 4,4'-diphenylmethane diincyanate, ethylene diisocyanate, 1,4-tetramethylene diincyanate (.

1.6-hexamethylenecyane), 1.12-
Aliphatic diisocyanate tertiary products such as dodecane diisocyanate, cyclobutene-1,3-diisocyanate,
3M forms of alicyclic diisocyanates such as cyclohexane-1,3- and 1,4-diincyanate, influorone diisocyanate, triisocyanate compounds 2 such as triphenylmethane-4,4:4''-triisocyanate, polyphenylmethyl poly Examples of the isocyanate used include those obtained by reacting a condensate of aniline and formaldehyde with phosgene.These polyincyanates that can serve as crosslinking components can be used for all or part of the polyincyanate component.

Among the polycarboxylic acids and/or polycarboxylic acids having an acid anhydride group, trimellitic acid is an example of a compound that can serve as a trifunctional or higher functional crosslinking component.

Trimesic acid, pyromellitic acid, )')su(2-h-ruboxyethyl)in cyanurate, tricarpallic acid, nitrilotriacetic acid, nitrilotripropionic acid, etc. are used.

In the present invention, the polycarboxylic acid and polycarboxylic acid having an acid anhydride group to be reacted with the polyincyanate are 1
Either or both may be used.

What are the polycarboxylic acids that can serve as these crosslinking components?

It can be used for all or part of polycarboxylic acids and/or polycarboxylic acids having acid anhydride groups.

In addition to the method described below to obtain a gelled particulate polymer using a trifunctional or higher functional crosslinking component, there are methods such as a method of gelling using a side reaction and a method of gelling by sintering. For example, when reacting a bifunctional polyisocyanate with a polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group at an equivalent ratio of substantially 1.0, the two reactions are carried out at a high temperature of 120'C or higher for a long time. When passed through, a gelled particulate polymer is obtained due to a side reaction.

A first non-aqueous organic liquid as a continuous phase and a reactant as a dispersed phase (fI, (II) and/or (Ill) above)
The ratio of the amount of the reactant to the total amount of the first non-aqueous organic liquid and the reactant is preferably 10 to 80% by weight.

From the viewpoint of production efficiency and cost, a weight ratio of 40 or more is preferable.

The ratio of the amount of the second non-aqueous organic liquid to the reactant is within a range such that the amount of the second non-aqueous organic NK body is 0.5 to 70% by weight relative to the total amount of the second non-aqueous organic liquid and the reactant. is preferred. If the amount is less than 0.5, the polymerization reaction will proceed only at high temperatures, making undesirable side reactions more likely to occur. When the number of stitches exceeds 70, a continuous phase with a high specific gravity is formed in which the reactant is dissolved in the second non-aqueous organic liquid, resulting in phase separation from the first non-aqueous organic liquid with a low specific gravity, resulting in dispersion. It becomes difficult to form phases.

-Also, even if a 9-dispersed phase is formed, aggregation tends to occur during the polymerization reaction, which is also disadvantageous in terms of cost. Particularly preferably 1
A range of 30% by weight is used.

d, 80 as reaction temperature of polyisocyanate, polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group
~250°C is preferred.

The polymerization reaction is preferably carried out in an anhydrous state. Therefore, it is desirable to carry out the process in an inert atmosphere such as nitrogen gas. As a matter of course.

The particulate polymer obtained by the production method of the present invention quickly becomes inert when the reactant, particularly polyisocyanate, comes into contact with water. It is impossible to create !I!! with a dispersion medium in one step.For the reaction, all the original 1-metal gold may be charged at the same time, or in stages depending on the purpose.

You may differ in response.

At least one component of the reactant is added to the second non-aqueous organic liquid D1.
It is desirable to be soluble or swellable or liquid at the reaction temperature. Preferred specific example and L7.

A homogeneous solution in which all components except the acid component are mixed together, or a homogeneous solution in which a homogeneous solution of polyisocyanate and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. The reaction proceeds by adding a finely powdered acid component. According to this method, the polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed.

A homogeneous solution in which all components except the polyisocyanate are mixed or a homogeneous bath solution of an acid component and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid to form a heterogeneous solution. The reaction may be quenched by adding polyinocyanin-1.

Of course, it is also possible to proceed with the reaction by mixing all the components from the beginning. Schiff retains the dispersion stabilizer of particulate polymers during polymerization reactions.

In order to reduce the particle size, it is possible to use a method of adding a dispersion stabilizer in stages. A dispersion stabilizer may be used as a solution binding agent.

The 7L particulate polymer obtained according to the present invention is optionally mixed with methanol, n-butanol, benzyl alcohol, and ε-caprolactam during or after the reaction.

Stabilization can be achieved by adding a suitable blocking agent having one active hydrogen in the molecule, such as methyl ethyl ketone oxime, acetaldoxime, phenol, or cresol.

The stirring method used in the reaction involves high-speed shearing using an emulsifier (Pomomi Kitsu).

Mechanical cutting of particles with a propeller-type stirrer.

A method such as fP pulverization or stirring is used.

It is preferable to use the emulsifier in an overhead mode where the conversion rate of the reactant to the polymer is low. A desirable stirring method is to use an emulsifier at the beginning of the reaction to reduce the diameter of the particles, and then use a propeller-type stirrer to further advance the reaction. be. According to this method, it is possible to obtain a particulate polymer having a relatively small particle size and having smooth grains. Depending on the synthesis system, it is also possible to use an emulsifier to make particles into small particles before the reaction.

According to the manufacturing method that makes Kinoe tq (a particulate polymer t),
.

In addition to this particulate polymer, a second non-aqueous liquid, a dispersion stabilizer, a reactant, etc. are combined in the dispersed phase obtained by dispersing in the first non-aqueous organic liquid. These are removed by purification.

The particulate polymer obtained by this method is: Average particle size is 0.
It is obtained in non-agglomerated particle form ranging from 0.05 to 2000 ttm and above. The preferred average particle size is 0.1~
5000μm, most preferably 0.5-100μm
It is. The particulate polymer can be recovered from the dispersion solution by filtration or decantation and then drying under normal pressure or reduced pressure.

If necessary, in the particulate polymer obtained by the present invention,
Adding one or more of hydroxyl group-containing polyester resins obtained using epoxy resins, amine resins, phenol formaldehyde resins, isocyanurate ring-containing polyisocyanates, and terephthalic acid and/or inphthalic acid as acid components. , can be a composite material.

As an epoxy resin, Ebikoh828, 1001゜1
Bisphenol-based epoxy resin such as 004.1007,
Epoxidized novolak resins such as DEN431 and 438 (all trade names manufactured by Dow Chemical Company).

Triglycidyl isocyanurate and the like are preferred.

As the amine resin, melamine formaldehyde resin and its alkoxy-modified resin 1, such as butquine benzoguanamine formaldehyde resin, hexamethine melamine resin, etc. are preferred. Preferred examples of the phenol formaldehyde resin include phenol formaldehyde resins, alkylphenol formaldehyde resins, melamine-modified phenol formaldehyde resins based on these resins, and penzoguana-modified phenol formaldehyde resins. As the incyanurate ring-containing polyisocyanate, aromatic diincyanate is used.

Particularly preferred are trimers obtained by reacting tolylene diisocyanate in the presence of a tertiary amine, or polyincyanate mixtures containing incyanurate rings containing all trimers. As a polyester resin having a hydroxyl group obtained using terephthalic acid and/or isophthalic acid as an acid component, tris(2-hydroxyethyl) with a 9-branched acid content is used.
Preferred are polynisder resins using incyanurate, polyesterimide resins, polyesteramide resins, and the like. Such particulate polymers and their composites exhibit good heat resistance, 9 mechanical properties, and electrical properties.

Heat-resistant paint, rfjf heat sheet, heat-resistant adhesive, heat-resistant laminated material, heat-resistant sliding material, heat-resistant molded product, glass fiber,
It is useful for heat-resistant composite materials with carbon fiber. Particularly in the case of fine particle systems, a relatively stable dispersed phase can be obtained, so that the dispersion solution can be used as a dispersion paint. Furthermore, the gelled particulate polymer can be used as a heat-resistant thixotropic agent, a heat-resistant filler, and a lubricating oil thickener.

It is useful as an adsorbent for inorganic elements and a material for separating organic compounds.

The present invention will be explained using Examples and Comparative Examples.

Example 1 (1) Synthesis of dispersion stabilizer In a four-loaf flask equipped with a thermometer, a stirrer, and two bulb condensers, 1529 gold of 15OPA-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) was placed. , the temperature was raised to 120°C. While passing nitrogen gas, a mixture of 10 g of lauryl methacrylate isag and 18.69° glycidyl methacrylate benzoyl peroxide paste (benzoyl peroxide content: 50) was added dropwise over 2 hours while stirring. Subsequently, the temperature was raised to 140'C, and the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution has a nonvolatile content of 40% by weight when dried at 170°C for 2 hours.
The number average molecular weight (determined by gel permeation chromatography using polystyrene of known molecular weight as a calibration curve; the same applies hereinafter) of the Adashi 1 dispersion stabilizer was 8,000.

(2) Synthesis of particulate polymer While passing nitrogen gas through a 500 ml four-hole flask equipped with a thermometer, a stirrer, and a bulb-and-tube condenser.

4. Dispersion stabilizer m liquid obtained from 4'-diphenylmethane diisocyanate 759° (1) (non-volatile content 40%) 1
99, 15OPAR-H1509, N-methylpyrrolidone 339 was added, and the temperature was raised to 90°C while stirring at 3 s or p, m. In this state, these mixtures became a homogeneous solution. Finely powdered trimellitic anhydride 729 was added in advance.

1 hour at 100°C, 1 hour at 115°C, then 125°C
The reaction was allowed to proceed for 4 hours. Continuous phase l5OPAR
-I- (Since we obtained brown particulate polymer dispersed in
This was collected by filtration, further boiled with methanol and separated under reduced pressure.

It was dried at 60°C for 5 hours. The infrared absorption spectrum of this particulate polymer includes an imide bond at 1780 cm-”;
Absorption of amide bonds was observed at 1650 cm-1 and 1540 cm-1. The main particle diameter of this polyamide-imide particulate polymer was about 10 to 60 μm.

Example 2 The dispersion stabilizer solution obtained in Example (1) was
A particulate polymer was synthesized and treated in exactly the same manner as in Example 1 (2) except that 100 g of 09, 180P, and 1-H were used.

The infrared absorption spectrum of the obtained particulate polymer has 178
Imide bond at 0cm'', 1650cm-' and 1540
Absorption of amide bond was observed at cm-'.

The main particle diameter of this polyamide-imide particulate polymer is about 30
It was ~40 μm. Furthermore, 10 g of the obtained polyamide-imide particulate polymer, 10 g of bisphenol type epoxy resin Epicoat 828 (trade name manufactured by Shell Chemical Co., Ltd.) and 2f of curing aid) Z-CN (trade name manufactured by Shikoku Kasei Co., Ltd.) 0.19
were distributed and heated according to a conventional method at 130°C for 3 hours, 160°C for 5 hours, and 200°C for 10 hours to prepare HDT test pieces.

1-IDT exhibited good heat resistance at 177°C.

Example 3 (1) Synthesis of dispersion stabilizer Using the same apparatus as in Example 1, (1), 152 g of 15OPAR-H and 839 g of lauryl methacrylate were placed in a flask. Add 7.4g of glycidyl methacrylate and
The temperature was raised to 0°C. While passing nitrogen gas.

Pre-prepared lauryl methacrylate 839, glycidyl methacrylate 29.89. Benzyl peroxide paste (benzoyl peroxide content 50%) 2.0
The mixture was added dropwise over 2 hours while stirring.

Continue to incubate at 100℃ for 1 hour, and
009 was added. The temperature was further raised to 140°C, and the reaction was continued at the same temperature for 4 hours.

When this dispersion stabilizer solution was dried at 170° C. for 2 hours, the nonvolatile content was 42.2% by weight, and the number average molecular weight of Dispersion Stabilizer 7 was 54,000.

(2) Synthesis of particulate polymer The dispersion stabilizer solution obtained in Example (1) was prepared in 8.
Example 1 except that 5g was used. A particulate polymer was synthesized and treated in exactly the same manner as in (2).

The infrared absorption spectrum of the obtained particulate polymer has 178
Imide bond 1650ca-' and 1540c to 0cm-''
+n'' absorption of amide bond was observed.

The main particle diameter of this polyamide-imide particulate polymer is 20~
It was 200 μm.

Example 4 4.4'-diphenylmethane diinciai, -257
．． 19. ) Limellitic anhydride 246.99°N-methylpyrrolidone 113.1 g, 15OPAR-H493
, 59 and Example 3, 89.49 g of the dispersion stabilizer solution obtained in (1) were mixed and the reaction was allowed to proceed for 1 hour at 100° while stirring at high speed using a homogenizer.

Thereafter, it was transferred to the same apparatus as in Example 1, +1), and 11
5'C for 1 hour, then the temperature was further raised to 125°C to proceed with the reaction for 4 hours, and after one reaction was completed, it was treated with methanol and dried.

The infrared absorption spectrum of the obtained particulate polymer has 178
Imide bond at 0 cm-1, 1650 cm-1 and 154
Absorption of amide bond was observed at 0 cm''.

The main particle diameter of this polyamide-imide particulate polymer is about 0.
It was 5 to 2 μm.

Example 5 (1) Synthesis temperature H of tolylene diisocyanate trimer
Tolylene dicyanate 10009, anisic acid 0.52 in a fourth flask equipped with a stirrer and a bulb and tube condenser.
G, 0.3009 g of dimethylamine ethanol was added, and the temperature was raised to 80° C. while passing nitrogen. At the same temperature, the content of incyanate groups (initial concentration = 48 M%) was reacted to 16% by weight to 32% by weight. In the infrared absorption spectrum of this product, absorption of isocyanate rings was observed at 1710 cm'' and 1410 cm-', and absorption of isocyanate groups was observed at +2260 cm''.

(2) Synthesis of gelled particulate polymer 4.4'-diphenylmethane diisocyanate 4-s, 4-ta while passing nitrogen gas through a four-bottle flask equipped with a thermometer, a stirrer, and a 9-ball condenser. , (2)
48.4 l.lisi/ndiisocyate trimer obtained in
9. Example 3, dispersion stabilizer solution obtained in (1) (non-volatile content 4227Jj%) 19.0 g, 15OP
A, R-H 150g, N-methylpyrrolidone 339.
) Limelinotic anhydride 37.29 was added and heated at 110°C for 1 hour, at 120°C for 1 hour, at 130°C for 1 hour, at 140°C.
The reaction was carried out at 150°C for 1 hour, 150°C for 1 hour, and 160°C for 2 hours. A part of the brown particulate polymer dispersed in 15OPA-11 was taken out with a pipette, and N-methylbi
The particulate polymer was added to 1 J.

It did not dissolve in N-methylpyrrolidone, and N-methylpyrrolidone did not color. This was then collected by filtration, washed with II-hegisan and then with atenthone, and then dried at 60° C. for 5 hours under reduced pressure.

The infrared absorption spectrum of this particulate polymer.

Imide bond at 1780cm'', 1650cm-' and 1
Absorption of an amide bond was observed at 540 cm-''.

When this particulate polymer was observed with a scanning Shinkoura microscope, it was found to be spherical in shape, with a main particle diameter of approximately 5 to 30 μm. 15OI)AR-H7f3g, stearyl methacrylate-I-110.5g and glycidyl methacrylate 6.8g in a flask using
g and the temperature was raised to 100°C. I S 0PAR-I-1769 was prepared by passing nitrogen gas through it.
, stearyl methacrylate) 110.59. 27.2 g of glycidyl methacrylate and benzoyl peroxide paste ('J17ii benzoyl oxide content 50 nails i≠) 1.
The mixture of No. 09 was added dropwise over 2 hours while stirring. Furthermore, 15OPAR-f (3009) was added dropwise over 1 hour, and then the temperature was raised to 140°C and the reaction was carried out with milk at the same temperature for 5 hours. This dispersion stabilizer solution had a non-volatile content of 30% when dried at 170°C for 2 hours. Yes.

The number average molecular weight of the dispersion stabilizer was 110,000.

(2) Synthesis of Particulate Polymer A particulate polymer was synthesized and treated in exactly the same manner as in Examples 1 and (2), except that the dispersion stabilizer solution obtained in (1) was used.

stomach! The infrared absorption spectrum of the particulate Jll aggregate includes an imide bond at 1.780 cm and an imide bond at 1650 cm.
-' and 1540 cm'' absorption of amide bond was observed.

The main particle diameter of this polyamitoy particulate polymer aggregate is approximately 25
It was ~35 μm.

Example 5 Example 7 Using the same apparatus as in Example 1 and (2), open the 4,4'-diphenylmethane diincia door 59. while passing the distillate gas. -X, male side 6, +1. ) night (non-volatile content 30% by weight) 309, l5
OJ, “AR-H130g, N-notirubi+7ridone 3
39 gold coins.

The temperature was raised to 90°C while stirring. Add 64.79 g of pyromellitic anhydride, which has been finely powdered in advance, and
1 hour at 0℃, 1 hour at 120℃.

The reaction was continued at 140° C. for 1 hour and further heated to 180° C., and the end point was when the acid value of the 9 polymer reached 60 CK, OHmg/9]. A brown particulate polymer dispersed in 15OPAI (, -H) was obtained, which was recovered by filtration, boiled with methanol, and then dried at 60° C. for 5 hours under reduced pressure.

The infrared absorption spectrum of this particulate composite is 1780c.
Absorption of imide bond was observed in ``m''.

No absorption of amide bonds was observed at 1650 cm-' and 1540 cm-1. The main particle diameter of this polyimide particulate polymer was approximately 10-80 μIn.

Example 8 Using the same equipment as in Example 1 (21), while passing nitrogen gas, 75 g of 4,4'-diphenylmethane diincyane-1, the dispersion stabilizer obtained in Example 6 (1) Solution (30 layers of non-volatile content) 309, ■5op
Add 130g of -H and 339g of N-methylpyrrolidone to A1.

The temperature was raised to 90°C while stirring. 493 g of isophthalic acid, previously pulverized, was added.

1 hour at 100℃, 1 hour at 115℃, then 130℃
The temperature was raised to 70 (KOH
■/g] was taken as the end point.

A white particulate polymer dispersed in the continuous phase 15OPAR-H was obtained, which was recovered by one filtration.

After washing with n-hegisan, it was dried under reduced pressure at 60°C for 5 hours. In the infrared absorption spectrum of this particulate polymer, no imide bond absorption was observed at 1.780 cm-', but only amide bond absorption was observed at 1650 cm-' and 1540 cm-'. . The main particle diameter of this polyamide particulate polymer was approximately 20 to 80 μm.

Comparative Example 1 (1) Synthesis Example 1 of Dispersion Stabilizer. Using a device similar to (1), add I to the flask.
152 g of 5OPAR-H was added and the temperature was raised to 160°C. While passing nitrogen gas, lauryl methacrylate 183.39. A mixture of 30.6 g of glycidyl methacrylate and 11.7 g of benzoyl peroxide paste (benzoyl peroxide content: 50%) was added dropwise over 2 hours with stirring. Subsequently, the reaction was continued at the same temperature for 4 hours.

When this dispersion stabilizer solution was dried at 170° C. for 2 hours, the nonvolatile content was 25 times, and the number average molecular weight of one dispersion stabilizer was 2,600 lζ.

(2) Synthesis of particulate polymer 1 A particulate polymer was synthesized in exactly the same manner as in Example 1 and (2+) except that the dispersion stabilizer solution obtained in (1) was used. At the end, it agglomerated after 15 minutes.

Comparison fl12 (1) Synthesis of dispersion stabilizer Example 1 Using the same apparatus as in (1), 152 g of 15OI)AR-H was placed in a flask and the temperature was raised to 80°C. While passing nitrogen gas, lauryl methacrylate 183.09. A mixture of 12.0 g of glycidyl methacrylate and 1.09 g of benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) was added dropwise with a knife for 2 hours while stirring. Furthermore l5OPAR-
After dropping 100 g of H over 1 hour and keeping the temperature at 80°C for 1 hour.

The temperature was raised to 140°C, and M1 reaction was carried out at the same temperature for 4 hours.

When this dispersion stabilizer solution was dried at 170° C. for 2 hours, the nonvolatile content was 50% by weight, and the number average molecular weight of the dispersion stabilizer was 250,000.

(2) Synthesis of particulate polymer Synthesis was carried out in exactly the same manner as in Examples 1 and (2) except that 38 g of the dispersion stabilizer solution obtained in (1) was used, but the temperature was raised to 115 °C. Aggregation occurred after 30 minutes.

Comparative Example 3 (1) Synthesis of dispersion stabilizer Example 1 Using the same equipment as in (1), 3 g of 15OPAR-H and 97.8 g of lauryl and methacrylate were placed in a flask, and the temperature was raised to 80°C. did. While passing nitrogen gas, a mixture of 97.8 g of lauryl methacrylate and benzoyl peroxide paste (benzoyl peroxide content: 50 for Shigekawa), which had been prepared in advance, was added dropwise over 2 hours while stirring. Furthermore l5OPA
After dropping 74.3 g of R-1-i over 1 hour, the mixture was kept at 80°C for 1 hour.

The reaction was carried out at 100°C for 1 hour and at 140°C for 5 hours.

This dispersion stabilizer solution was dried at 170° C. for 2 hours; the nonvolatile light content at this time was 53%, and the number average molecular weight of the Uri 1 dispersion stabilizer was 134,000.

(2) Synthesis of particulate polymer Dispersion stabilizer solution obtained in (1) was added to 3097+j
The synthesis was carried out in exactly the same manner as in Examples 1 and (2) except that trimellitic anhydride was added and
When reacted for 0 minutes, aggregation occurred.

Comparative Example 4 The entire synthesis was carried out in exactly the same manner as in Example 1, (1) except that 1.0 g of the dispersion stabilizer solution obtained in Example 1, (1) was used. was added and the temperature was raised to 115°C, after which it coagulated in 30 minutes.

As is clear from the above, it is shown that a particulate polymer with excellent heat dissipation properties can be stably produced using Fukkatsu Hitotto.

5”!・4ノ

Claims (1)

[Claims] 1. A first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a particulate polymer to be produced. polyisocyanate) (1
) and polycarboxylic acid (It) and/or polycarboxylic acid +II [l having an acid anhydride group to form a particulate polymer dispersed in the first non-aqueous organic liquid. In the method for producing a polymer, as the dispersion stabilizer, an ethylenically unsaturated monomer having a side chain consisting of a hydrocarbon group having 6 or more carbon atoms and an ethylenically unsaturated monomer having an epoxy group +B) are used in moles. Prisoner/(B) in ratio from 1/1 to 6/1
The number average molecular weight obtained by reacting in the range of 6000
The above epoxy group-containing vinyl polymer is mixed with a second non-aqueous organic liquid, polyinocyanate. A method for producing a particulate polymer, characterized in that it is used in an amount of 0.5% by weight or more based on polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group. 2. The particulate polymer according to claim 1, wherein the epoxy group-containing vinyl polymer is a random copolymer of lauryl methacrylate, stearyl methacrylate, lauryl acrylate, or stearyl acrylate and glycidyl acrylate or glycidyl methacrylate. Production method. 3. The particulate form according to claim 1 or 2, wherein the first non-aqueous organic liquid is an aliphatic or alicyclic hydrocarbon, and the second non-aqueous organic liquid is N-methylpyrrolidone. Method for producing polymers. 4. Polyisocyanate (1) contains 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, tolylene diisocyanate, triphenylmethane-4,4', 4''-)riisocyanate or incyanurate ring 5. A method for producing a particulate polymer according to claim 1, 2 or 3, which is a polyisocyanate having an acid anhydride group. 5. Polycarboxylic acid [11] having an acid anhydride group is trimellitic anhydride , pyromellitic dianhydride. 3,3', 4,4'-benzophenonetetracarboxylic dianhydride or 2,2-bis[:4-(3,4-dicarboxyphenoquine)phenyl]globannianhydride A method for producing a particulate polymer according to claim 1, 2, 3 or 4. 6. The polycarboxylic acid (river) is Innotal NL polymer, trimesic acid, trimesic acid, Tris(2-carboxyethyl)
A method for producing a particulate polymer according to claim 1, 2, 3, 4.1J11 or 5, which is prepared using isocyanate or nitrilotriacetic acid.