JPS582348A - Preparation of granular polymer containing imide group - Google Patents

Abstract

PURPOSE:To prepare the titled polymer having excellent heat resistance, mechanical characteristics and electrical characteristics, and suitable for heat-resistant sheet, etc., by reacting a polyisocyanate with a polycarboxylic acid containing acid anhydride group, etc. in the presence of a non-aqueous organic liquid. CONSTITUTION:A granular polymer having an average particle size of 0.05- 2000mu and containing imide group is prepared by mixing (A) a polyisocyanate (preferably 4,4'-diphenylmethane diisocyanate, etc.) with (B) a polycarboxylic acid containing acid anhydride group (preferably trimellitic anhydride, etc.) and if necesary (C) a polycarboxylic acid other than the component (B) (e.g. trimellitic acid) in the presence of an essentially insoluble non-aqueous organic liquid (e.g. acetone), and heating and stirring the mixture. The equivalent ratio of the total carboxyl group of the polycarboxylic acid to the total isocyanate group of the polyisocyanate is preferably 0.5-2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing particulate polymers containing imide groups. More specifically, the main polyisocyanate and a polycarboxylic acid containing an acid anhydride group are reacted in a solution state in an expensive solvent such as -N-methylpyrrolidone, dimethylformamide, or dimethylacetamide.
It has been proposed to obtain imide group-containing polymer solutions 9, such as polyamide solutions and polyimide solutions. However, in order to obtain a solid polymer from such a polymer solution, it is necessary to remove or recover the solvent by an 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 containing imide groups generally have rigid and highly polar molecular structures and are characterized by high glass transition temperatures.

Therefore, when applying the bulk polymerization method, it is generally necessary to
Since the reaction must proceed under harsh conditions of high pressure, it is difficult to control each reaction and suppress side reactions. There have been no examples of successful practical application.

The inventors. As a result of repeated studies on a method for producing a particulate polymer containing an imide group that is inexpensive and has excellent heat resistance, a method for producing a particulate polymer containing an imide group dispersed in a non-aqueous organic liquid was completed. I ended up doing it.

In the present invention, polycarboxylic acids (formerly called polyisocyanates) (If, and polycarboxylic acid (III) other than polycarboxylic acid (II) containing an acid anhydride group as necessary
The present invention relates to a method for producing particulate polymers containing imide groups by reacting them.

According to the production method of the present invention, the particulate polymer containing imide groups is obtained as a dispersion of relatively small particles in a non-aqueous organic liquid, and therefore can be easily recovered from the dispersion by an r-filtration operation. Furthermore, unlike solution polymerization methods that use expensive solvents such as N-methylpyrrolidone, in the production method of the present invention, the non-aqueous organic liquid is essentially insoluble in particulate polymers containing imide groups. Some cheap general purpose solvents can be used. Unlike solution polymerization methods, which have a limit to high solid fractionation due to the insolubility of imide group-containing polymers in solvents.

According to the present invention, high solids contents of 50 weight percent or more can be obtained in non-aqueous organic liquids.

In addition, the conversion rate of monomers into particulate polymers in the present invention can be sufficiently increased in the reaction melting range of solution polymerization, and the reaction can be completed under relatively mild conditions, so side reactions etc. No loss of purity. In addition, one distinctive feature that differs from the solution polymerization method of the present invention is that it is possible to directly obtain a three-dimensional network-formed (gelled) particulate polymer that is substantially insoluble in a solvent. Such gel particles can be used as an adsorbent for inorganic elements or as a material for separating organic compounds.

The non-aqueous organic liquid used in the present invention is a non-aqueous organic liquid that is essentially insoluble in the particulate polymer containing imide groups and has inert properties that do not inhibit the polymerization reaction. Here, 1. Essentially insoluble means that in addition to being completely insoluble in particulate polymers containing imide groups, it also encompasses non-aqueous organic liquids that are not completely insoluble but have extremely low solubility. shall be used in This non-aqueous organic 5-liquid with extremely low solubility swells the imide group-containing particulate polymer during the polymerization process, resulting in a higher reaction rate than using a completely insoluble non-aqueous organic liquid. .

It has been found that it has the desirable property of producing a particulate polymer with a high degree of polymerization. The non-aqueous organic liquid that is completely insoluble and the non-aqueous organic liquid that has extremely low solubility that causes swelling may be used alone or in combination.

The non-aqueous organic liquid that is essentially insoluble in the imide group-containing particulate polymer produced in the present invention is 1
For example, ketones such as acetone, methyl isobutyl ketone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, cellosolves such as methyl cellosolve acetate and ethyl cellosolve acetate, and ethers such as tetrahydrofuran and dioxane.
1. n-hexane, octane, dodecane, I! 90 pages
ARI-E, l5OPAR-H, l5OPAR-K
(The above are trade names manufactured by Esso Standard Oil Co., Ltd.) etc. 6- Aliphatic or fatty flR group Id hydrocarbons such as petroleum-based saturated aliphatic or fat-encrusted hydrocarbons with a boiling point range of about 40 to 300°C 1i, benzene , toluene, xylene and Nl5SEK
I HISOL-100, Nl5SEKIHISOL-
Aromatic RS hydrocarbons such as petroleum-based aromatic hydrocarbons with a boiling point range of about 80 to 300°C such as 1SO (all trade names manufactured by Nippon Petrochemical Co., Ltd.), acetonitrile, γ-7 tyrolactone, ethylene carbonate, propylene carbonate, etc. is used. Considering the reaction temperature, the boiling point is 80
℃ or higher is preferable. It is preferable to solubilize a simple substance in order to suppress side reactions and carry out the reaction at a relatively low temperature. However, a part of non-aqueous organic liquid soluble in the particulate polymer containing imide groups such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, phenol, and cresol fZ can be used in combination.

The amount used is enough to swell the particulate polymer,
The particulate polymer dispersed in the non-aqueous organic liquid can be used as long as it does not aggregate or become a solution. This soluble well water organic liquid.

Preferably, the particulate polymer containing imide groups has poor compatibility with essentially insoluble non-aqueous organic liquids. In this case, the soluble non-aqueous organic liquid is efficiently distributed in the dispersed phase of the particulate polymer, thereby promoting the single polymerization reaction and making it possible to obtain a particulate polymer with a high degree of polymerization.

Examples of the polyisocyanate used in the present invention include tolylene diisocyanate, xylylene diisocyanate, 4,4-diphenyl ether diisocyanate,
Aromatic diisocyanates such as naphthylene-1,5-diisocyanate and 4,4'-diphenylmethane diisocyanate.

aliphatic diisocyanates such as ethylene diisocyanate), 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate, cyclohexane 1,3- and 1 .4-diisocyanate, alicyclic diisocyanate such as isophorone diisocyanate, triphenylmethane-4,44-)
Polyisocyanates such as lysocyanate and isocyanurate ring-containing polyisocyanates obtained by trimerization of these polyisocyanates are used.

Considering heat resistance etc.

It is preferable to use aromatic diisocyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and isocyanurate ring-containing polyisocyanates obtained by trimerization of these aromatic diisocyanates. A suitable method for producing isocyanurate ring-containing polyisocyanates is disclosed in Japanese Patent Application No. 1983-1.
No. 48820. Isocyanurate ring-containing polyisocyanates are used as branching components, and the isocyanurate ring core provides excellent heat resistance. Difunctional polyisocyanates are used in the synthesis of particulate polymers containing imide groups that are substantially linear and thermoplastic. In addition, for the synthesis of particulate polymers containing 9-branched thermosetting imide groups and particulate polymers (gel particles) containing 2 imide groups that are insoluble in solvents and formed into 9-dimensional networks, trifunctional A polyisocyanate of higher than 100% is used. These polyisocyanates may be used alone or in combination depending on the purpose. Polyisocyanates are used to control the reaction rate in the polycondensation reaction process and to obtain stable particulate polymers, such as methanol, n-butanol, benzyl alcohol, ε-caprolactam, methyl ethyl ketone oxime, and phenol.

One stabilized with a suitable blocking agent having one active hydrogen in the molecule, such as cresol, may be used.

Polycarboxylic acids containing acid anhydride groups include trimellitic anhydride, 1,2.4-butanetricarboxylic acid-1,2-anhydride, 3.4.4-benzophenonetricarboxylic acid-3, Tricarboxylic acid anhydrides such as 4'-anhydride, 1゜2.3.4-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, bicyclo-(2,2,2
)-octene-(7)-2,3,5,6-tetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-C2,2,2]-oct-(
Aliphatic and ring-based tetrabasic acids such as carene-2:3,5:6-tetracarboxylic dianhydride, pyromellitic acid, 3.3', 4.4'-benzophenonetetracarboxylic acid, bis( 3,4-dicarboxyphenyl)ether, 2,3,6.7-naphthalenetetracarboxylic acid, 1
．． λ5.6-naphthalenotetracarboxylic acid, ethylene glycol bistrimelitate, a2-bis(3,4-biscarboxyphenyl)furopane, 2.2', 3.
3'-diphenyltetracarboxylic acid, perylene-3,4
, 9,10-tetracarboxylic acid, aromatic tetrabasic acids such as 3,4-dicarboxyphenylsulfone, thiophene-2
, 3,4,5-tetracarboxylic acid, pyrazinetetracarboxylic acid, etc.? J elemental cyclic basic acid which tetrabasic acid di or -
Examples include anhydrides.

A polyamide-imide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxy group, such as tricarboxylic anhydride, and a polyisocyanate. still,
A polyimide can be obtained from a polycarboxylic acid containing only an acid anhydride group, such as tetracarboxylic dianhydride, and a polyisocyanate. Generally heat resistant,
Considering cost etc., trimellitic acid anhydride, 3.
3', 4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, and the like are preferred.

If necessary, polycarboxylic acids other than the polycarboxylic acids containing acid anhydride groups described above can also be used. Examples of such polycarboxylic acids include trimellitic acid, trimesic acid, tris(2-carboxyethyl)i, isocyanurate, terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and the like. These polycarboxylic acids are flexible.

Solubility in solvents, melt flowability (processability) during molding, etc.? It can be used to modify resin properties. The amount of polyisocyanate and polycarboxylic acid to be used is determined by the equivalent ratio of all carboxyl groups in polycarboxylic acid to all isocyanate groups in polyisocyanate (total carboxyl groups/
It is preferable that the total number of isone anate groups is within the range of 0.5 to 2.0. Here, one equivalent of acid anhydride group of polycarboxylic acid is taken as one equivalent of carboxyl group. Fully polymeric and advanced! When a particulate polymer containing an imide group having heat resistance and elasticity is required,
The equivalent ratio of carboxyl group to incyanate group is preferably 0.85 to 1.15. More preferably, they are adjusted to have substantially equivalent weights. The reaction temperature for the reaction between polyisocyanate and polycarboxylic acid is 80 to 25
0°C is preferred. The progress of the reaction can be gauged by observing the bubbles of carbon dioxide gas generated.

Preferably, the polymerization reaction is carried out in substantially anhydrous conditions. Therefore, it is desirable to carry out the process under an inert atmosphere such as nitrogen gas. Naturally, 1 the imide group-containing particulate polymer obtained by the production method of the present invention is produced by contacting the monomer, particularly the polyisocyanate, with water.

−】　3− To rapidly transform into inert compounds.

It is not possible to produce water as a dispersion medium. For the reaction, all the raw materials may be charged at the same time, or depending on the purpose, they may be charged in stages to avoid the 9 reactions. : The method of introducing monomers in the present invention requires some modification depending on the properties of the monomers. Preferably, at least one component of the monomer is soluble in the non-aqueous organic liquid or is liquid at zero reaction temperature. The reactive monomer which is solid at the reaction temperature is used by being dissolved in a non-aqueous organic liquid before charging or during the reaction, or by being fused with another monomer which is liquid at the reaction temperature. As a preferred example, a reaction is carried out by adding a finely powdered acid component to a homogeneous solution in which a non-aqueous organic liquid and a polyisocyanate are mixed, or a heterogeneous solution in which a polyisocyanate having the width of oil droplets is dispersed in an organic liquid. You may proceed.

The reaction may proceed by adding polyisocyanate to a homogeneous solution of a mixture of a non-aqueous organic liquid and a polycarboxylic acid or a heterogeneous solution of a polycarboxylic acid in the form of oil droplets dispersed in a non-aqueous organic liquid. .

Stirring methods used in the reaction include stirring methods involving high-speed shearing using an emulsifier (homomixer), precise cutting of particles using a propeller-type stirrer, and stirring methods that do not involve pulverization. The emulsifier is preferably used in areas where the conversion of reactive monomer to polymer is not very high. A more sophisticated stirring method is to use an emulsifier to reduce the particle size at the beginning of a reaction, and then use a propeller-type stirrer near the polymerization group where the particles have good dispersion stability to proceed with the reaction further. . According to this method, a particulate polymer having a relatively small particle size and a uniform particle size can be obtained.

The particulate polymer containing imide groups obtained in the water droplet is obtained in a non-agglomerated particle form with an average particle size ranging from 0.05 to 2000 microns and above. The preferred average particle size is from 0.1 to 500 microns, most preferably from 0.5 to 100 microns. The particulate polymer can be recovered from the dispersion solution by filtration or decantation and then drying under normal pressure or reduced pressure.

According to the present invention, one type of particulate polymer containing imide groups is obtained as a thermoplastic or thermosetting particulate polymer soluble in a solvent.

To such polymers, if necessary, epoxy resins.

Ami 7m+1, by adding any one or more of a hydroxyl group-containing polyester resin obtained using a phenol formaldehyde isocyanurate ring-containing polyisocyanate and terephthalic acid and/or isophthalic acid as an acid component.

It can be a composite material. Epoxy resins include Epicoat 828, 1001, and 1004.

]007'J bisphenol-based epoxy resin.

Evosilized novolac resins such as DEN 431 and 438 (trade names manufactured by Dow Chemical Company) are preferred. Amino 14 +1 includes melamine formaldehyde resin and its alkoxy-modified resin.

For example, butoxybenzoguanamine formaldehyde resin. Hexamethoxymelamine resin and the like are preferred. As a phenol formaldehyde resin. Phenol formaldehyde Dorkylphenol formaldehyde resin, melamine modified phenol formaldehyde resin based on these resins. Penzodaanamine-modified phenol formaldehyde resin and the like are preferred. The isocyanurate ring-containing polyisocyanate is preferably a trimer obtained by reacting an aromatic diisocyanate, especially tolylene diisocyanate in the presence of a tertiary amine F, or an isocyanurate ring-containing polyisocyanate mixture containing a trimer. . Polyester resins with hydroxyl groups obtained using terephthalic acid and/or inphthalic acid as acid components include:
Polyester resins and polyesterimide resins using tris(2- and droxyethyl) isocyanurate as a branching component. Polyesteramide resin and the like are preferred. Particulate polymers containing such imide groups and composite materials thereof have good heat resistance. Mechanical properties. Shows electrical characteristics. Heat resistant paint.

Heat-resistant sheets, heat-resistant adhesives. Heat-resistant laminated material. Heat-resistant molded product, glass fiber. It is useful for heat-resistant composite materials with carbon fiber.

The imide group-containing particulate polymer obtained by the production method of the present invention is obtained in the form of three-dimensionally networked gel particles that are insoluble in solvents.

These gel particles are adsorbents for inorganic elements. It is also useful as a material for separating organic compounds.

The present invention will be explained below using examples.

Example 1 Temperature needle. Stirring machine. 4,4-diphenylmethane diisocyanate 75i in a four-loaf flask equipped with a bulb condenser.
, add 308t of cyclohexanone.

The temperature was raised to 80°C while stirring. Trimellitic anhydride 57 finely powdered in a mortar? Add. 15 in nitrogen stream
The temperature was raised to 0°C over 3 hours. The reaction was continued for 4 hours at the same temperature. A bright red particulate polymer dispersed in cyclohexanone was obtained. Collect this in one pass. It was dried for 18 hours at 60°C under reduced pressure. The infrared absorption spectrum of this particulate mass includes imide fa at 1780 crn-' and 165
Absorption of amide binder was observed at 0cm-' and 1540cm-''.Reduced viscosity was 0.13 (0.5FF/
dimethylformamide 100d solution). The particle size of this polyamideimide particulate polymer averaged about 10 microns.

Example 2 Into a fourth flask equipped with a temperature needle, a stirrer, and a bulb condenser, 15opAa$-n (trade name manufactured by Nip Standard Oil Co., Ltd.) 122P, N-methylpyrrolidone 13i,) was added.
Limellitic anhydride 57? It was placed.

The temperature was raised to 180° C. to obtain a transparent solution separated into two layers. 4,4-diphenylmethane diisocyanate was heated at 60°C in a nitrogen stream while vigorously stirring the resulting solution with an emulsifier.
40f of the melted material was added dropwise over 1 hour. The reaction was further continued at the same temperature until no carbon dioxide gas was produced. Continue to replace the emulsifier with a propeller agitator, 4.4
'-Diphenylmethane diisocyanate melted at 60°C 35? was added dropwise over 1 hour. The reaction was continued for an additional 4 hours while keeping the temperature at 180°C. A bright-colored particulate polymer dispersed in 1SOPAR-H was obtained, which was collected by filtration, washed with n-hexane, and then washed under reduced pressure.
It was dried at 60°C for 5 hours. In the infrared absorption spectrum of this particulate polymer, absorptions of an imide bond at 1780 crn-1 and amide bonds at 1650 cm and 1540 crn were observed. The reduced viscosity was 0.3 (0.5F/dimethylformamide 100mj solution). The particle size of this polyamide-imide particulate polymer is approximately 50
0 microns, with an average of about 20 microns.

Example 3 4,4-diphenylmethane diisocyanate 125 was added to a fourth flask equipped with a thermometer, stirrer, and two bulb condensers.
fF and 286 pi of cyclohexanone were added, and the temperature was raised to 80°C while stirring. Finely powdered in a mortar 3, 3:
4.4. 161 t of '-benzophenone tetracarboxylic dianhydride was added, and the temperature was raised to 110° C. over 3 hours in a nitrogen stream. Subsequently, the temperature was raised to 135°C, and the reaction was continued at the same temperature for 3 hours. A bright yellow particulate polymer dispersed in cyclohexanone was obtained, which was recovered by filtration and dried under reduced pressure at 60° C. for 5 hours. In the infrared absorption spectrum of this particulate polymer, an imide bond absorption was observed at 1780 crn-''. The average particle size of this polyimide particulate polymer was 20 mixene.

Example 4 (1) Synthesis component of incyanurate ring-containing polyisocyanate Gram tolylene diisocyanate 600 xylene
600 2-dimethylaminoene sixol (catalyst) 1.
8.Pour the above ingredients into a four-bottle flask equipped with a thermometer and a stirrer, and raise the temperature to 140°C in a nitrogen stream. At the same temperature, the content of isocyanate groups (initial concentration: 48 weight percent) becomes 25 weight percent. I admired the reaction. The infrared spectrum of this thing has 1710 cm-”,
14] Absorption of isocyanurate ring was observed at 0crn-”.

Absorption of isocyanate groups was observed in 2l-2260t-n+.

(2) Synthesis of particulate polymer containing imide groups Thermometer, 15 liters in a four-loaf flask equipped with a stirrer 1 before fractional distillation
OPAR-H (product name manufactured by Nip Standard Oil Company)
22Of, N-methylpyrrolidone 22p,) limelinotic anhydride 967 was added, and the temperature was raised to 180°C to obtain a clear solution that separated into two layers. While vigorously stirring in an emulsifier in a nitrogen stream, 51 L of isocyanurate ring-containing polyisocyanate (50% solution) synthesized in (1) above and 4.4
A mixed solution of 100P ('-diphenylmethane diisocyanate) was added dropwise over 20 minutes.

Subsequently, the reaction was continued at the same temperature for 6 hours by replacing the milk stirrer with a propeller stirrer. Xylene distilled out during the reaction was removed from the system. A particulate polymer dispersed in l80PAR-H was obtained, which was recovered by filtration and n-
After washing with hexane, it was dried at 150° C. for 5 hours under reduced pressure.

The infrared absorption spectrum of this particulate polymer has 22- Imide bond at 1780 cm-', 1650z.

Absorption of an amide bond was observed at 1540 cm-''.

This polyamide-imide particulate polymer was a gel particle insoluble in polar solvents such as N-methylpyrrolidone and dimethylformamide. The particle size ranges from large to approximately 200 microns.

Its average particle size was about 20 microns.

23- 375-

Claims (1)

[Scope of Claims] 1. In the presence of the present non-aqueous organic liquid, which is essentially insoluble with respect to the particulate polymer containing imide groups to be produced, polyisocyanate, i, ltom acid anhydride A polycarboxylic acid (If) containing a group and optionally an acid anhydride group (containing an imide group characterized by reacting with a polycarboxylic acid (■) other than the former ゛) Method for producing a particulate polymer. 2. The polyisocyanate (1) is 4,4'-diphenylmethane syrecyanate, tolylene diisocyanate, xylylene diisocyanate, or isocyanurate a
3. A method for producing a particulate polymer containing an imide group according to claim 1, which is a polyisocyanate containing an acid anhydride group. A method for producing a particulate polymer having an imide group according to claim 1 or 2, which is anhydride, pyromellitic anhydride, and luponic dianhydride.
. 4. Particles containing an imide group according to claim 1', 2 or 3, wherein the particulate polymer containing an imide group is a particulate polyimide or a particulate amide imide. A method for producing a polymer. ” ′