JPH0374425A - Production of heat-resistant polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer, excellent in light resistance, also good in heat insulating properties, etc., and useful as a composite material, etc., by reacting an organic polyfunctional isocyanate with a polyfunctional carboxylic acid in the coexistence of an organic polyfunctional carboxylic acid having hydrophilic groups. CONSTITUTION:(D) An organic polyfunctional isocyanate is reacted with (A) an organic polyfunctional carboxylic acid or (B) an organic polyfunctional carboxylic acid anhydride containing (C) an organic polyfunctional carboxylic acid, having hydrophilic groups and coexisting in part thereof in a polar solvent in the presence of an alkali compound to afford the objective polymer. Furthermore, the hydrophilic groups in the component (C) are sulfone groups and an organic diisocyanate is preferably reacted with an organic dicarboxylic acid and an organic dicarboxylic acid having sulfone group.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides light resistance without impairing the heat resistance of a heat-resistant polymer obtained from an organic polyvalent isocyanate and an organic polyvalent carboxylic acid or an organic polyvalent carboxylic acid anhydride. It is about how to improve your sexuality.

(Prior art) Fully aromatic boryamides or boria-a toimides are produced from aromatic polyvalent amines and aromatic polyhydric acid chlorides, and are used for heat-resistant clothing, sports clothing, etc. However, dyeability is poor when used as is. It is extremely poor, and various efforts have been made to improve the dyeing property.For example, sulfo-substituted amides,
Those modified with quaternary ammonium-containing amides, etc. (Japanese Patent Publication No. 11168-1983), those in which a monohydroxy compound containing a sulfone group, tertiary amino group, etc. is reacted and added to the polymer end (Japanese Patent Publication No. 8533-1983), etc. There is. However, in these methods, the heat resistance is considerably impaired, the material becomes colored upon heating, and the light resistance is also insufficient.

On the other hand, methods for producing fully aromatic polyamides and polyamitimides from aromatic polyvalent isocyanates and aromatic polyvalent carboxylic acids are also known. For example, monoalkali metal salts of aromatic polyvalent carboxylic acids (Japanese Patent Publication No. 63-28088), There is a method of manufacturing using an alkali metal fluoride (Japanese Unexamined Patent Publication No. 62-15612) as a catalyst. According to this method, it is possible to dye without impairing heat resistance, but light resistance is still insufficient.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a method for improving the light resistance of heat-resistant polymers such as fully aromatic polyamides and polyamitoimides produced from aromatic polyvalent isocyanates and aromatic polyvalent carboxylic acids without impairing the heat resistance. It is in.

[Means for solving problems]

The present inventors have arrived at the present invention as a result of intensive study on the above problem.

That is, the present invention provides a method for producing a heat-resistant polymer from an organic polyvalent isocyanate and an organic polyvalent carboxylic acid or an organic polyvalent carboxylic acid anhydride in a polar solvent in the presence of an alkali compound. This is a method for producing a heat-resistant polymer, characterized in that an organic polycarboxylic acid having a wood-philic group is allowed to coexist in a part of the organic polycarboxylic acid anhydride.

Organic polyvalent isocyanates that can be used in the present invention include:
-a All known organic polyvalent isocyanates can be used, but in particular those described in JP-A-57451615, such as 1,2-diisocyanate ethane, cyclohexane-1,4-diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), m-xylene diisocyanate 1, phenylene-1,4 diisocyanate, phenylene-1,3-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-
Diisocyanate, diphenylmethane-4,4°-diisocyanate, diphenyl ether-4,4'-diisocyanate, 1,5-naphthalene diisocyanate and the like are preferred.

Examples of organic polycarboxylic acids or organic polycarboxylic anhydrides that can be used in the present invention include the following.
9223, for example dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and hexahydroterephthalic acid. , diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,41-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, 4 .4
Examples include '-diphenylmethane-bis-trimellitic imide acid and 4,4'-diphenyl ether-bis-trimellitic imide acid. Tricarboxylic acids include butane, -1,2,4-)dicarboxylic acid, cyclohexane-1,2,3-)dicarboxylic acid, cyclopentadienyl-3,4,4'-)dicarboxylic acid, and cyclopentadienyl -1,2,4-)dicarboxylic acid, benzene-1,
2,4-) dicarboxylic acid, naphthalene-1,4,5-)
Dicarboxylic acid, biphenyl-3,4,4''-tricarboxylic acid, diphenylsulfone-3,4,3'-tricarboxylic acid, diphenyl ether-3,4,3'-tricarboxylic acid, benzophenone-3,4,4'-tricarboxylic acid There are acids etc.

Examples of organic polycarboxylic acid anhydrides include, for example, acid anhydrides derived from tricarboxylic acids, which contain 1 carboxyl group and 1 acid anhydride group in the molecule, and include the following: Examples include trimellidic anhydride and benzene-1,2,3-tricarboxylic anhydride.

The alkali compounds used in the present invention are not particularly limited, but include, for example, alkali metal hydroxides, alkali metal carbonates (Japanese Patent Publication No. 61-14219), monoalkali metal salts of organic polyhydric carboxylic acids (Japanese Patent Publication No. 63/1986). -28088,
JP-A-57-179223) and alkali metal fluorides (JP-A-62-156120) are suitable.

The organic polyvalent carboxylic acid having a woody group used in the present invention includes MOsS-R-(COOH)n, M: alkali metal, R: aromatic residue having a valence of 3 or more, n r an integer of 2 or more (HOOC)
A compound represented by n-R-(COO?ri), (HOOC
) n-R-CHiOH, etc. Specific examples of 0MO*5-R-(COOI+) include sodium isophthalate-5-sulfonate, sodium terephthalate-2-sulfonate, 4. 4'-diphenyl ether-dicarvone i! *-2,2'-disodium sulfonate, 4゜4'-diphenyl-dicarboxylic acid-2,2'-disodium sulfonate, 4,4'-diphenylsulfide-dicarboxylic acid-2,2゛-disodium sulfonate, etc. Potassium and lithium salts of the above compounds can also be used. Also (HOOC) n
-R- (COOM) or (HOOC)n-R-CHi
Compounds represented by OH include trimellitic acid monosodium salt, sodium 3-carboxylate-4,4'-
Examples include diphenyl dicarboxylic acid, and potassium and lithium salts thereof are also used.

Combinations of heat-resistant polymers consisting of organic polyvalent isocyanate and organic polyvalent carboxylic acid or organic polyvalent carboxylic acid anhydride include: organic polyvalent isocyanate and organic polyvalent carboxylic acid, ii. organic polyvalent isocyanate and organic polyvalent carboxylic acid. They can be broadly classified into acids and organic polycarboxylic acid anhydrides, and the polymers produced in bulk have a skeleton formed from amide groups, and in the case of No. 11, the skeleton is formed from amide groups and imide groups. ], ii In the polymers obtained by any of the combinations, an organic polyvalent carboxylic acid or an organic polyvalent carboxylic acid anhydride is partially combined with an organic polyvalent carboxylic acid having a hydrophilic group to form a hydrophilic group in the polymer. can be introduced.

In the method of the present invention, an organic polyhydric incyanate and an organic polycarboxylic acid or an organic polycarboxylic acid anhydride and an organic polyhydric carboxylic acid having a hydrophilic group and Alkali metal fluoride with inert gas,
For example, heating is performed at a temperature of 20° C. to 250° C., preferably 100° C. to 200° C., for 1 to 20 hours in a nitrogen atmosphere.

The amount of the organic polycarboxylic acid having a hydrophilic group used in the reaction is 0.5 mol% to 50 mol%, preferably 2 mol% to 30 mol%, based on the organic polycarboxylic acid or organic polycarboxylic acid anhydride. % range.

If it is less than 0.5 mol%, the effect of improving light resistance will be small, and if it is more than 50 mol%, the mechanical strength of the polymer will decrease, which is not preferable.

For 1.0 mol of organic polyvalent isocyanate used in the reaction, the total amount of organic polyvalent carboxylic acid or organic polyvalent carboxylic acid anhydride and organic polyvalent carboxylic acid having a hydrophilic group is 0.
．． It is used in the range of 70 to 1.30 mol, but especially 0.9
It is preferable to use the alkali compound in the range of 5 to 1.10. Outside this range, a heat-resistant polymer with a high molecular weight cannot be obtained. The amount of the alkali compound used as a catalyst is 0.01 to the organic polyvalent isocyanate. -10 mol% is preferred, particularly 0.1 to 5 mol%. If the amount is less than this range, it will be difficult to obtain a high molecular weight polymer, and if the amount is more than this range, the catalyst residue remaining in the produced polymer will be reduced. The raw materials, isocyanate, carboxylic acid or acid anhydride, organic polyhydric carboxylic acid with a hydrophilic group, and alkali compound may be introduced into the reaction system at the same time. , may be added to the reaction system in any order, but usually at the same time at room temperature,
Alternatively, it is preferable to use a solvent and feed the raw materials into the solvent. In some cases, the raw material isocyanate and either a carboxylic acid or an acid anhydride and an organic polycarboxylic acid having a hydrophilic group, preferably. The isocyanate is preferably added and reacted continuously at a predetermined reaction temperature, and the amount of the solvent to be used can be appropriately selected depending on the performance of the final polymer and the reaction temperature.

Generally, it is preferable to select conditions that do not interfere with stirring due to thickening during polymerization.

Examples of organic solvents used in the present invention include N, N-
Chain-like or cyclic amides or phosphorylamides of dimethylacedeamide, N,N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-yodasiridone, γ-butyrolactone, hexamethylphosphoric triamide , or sulfoxides or sulfones such as dimethyl sulfoxide, diphenyl sulfone, ureas such as tetramethylurea, or benzene, toluene, xylene, decalin, cyclohexane,
Heptane, hexane, pentane, methylene chloride, chlorobenzene, dichlorobenzene, tetrahydrofuran, etc. are used.

After the polymerization is complete, to separate the polymer as a solid, the polymer can be separated into a non-solvent (e.g. methanol, water, acetone or a solution of a salt such as lithium chloride, sodium chloride or calcium chloride in these solvents). The reaction solution is added to precipitate the polymer.The precipitated polymer is also thoroughly washed with the same non-solvent to remove the remaining catalyst and other impurities.After washing, the polymer is washed at room temperature or high temperature. In some cases, it is dried under reduced pressure.The polymer thus obtained can be subjected to melt molding, or in some cases, it can be redissolved in a solvent and used as a varnish, adhesive, or used in the production of cast films and fibers. Also, the polymerization solution can be used as it is as a dope for spinning.Alternatively, the polymerization solution can be cast directly onto a glass plate, the solvent removed under reduced pressure, and then washed with hot water to produce a film1.
[Examples] The method of the present invention will be explained below using Examples, but the present invention is not limited to these.

Example 1 3.01 g (0,018 mol) of terephthalic acid and 25.59 g (0,154 mol) of isophthalic acid were placed in a 501)d separable flask equipped with a stirrer, a thermometer, a condenser, a dropping funnel, and a nitrogen inlet tube. mole), isophthalic acid-
Sodium 5-sulfonate 4.85 g (0,018
Morun Monosodium Isofucrate 0.339 g
(0,0018 mol) and solvent 1,3-dimethyl-2-
Add 300- of imidasilidinone and heat the mixture to 200°.
C. and tolylene-2,6-diisocyanate 31
．． 72 g (0,1821 mol) was added dropwise over 2 hours and stirring was continued for another 2 hours. The polymerization solution gradually became viscous. A portion of this polymerization solution was taken out and 1,3-dimethyl-2
-Polymer concentration 0°Ig/100a with imidazolidinone
The viscosity was measured at 30°C. As a result, the logarithmic viscosity was 2.1. Further, this polymerization solution was cast onto a glass plate and dried under reduced pressure at 80°C for 1 hour, and the obtained film was peeled off from the glass plate, fixed on a frame, and immersed in hot water at 90 to 100°C. The catalyst etc. were sufficiently removed. The film thus obtained! From the R spectrum, 1
660 cm-', absorption of amide at 1530C1-1, 1
Absorption based on SO was observed at 2,000'' and 104,104O'.

Also calculated from elemental analysis values (tI C68, 66%, H4
, 54%, 810.67%, 31.22%, Na0.8
8%, analysis value C67, 62%, H4, 49%,
N1.057%, 31.19%, Na 0.82%. The tensile strength of this film is 1180kg/
The elongation in cm was 21%. In order to evaluate the light resistance of the film, 2.
It was irradiated for 0 hours.

When the coloring after irradiation was observed, it was slightly yellow.

The film was also placed in a dryer at 250° C. for 1 hour to observe its thermal coloring properties. As a result, the film was not colored.

Example 2 The amount of isophthalic acid in Example 11N1 was 25.59 g (0
Polymerization was carried out in the same manner as in Example 1, except that the amount of sodium isophthalate-5-sulfonate was changed to 1.50 g (0,009 mol), and a film was produced.

The obtained polymer had a logarithmic viscosity of 2.3. The coloration of this film after 20 hours of FOM irradiation was pale yellow with little change in color. Further, there was no thermal coloration after 1 hour at 250°C.

Example 3 The amount of isophthalic acid in Example 1 was changed to 21.07 g (0,
Polymerization was carried out in the same manner as in Example 1 to produce a film, except that the amount of sodium isophthalate-5-sulfonate was changed to 9.72 g (0,036 mol).

The logarithmic viscosity of the obtained polymer was 2.0.

The coloring of this film after 20 hours of FOM irradiation was slightly yellow, and the color change was extremely small.

Comparative Example 1 The amount of isophthalic acid in Example 1 was changed to 30.10 g (0,
163 mol) and polymerization was carried out in the same manner as in Example 1, except that isophthalic acid-5-sulfonic acid was not used, and a film was produced. The obtained polymer had a logarithmic viscosity of 2.4. The coloring of this film after 20 hours of FOM irradiation was yellow, with a large color change, and no thermal coloration was observed after 71 hours at 250°C.

From these Examples 1 to 3 and Comparative Example 1, when an organic polycarboxylic acid having a hydrophilic group is introduced into these polymer skeletons, light resistance can be improved without deteriorating thermal performance.

Comparative Example 2 Dehydrated N,N'-dimethylacedeamide (DMAC)
Metaphenylenethia distilled to 725-64.62
, (0,5976 mol) and dry ice-
Cooled to -15°C in a methanol bath. 109.
33 g (0,5387 mol) of sodium isophthaloyl chloride-4-sulfonate 14.02 g (0,
0598 mol) was added dropwise while stirring to keep the temperature below 20°C. After the completion of 9 dropwise additions, the temperature was raised to 30°C over 30 minutes and maintained at that temperature for 129 minutes. After the reaction was completed, 45 g of anhydrous calcium hydroxide was added and heated at 100° C. for 90 minutes to neutralize the generated hydrogen chloride. A portion of this polymerization solution was dropped into a large amount of water while stirring, and DMAC1 calcium hydroxide was removed from the precipitated polymer. The obtained polymer was heated to 80°C.
It was dried under reduced pressure for 15 hours. DMAC this polymer powder
Dissolve to a concentration of 0.1 g/100 ad in 3
The logarithmic viscosity was measured at 0°C and found to be 1.2. The remaining polymerization solution was cast onto a glass plate and dried under reduced pressure at 80°C for 1 hour, and the resulting film was peeled off from the glass plate, fixed on a frame, and injected with calcium hydroxide in hot water at 90 to 100°C. , DMAC was sufficiently removed. Furthermore, this film is 8
It was dried under reduced pressure at 0°C for 2 hours. FOM20 of this film
The coloring after time irradiation was yellow and the color change was relatively large.

Further, the heat coloring after 1 hour at 250°C was brown, and the color change was large.

Example 4 Polyamideimide was polycondensed using the same apparatus as in Example 1. Trimelidic anhydride 18.05g (0
,0939 mol), trimellidic acid-2-monosodium salt 2.41 g (0.0104 mol), potassium carbonate 0.144 g (0.0OIG4 mol) and 1.3-
Prepare dimethyl-2-imidasilidinone 3001d,
The mixture was heated to 200° C. with stirring under nitrogen. Maintaining the mixture at this temperature, diphenylmethane-4,4'
-diisocyanate) 26.26g (0,1049
A solution prepared by dissolving 50 ml of N,N'-dimethylethylene urea was added dropwise over 4 hours. After further reaction for 2 hours, the mixture was cooled to room temperature. This product was poured into a large amount of water to precipitate the polymer, filtered, thoroughly washed with a large amount of water, and dried under reduced pressure at 150° C. for 3 hours. 3 in 1,3-dimethyl-2-imidazolidinone of the obtained polymer
The logarithmic viscosity at 0°C was 1.82.

The IR spectrum of this polymer is based on the imide group 17
71cm-'%1720cm-' absorption and 16600II-' based on the amide group, 1530 yen, and 1200es-' based on the sulfone group! Absorption of 040es-' was observed.

A solution of this polymer in N-methylpyrrolidone (
10% by weight) in the same manner as in Example 1. The tensile strength of this film is 1250 kg/d,
At an elongation of 30, the Tg of the film was 267°C. The 5% weight loss temperature of this film measured by thermobalance was 461°C.
Met. The coloration of this film after 20 hours of FOM irradiation was pale yellow, with little change in color. Also 250℃/
There was almost no thermal coloring after 1 hour.

Comparative Example 3 Polyamideimide was polymerized in the same manner as in Example 4 except that trimellidic acid-2-monosodium salt was not used.

Trimelic acid anhydride 20. Olg (0,1042 mol), 910.144 g (0,0010 mol) of potassium carbonate and 250 m of N,N'-dimethylethylene urea were charged, the mixture was maintained at 200°C, and diphenylmethane-4
,4'-diisocyanate) 26.08g (0,1
042 mol) to N, N'-dimethylethylene urea 50
A solution dissolved in M1 was added dropwise over 4 hours. After further reaction for 2 hours, the mixture was cooled to room temperature. This product was poured into a large amount of water to precipitate the polymer, filtered, thoroughly washed with a large amount of water, and dried under reduced pressure at 150℃ for 3 hours. The obtained polymer was identified as boria-a toimide from the IR spectrum, and the logarithmic viscosity was 1.8. A solution of this polymer dissolved in N-methylpyrrolidone for 11 hours was cast onto a glass plate, and a film was produced in the same manner as in Example 1. The tensile strength of this film is 1290kg/C1
i, elongation was 25%. The Tg measured by a differential scanning calorimeter (DSC) was 265°C, and the 5% weight loss temperature measured by a thermobalance was 467°C. FOM20 of this film
The coloring after time irradiation was yellow and the color change was large.

Further, there was almost no thermal coloring after 1 hour at 250°C.

(Effects) In addition to heat resistance and light resistance, the polymer according to the present invention has heat insulation properties,
It has excellent radiation resistance, thermal dimensional stability, mechanical properties, electrical properties, chemical resistance, and flame retardancy, so it is suitable for various industrial materials, protective materials, composite materials, reinforcing materials, electrical insulation materials, etc. It can be widely used as a high-performance industrial material, as well as in the electrical, electronic, automobile, vehicle, and aircraft industries, as well as the clothing and interior fields, including molded products, films, mats, fibers, varnishes, adhesives, and the like.

Claims (1)

[Claims] 1. In producing a heat-resistant polymer from an organic polyvalent isocyanate and an organic polyvalent carboxylic acid or an organic polyvalent carboxylic acid anhydride in a polar solvent in the presence of an alkali compound,
A method for producing a heat-resistant polymer, characterized in that an organic polycarboxylic acid or an organic polycarboxylic acid anhydride coexists with an organic polycarboxylic acid having a hydrophilic group. 2. The method according to claim 1, wherein the hydrophilic group of the organic polycarboxylic acid having a hydrophilic group is a sulfone group. 3. The method according to claim 1, which comprises reacting an organic diisocyanate with an organic dicarboxylic acid and an organic dicarboxylic acid having a sulfone group. 4. The method according to claim 1, characterized in that a compound selected from the group consisting of an organic diisocyanate, an organic tricarboxylic acid or a tricarboxylic acid anhydride, and an organic polyhydric carboxylic acid having a hydrophilic group are reacted.