JPS6112730A - Preparation of copolymer - Google Patents

Abstract

PURPOSE:To prepare an aromatic polyester amide having improved heat resistance and processing properties, by reacting an isophthalic acid dihalide with an aromatic dihydroxy compound and an aromatic hydroxyamino compound. CONSTITUTION:An isophthalic acid dihalide shown by the formula I (X is chlorine or bromine; R0 is H, chlorine, bromine, or methyl) as a starting raw material is copolymerized with (B) 5-80mol% aromatic dihydroxy compound shown by the formula II, and (C) 20-95mol% aromatic hydroxyamino compound shown by the formula III (R1-R8 are H, halogen, or 1-4C alkyl; Z1 and Z2 are 1-3C alkylene, isopropylidene, O, S, etc.; n is 0, or 1) in a blending ratio of preferably equimolar component A based on the total amounts of the components B and C in the presence of an acid-acceptor in an organic solvent. Or, a solution of the component A in an organic solvent is blended with an alkali aqueous solution of the components B and C, and copolymerized, to give the aimed copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for producing a copolymer, and more particularly to a method for producing an aromatic polyesteramide having excellent heat resistance and processability.

[Technical background of the invention and its problems]

Aromatic polyesters and aromatic polyamides are conventionally known as engineering plastics. The former has low hygroscopicity and excellent moist heat properties, but has the disadvantages of poor thermal stability, difficulty in molding, and furthermore, is susceptible to hydrolysis. The latter has excellent heat resistance, but
Generally, it has a high hygroscopicity and a high melting point, which makes it extremely difficult to mold.

Therefore, in order to solve the drawbacks of aromatic polyester and aromatic polyamide and to obtain a polymer that has the excellent properties of both, research has been conducted on aromatic polyester amide having ester bonds and amide bonds in the same molecule. was advanced.

As a result of this research, for example, Japanese Patent Publication No. 39-26012 describes 2,2-bis(4hydroxyphenyl)propane, hexamethylenediamine and phthalic acid dichloride (isophthalic acid dichloride: terephthalic acid dichloride-50:
50) discloses a method for obtaining aromatic polyesteramides. This polymer has a softening temperature of 228-236
℃, but it had poor thermal stability at high temperatures and was not viable. 2.2- in Special Publication No. 48-19237
Bis(4'-human xyphenyl)furopane, 2.2-
Aromatic polyesteramide has been obtained from bis(4-aminophenyl)propane and terephthaloyl chloride by interfacial polymerization, but the secondary rearrangement temperature of this polymer is 262°C, but the decomposition temperature is low at 350°C or higher, and It had the disadvantage of being poorly soluble in many organic solvents. In addition, special public service 1977-
Publication No. 20555 discloses a method for obtaining aromatic polyesteramide from isophthalic acid chloride, 4-amino-4-hydroxydiphenyl ether, and 4.4-diaminodiphenyl ether, but this polymer has a low degree of polymerization and a low decomposition temperature. The temperature was as low as 365°C. As described above, conventional aromatic polyesteramides have various drawbacks, are extremely unsatisfactory even as heat-resistant polymers, and have not been put into practical use industrially. Furthermore, in the production of aromatic polyesters and aromatic polyesteramides, isomers of aromatic dicarboxylic acid dichloride have usually been used as a mixture in order to improve the toughness of the copolymer.

In other words, copolymers obtained using isophthalic acid dichloride or terephthalic acid dichloride H9 alone are brittle and cannot be molded, and the copolymers crystallize during the reaction, making it impossible to expect an increase in molecular weight. .

[Purpose of the invention]

An object of the present invention is to provide a method for producing a high molecular weight aromatic polyester amide having excellent processability and heat resistance by using isophthalic acid dihalide alone.

[Summary of the invention]

5 to 80 mol% of isophthalic acid dihalide of the following general formula (wherein, X represents a chlorine atom or a bromine atom, and Ro represents a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group) is used as an aromatic compound of the following general formula. group dihydroxy compound and 20 to 95 moles of aromatic hydroxyamino compound (in formula 1, sL to R8 may be the same or different, and each represents a hydrogen atom, a halogen atom, or a C1 to C4 alkyl group, and Zl and z2 are the same or They may be different, each including a direct bond, a C1-C3 alkylene group, 2 isopropylidene groups, a C6-C6 cycloalkylene group, -o-
, -s-, -so, , -co-, -. n is 0
Or represents 1. ) is a method for producing a copolymer.

Specific examples of isophthalic acid dihalides used in the method of the present invention include isophthalic acid dichloride, isophthalic acid dibromide, 3-methyl-1゜5-dichloroformylbenbene, 3-chloro-1゜5-dichloroflumylbay, etc. These compounds can be used alone or in combination of two or more.

Specific examples of aromatic dihydroxy compounds used in the method of the present invention include bis(4-hydroxyphenyl)methane,
Bis(4-hydroxy-3-methylpheny A/)methane, bis(4-hydroxy-8゜5-dichlorophenyl)
Methane, bis(4-hydroxy-8,5-dibromophenyl)methane, bis(4-hydroxy-3,5-difluorophenyl)methane, bis(4-hydroxyphenyl)gent.

Bis(4-hydroxyphenyl) sulfide.

Bis(4-hydroxyphenyl)sulfone 41
4-dihydroxydiphenyl ether, 1.1-bis(
4-hydroxyphenyl)ethane, 2,2- and bis(4
-hydroxy-3-methylphenyl) 70 pans, 2.2
-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)furopane, 1゜1-bis(4-hydroquinphenyl) -2,2,2- Trichloroethane, ■, 1-
Bis(4-hydroxyphenyl)cyclohexane, 4.
Examples include 4-dihydroxydiphenyl, 2,2-bis(4'-hydroxyphenyl)butane, and α,α-(4,4-dihydroxydiphenyl)-p-diisopropylbenzene. In addition, the hydrogen atom of the aromatic nucleus of the above aromatic dihydroxy compound may be a chlorine atom, a bromine atom,
Compounds substituted with groups inert to polymerization, such as fluorine atoms, methyl groups, ethyl groups, propyl groups, etc., can also be used.

These aromatic dihydroxy compounds may be used alone or as a mixture of two or more.

Specific examples of aromatic hydroxyamino compounds used in the method of the present invention include 4-hydroxy-4-aminodiphenyl, 4-hydroxy-4-aminodiphenylmethane,
2.2-(4-hydroxy-4-aminodiphenyl)propane, g, 2-(4-hydroxy-4-aminodiphenyl)butane, l.

methyl-4-aminodiphenyl), furopane, 2,2-minodiphenyl) 7'E=pan, 2,2-(4-hydropane, 3-methyl-4-hydroxy-4-aminodiphenyl, 8,3-dimethyl-4 -hydroxy-4-aminodiphenyl, 3,5-dimethyl-4-hydroxy-4-aminodiphenyl, 3-methyl-4-hydroxy-4-
aminodiphenyl sulfide, 3-methyl-4-hydroxy-4-aminodiphenylmethane, 8.5-dimethyl-4-human oxy-4-aminodiphenylmethane,
2.2-(3-Methyl-4-hydroxy-4-aminoschiff-hydroxy-4-aminodiphenyl)furopane.

2.2-(3,5-dimethyl-4-hydrocene-4-aminodiphenyA/)propane, 9.2-(3-ethyl-
4-Hydroxy-4-aminodiphenyl)furopanes
2.2 (3tert-butyl-4-hydroxy-
4-aminodiphenyl)furopane, 2.2-(3-chloro-4-1-hydroxy-4-aminoschiff 4-hydroxy-4-aminodiphenyl)furobane, 5-tetrabromo 4-hydroxy-4-aminodiphenyl)propane, 4
-Hydroxy-4-aminodiphenyl sulfide, 4
Examples include -hydroxy-4-aminodiphenyl ether, 4-hydroxy-4-aminobenzophenone, 4-hydroxy-4-aminostilbene, and 4-hydroxy-4-aminodiphenyl sulfone. These compounds may be used alone or in combination of two or more.

In the present invention, the amount of the aromatic dihydroxy compound used is 5 to 80 mol%, preferably 10 to 80 mol%, based on the total amount of the aromatic dihydroxy compound and the aromatic hydroxyamino compound.
It is in the range of 75 mol%. If the amounts of both compounds used are out of this range, the copolymer will crystallize and have a low molecular weight, or its moldability will be impaired. Furthermore, the amount of isophthalic acid dino-ride used is preferably equimolar to the total amount of the aromatic dihydroxy compound and the aromatic hydroxyamino compound, but it may be used in an excess or insufficient amount within the range of 10 mol% or less. It is possible.

The copolymers of the present invention can be produced in several ways.

The first method uses isophthalic acid dihalide as a starting material, and mixes it with an aromatic hydroxyamino compound and an aromatic dihydroxy compound in an inert organic solvent, such as methylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane. , chlorobenzene, benzene, toluene, xylene.

Tetrahydrofuran, cyclohexanone, N,
Dissolved in N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane or pyridine, etc.
More than an equivalent amount of the acid acceptor, e.g. triethylamine, ) to the acid produced! J-n-propylamine, N,N-dimethylaniline N.

N-dimethyl-m(or-p)-toluidine.

Polycondensation is carried out in a homogeneous solution state in the presence of quinoline or pyridine. The second method uses isophthalic acid dihalide as a starting material, which is mixed with an inert organic solvent that is immiscible with water, such as methylene chloride, chloroform, or carbon tetrachloride.

1.1.2-Trichloroethane, chlorobenzene, 〇-
It dissolves in dichlorobenzene, benzene, toluene, xylene, cyclohexanone, etc., while aromatic hydroxyamino compounds and aromatic dihydroxy compounds dissolve alkali metal hydroxides, carbonates, or hydrogen carbonates in an amount equivalent to or more than the acid produced. This is an interfacial polycondensation method in which a salt is mixed in an aqueous solution and a reaction is carried out by bringing both solutions into contact.

The polymerization catalyst used in the second method of the present invention is triphenylmethylphosphonium iodide, tetra-n-butylphosphonium bromide, triethyldodecylphosphonium chloride, triethyldodecylphosphonium chloride, triphenyldodecylphosphonium chloride, triphenylcetylphosphonic. Muchloride, tri-n-butylcetylammonium bromide, trimethyldodecylammonium iodide, trinotyldodecylamsonium gromide, trimethylcetylamsonium chloride, trimethylcetylammonium bromide, tri-n-butylcetylammonium bromide, benzyltrimethylammonium Examples include chloride-18-crown-6, diimbu-18-crown-6° dicyclohexyl-18-kurakune-6, and the like. These polymerization catalysts can be used alone or in a mixture of two or more, and the amount used varies depending on the type of polymerization catalyst, type of starting materials, composition, reaction conditions, etc., but is based on the theoretical yield of the copolymer obtained.
It ranges from x to 10% by weight, preferably from 0.005 to 7% by weight.

The reaction temperature in the first method is in the range of -40 to 40°C, preferably -20 to 30°C, and the reaction time is in the range of 0.5 to 40°C.
zO time, preferably in the range of 2 to 10 hours. Further, the reaction temperature in the second method is in the range of -20 to 50°C, preferably -10 to 40°C, and the reaction time is 0.1°C.
~10 hours, preferably 0.2 to 7 hours.

In the present invention, phenol, 2.
6-dimethylphenol, p-(-butylphenol,
0-phenylphenol, p-phenylphenol+
Monovalent phenols such as p, '7 milphenol and 4-hydroxybenzophenone can be used together in an amount of 5 mol % or less based on the isophthalic acid dihalide.

[Embodiments of the invention]

The present invention will be explained below with reference to Examples and Comparative Examples. Examples and comparative examples were conducted under a nitrogen atmosphere unless otherwise specified. In addition, all parts are parts by weight, and the logarithmic viscosity ηlnh is calculated using cyclohexanone as a solvent and a copolymer concentration of 0.5 g/
dl! The viscosity of a dilute solution of is measured at 30°C, and was calculated from the following formula.

C (D in the formula is the flow time of the copolymer solution, to is the flow time of only the solvent, and C is the concentration of the copolymer.) The glass transition temperature of the copolymer was determined by differential scanning calorimetry. .

Example 1) Proper/181.84 parts, z, 2-bi, t, (4
-Hydroxyphenyl)propa:/182.04 parts and 0.813 parts of p-cumylphenol were dissolved in 1800 parts of sufficiently dehydrated tetrahydrofuran, and 340 parts of triethylamine was added. This solution was kept at 10°C,
Isophthalic acid diclide 325.1 while stirring thoroughly.
A solution of 9 parts dissolved in 350 parts of tetrahydrofuran was gradually added dropwise, and stirring was continued at this temperature for 6 hours.

The reaction system became non-uniform due to precipitation of triethylamine hydrochloride as a by-product, and the solution gradually became viscous. After the reaction is complete, the separated mother liquor, which is triethylamine hydrochloride, is poured into a mixed solution of methanol s, ooo parts and water s, ooo parts to precipitate a copolymer, and the copolymer is thoroughly washed with methanol. and dried under reduced pressure. The yield of the obtained copolymer was 550 parts (yield 96%). Furthermore, it was confirmed from infrared absorption spectroscopy, H nuclear magnetic resonance absorption spectroscopy, and elemental analysis that this copolymer was a polyesteramide. The ηinh of this copolymer is 1.1
1 (dl//g), and the glass transition temperature is 219°C
Met.

Example 2 68.19 parts of 2.2-(4-hydroxy-4-aminodiphenyl)propane and 2.2-bis(4-hydroxyphenyl) were added to an aqueous solution of 48.96 parts of sodium hydroxide dissolved in 100 parts of water. 75.09 parts of sulfone and 4 parts of Oyohitetler n-butylphosphonium bromide F were added. This solution was kept at 20°C and vigorously beaten and stirred.

A solution of 121.8 parts of isophthalic acid dichloride dissolved in 2,500 parts of dehydrated cyclohexanone was quickly poured into the mixture, and stirring was continued at 20°C for 1.5 hours. After the reaction was completed, the mixture was allowed to stand for a while, and the organic phase separated into two phases was thoroughly washed with water and poured into 15,000 parts of methanol to precipitate a copolymer. The copolymer was washed with methanol and dried under reduced pressure. The yield of the obtained copolymer was 205.8 parts (yield 93%). The ηinh of this copolymer is 1.27
The glass transition temperature was 220°C. When this copolymer was cast into a film from a cyclohexanone solution, a transparent and tough film was obtained.

When compression molded using a hot press at 280° C. and a pressure of 150 kg/7, a light yellow transparent and rigid molded product was obtained.

Example 3 Polymerization was carried out in the same manner as in Example 1, except that 198.04 parts of 2.2-(4'-hydropane) was used instead of 181.84 parts of 2.2-(4-4Froxy-4-aminodiphenyl)propane. The reaction was carried out. The yield of the obtained copolymer was 536 parts (yield = 92%), η1nth = 0.96 (di/
g) and the glass transition temperature was 209 °C.

Comparative Example 1 17.048 parts of 2.2-(4-hydroxy-4-aminodiphenyl)propane, 97.028 parts of 2.2-bis(4-hydroxyphenyl)propane, and 0.255 parts of p-')milphenol was dissolved in 600 parts of thoroughly dehydrated tetrahydrofuran, and 106 parts of triethylamine was added.
3 parts were added. While maintaining this solution at 10°0 and stirring thoroughly, a solution of 101.63 parts of isophthalic acid dichloride dissolved in 200 parts of tetrahydrofuran was gradually added dropwise, and stirring was continued at this temperature, and a copolymer precipitated. . After continuing stirring for 7 hours, the precipitate was separated and the mother liquor was treated in the same manner as in Example 1 to obtain a copolymer. η of this copolymer
inh was 0.43 (d//g). - The precipitate was poured into a large amount of water to dissolve and remove triethylamine hydrochloride. The obtained copolymer was thoroughly washed with water and then dried under reduced pressure.The copolymer was insoluble in most organic solvents, and the molded product was brittle and could not be put to practical use at all.

[Effect of the Invention 1 According to the present invention, an aromatic polyesteramide having excellent heat resistance and processability and having a high molecular weight can be easily produced.

Claims (3)

[Claims] (1) Isophthalic acid with the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a chlorine atom or a bromine atom, and R_0 represents a hydrogen atom, a chlorine atom, a bromine atom, or a methyl group.) An aromatic dihydroxy compound containing 5 to 80 mol% of dihalide with the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and aromatic hydroxy compounds with 20 to 95 mol% of the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Amino compounds (wherein R_1 to R_8 may be the same or different,
A hydrogen atom, a halogen atom, an alkyl group of C_1 to C_4, respectively, Z_1 and Z_2 may be the same or different, and a direct bond, an alkylene group of C_1 to C_3, an isopropylidene group, a cycloalkylene group of C_5 to C_8, - O-, -S-, -SO_2-, -CO-
represents. n represents 0 or 1. ) A method for producing a copolymer characterized by reacting with (2) A method for producing a copolymer according to claim 1, in which the reaction is carried out in an organic solvent in the presence of an acid acceptor. (3) The copolymer according to claim 1, wherein the reaction is carried out by mixing an organic solvent solution of isophthalic acid dihalide and an alkaline aqueous solution of an aromatic dihydroxy compound and an aromatic hydroxyamino compound in the presence of a polymerization catalyst. Production method