JPH0198629A - Novel polysulfone resin and its production - Google Patents

Abstract

PURPOSE:To obtain the title resin which is excellent in heat resistance, rigidity, toughness, etc., has a high flow during molding, can be molded under relatively gentle conditions, has a suitably low photoelastic constant and is useful also as an optical material, having repeating units of specified formulas. CONSTITUTION:A polysulfone resin having repeating units of formula I [wherein Y is direct bond, an ether bond, a thioether bond, -SO2-, a group of formula II (wherein R1 and R2 are each H, a 1-6C alkyl or a phenyl), a group of formula III (wherein n is 2-10), or a group of formula IV (wherein m is 4-8)] and having an intrinsic viscosity as measured in chloroform at 20 deg.C >=0.4dl/g. This resin is excellent in heat resistance, rigidity, toughness, etc., which are characteristic of polystyrene, has a high flow during molding, can be molded under relatively gentle conditions, has a suitably low photoelastic constant and can be effectively used as an optical material etc. This resin can be produced by reacting a bisphenol of formula V (wherein Y is an defined above) with a compound of formula VI (wherein X<1> and X<2> are each a halogen).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new polysulfone resin and a method for producing the same, and more specifically, it is suitable for the field of resin materials such as materials for optical equipment and various industrial materials. The present invention relates to a new polysulfone resin used in and a suitable method for producing the same.

[Conventional technology]

Polysulfone resin is a strong thermoplastic resin with excellent heat resistance and good rigidity, and can be processed into molded products of various shapes by injection molding, extrusion molding, vacuum forming, etc.

However, conventional porsulfone resins have drawbacks such as generally low fluidity and high temperatures required for molding.In addition, they have a large photoelastic coefficient and optical anisotropy due to distortion during molding. There were problems such as getting too big.

[Problem that the invention seeks to solve]

The first aspect of the present invention is that it does not have the above-mentioned problems, has excellent properties unique to polysulfone resin such as heat resistance, rigidity, and toughness, has high fluidity during molding, and can be molded under relatively mild conditions. , and has a moderately low photoelastic coefficient.
The second invention of the present invention aims to provide a novel polysulfone resin which is extremely advantageous in practice, such as being able to be effectively used as an optical material, etc., and the second invention of the present invention is a practical improvement of the polysulfone resin of the first invention. The purpose is to provide a manufacturing method.

[Means for solving problems]

The present inventors have discovered that a polysulfone that has a specific repeating unit consisting of a new polyphone monomer unit that does not have the above-mentioned problems and has an intrinsic viscosity of a specific value or more satisfies the object of the first invention. As a result of repeated studies on the production method, we found that a practically advantageous production method is to react the reaction product of a specific bisphenol with a strong alkali and bis(4-chlorophenyl)sulfone. Based on these findings, the present invention was completed.

That is, the first invention of the present invention provides the following: [However, in formula (1), Y is a single bond, an ether bond,
thioether bond, -3O,-, -C- (however, RI
and R"4, a hydrogen atom, an alkyl group of 01 to Ch,
Or represents a phenyl group. ), -←C1l□→a (however, n represents an integer from 2 to lO), ma (however, m
represents an integer from 4 to 8. ) represents.

The object of the present invention is to provide a polysulfone resin having a repeating unit represented by the formula and having an intrinsic viscosity of 0.4 a/g or more at 20°C in chloroform.

Further, the second invention of the present invention is an invention of a method for producing the polysulfone resin of the first invention [provided that the formula (
1), Y is a single bond, ether bond, thioether bond, -3O□-1-C- (However, R' and R2 are
Represents a hydrogen atom, a C3-C6 alkyl group, or a phenyl group. ), -G-CH, →A (however, n is 2 to 1
Represents an integer of 0. ), ma (where m represents an integer from 4 to 8).

] Bisphenols represented by -Momonen (II[) [However, in the formula, XI and ×2 each represent a halogen atom. Note that XI and x2 may be of the same type or may be of different types. The present invention provides a method for producing a polysulfone resin, which involves reacting a compound represented by the following formula.

The polysulfone resin of the present invention is characterized in that the main chain of the polymer compound constituting the resin has one or more types of the above-mentioned
) can be represented as being composed of repeating units represented by

That is, the above-mentioned hole (
Y in the repeating unit represented by 1) may be of the same type or different types.

Y in the polysulfone represented by the above-mentioned hole (I) includes a single bond, an ether bond, a thioether bond, -S
O,-, methylene group, 1.1-ethylidene group, 2.2-
A propylidene group is suitable, especially di-, -3O□-1
2,2-propylidene group and the like are preferred.

The polysulfone resin of the present invention is prepared at 20°C in chloroform.
The intrinsic viscosity at C is 0.4 d/g or more. The upper limit of this intrinsic viscosity is not particularly limited, but is usually about 3.0 dfl/g. If this intrinsic viscosity is less than 0.4 d/g, mechanical strength is low;
Also, 3. If it exceeds Oa/g, sufficient fluidity may not be obtained during processing.

The polysulfone resin of the present invention can be manufactured by various methods, but among them, it can be suitably manufactured by the manufacturing method of the second invention.

This second invention will be described in detail below.

That is, this second invention provides at least one of the above-mentioned -
The bisphenols represented by Mon'ena (II) are added to the bisphenols represented by Mon'ena (II) in the presence of at least one strong alkaline compound.
This is a method of reacting with bis(4-chlorophenyl)sulfone represented by I).

- Specific examples of compounds represented by Monka (II) (hereinafter sometimes simply abbreviated as bisphenols) include:
For example, 3,3'-diphenyl-4,4'-dihydroxybiphenyl, bis(3-phenyl-4-hydroxyphenyl) ether, bis(3-phenyl-4-hydroxyphenyl) sulfide, bis(3-phenyl-4-hydroxyphenyl) −
hydroxyphenyl) sulfone, bis(3-phenyl-
4-hydroxyphenyl)methane, 1,2-bis(3-
Phenyl-4-hydroxyphenyl)ethane, 1,3-
Bis(3-phenyl-4-hydroxyphenyl)propane, 1,4-bis(3-phenyl-4-hydroxyphenyl)methane, 1,6-bis(3-phenyl-4-hydroxyphenyl)hexane, 1.8 -bis(3-phenyl-4-hydroxyphenyl)octane, 1.10-bis(3-phenyl-4-hydroxyphenyl)decane,
1.1-bis(3-phenyl-4-hydroxyphenyl)ethane, 1,1-bis(3-phenyl-4-hydroxyphenyl)propane, 1゜1-bis(3-phenyl-
4-hydroxyphenyl)-1-phenylmethane, 2,
2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)methane, 3,3-bis(3-phenyl-4-
hydroxyphenyl)pentane, 1.1-piece (3-
Phenyl-4-hydroxyphenyl)-1-phenylethane, 1.1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, 1.1-bis(3-phenyl-4-hydroxyphenyl)cyclopencune, 2,2 −
Examples include bis(3-phenyl-4-hydroxyphenyl)octane and diphenyl-bis(3-phenyl-4-hydroxyphenyl)methane.

Among these, 3,3'-diphenyl-4'4'-dihydroxybiphenyl, bis(3-phenyl-4-hydroxyphenyl) ether, bis(3-phenyl-4-
hydroxyphenyl) sulfide, bis(3-phenyl-4-hydroxyphenyl) sulfone, bis(3-phenyl-4-hydroxyphenyl)methane, 1.1-bis(3-phenyl-4-hydroxyphenyl)ethane, 2
゜2-bis(3-phenyl-4-hydroxyphenyl)
Propane and the like are suitable.

In addition, these bisphenols may be used individually by 1 type, and may use 2 or more types together.

xl and in the above-mentioned hole (1) are each a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and x
l and Xt may be of the same type or different types. Among these, those in which both XI and xR are chlorine atoms are particularly preferred from a practical standpoint.

Specific examples of the compound represented by the general formula (III) (hereinafter sometimes simply abbreviated as sulfones) include bis(4-fluorophenyl)sulfone, bis(4-fluorophenyl)sulfone, bis(4-fluorophenyl)sulfone,
-chlorophenyl) sulfone, bis(4-bromophenyl) sulfone, bis(4-iodophenyl) sulfone, etc., and bis(4-chlorophenyl) and sulfone are particularly preferred in terms of width.

Note that these sulfones are usually used alone, but two or more types may be used in combination if desired.

Examples of the strong alkali compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, etc. Among these, caustic alkalis such as sodium hydroxide, sodium hydroxide, and potassium hydroxide are preferred, and sodium hydroxide is particularly preferred.

Note that these strong alkali compounds may be used alone or in combination of two or more.

As the procedure or production process for carrying out the above reaction, various methods can be applied, such as methods used to obtain known polysulfone from known bisphenols, strong alkali compounds, and dihalogen aromatic compounds. Generally, the following steps can be suitably used. That is, in the first step, the compound represented by the above-mentioned -Momona (II) (bisphenols) is dissolved in an appropriate solvent, and the above-mentioned strong alkaline compound such as sodium hydroxide is dissolved in an inert atmosphere. Add the aqueous solution and heat while stirring.

Here, the ratio of the bisphenols (component (A)) to the strong alkaline compound [component (B)] is usually 1.9% of the component (B) per mole of the component (A).
About 5 to 2.20 mol, preferably 1.98 to 2.10
It is preferable that the amount is on the order of moles.

If the proportion of component (B) used is too small, the conversion rate of component (A) will be low.On the other hand, if it is too large, excess alkaline components will remain in the polymer, making the neutralization and purification steps complicated. Become.

Although it cannot be specified uniformly because it varies depending on the type and amount of the solvent etc. added to form the reaction system in the first step, it is usually 2 per gram atom of the strong alkaline compound used.
The amount is preferably about 0 to 80 g, preferably about 40 to 60 g. If the amount of water used is too small, the solubility of the strong alkaline compound used may be low, making it difficult for the reaction to proceed smoothly; on the other hand, if it is too large, the amount of water to be distilled off in the subsequent process will be reduced. It is not economical as it becomes too much.

Examples of the solvent used include N-methylpyrrolidone, N,N-dimethylformamide, and N.

N-dimethylacetamide and dimethylsulfoxy-methylpyrrolidone are preferred. These solvents may be used alone or in combination of two or more. Also,
These solvents can also be used as mixed solvents with other inert solvents, especially toluene, xylene,
By using it as a mixed solvent with chlorobenzene or the like, water can be efficiently distilled off as described below.

Particularly preferred among these solvents is a mixed solvent of N-methylpyrrolidone and chlorobenzene. The ratio of N-methylpyrrolidone and chlorobenzene used is usually 1:0.1 to 1:3, preferably 1:0.5.
A preferable range is 1:1 to 1:1.

In addition, when using this mixed solvent, for example,
A preferred method is to first dissolve the bisphenols in N-methylpyrrolidone and then add chlorobenzene to this solution.

The amount of solvent used is desirably such that the reaction system is maintained uniformly. The specific amount used varies depending on the type of bisphenol used, the type and composition of the solvent, and cannot be uniformly prescribed, but it is usually 100 to 10,100 O per mole of bisphenol used! degree, preferably 200
It is suitable that the area is approximately 500 m2.

The reaction temperature in this first step is usually 30 to 120°C.
The temperature is preferably about 50°C to 80°C.

When the reaction is carried out as described above, a salt of the bisphenol and the strong alkaline compound used in the reaction solution and water as a by-product are produced, but this by-produced water and the water used are collected after the reaction is completed or during the course of the reaction. Distilled together.

This water is usually removed by distillation, but in this case, a part of the solvent, especially a relatively low boiling point solvent such as toluene, chlorobenzene, xylene used as a mixed solvent, is distilled off together with the water. A method is preferably used.

For example, when a mixed solvent of N-methylpyrrolidone and chlorobenzene as described above is used as the solvent, water in the system may be distilled off together with chlorobenzene at a temperature generally in the range of 120 to 140°C.

In the second step, the reaction product liquid obtained by distilling off water and excess solvent in the first step and a bis(4-halogenophenyl)sulfone such as bis(4-chlorophenyl)sulfone, preferably A solution obtained by separately dissolving sulfones in the same solvent as above is mixed, and the reaction product of bisphenols with a strong alkaline compound and the above sulfones are condensed and polymerized to produce the desired polysulfone.

The proportion of sulfones used is generally 1.95 to 2.10 mol, preferably 1.98 to 2.05 mol, per 1 mol of bisphenols used.

Here, as the solvent used for the above-mentioned sulfones, the above-mentioned examples can be mentioned, but among them, a mixed solvent of N-methylpyrrolidone and chlorobenzene can be particularly preferably used. The amount of solvent used is desirably such that the reaction system can be kept uniform.

The reaction temperature is preferably about 120 to 200°C, preferably about 140 to 160°C. Note that this reaction can usually be suitably carried out by increasing the reaction temperature as appropriate; in this case, as the reaction progresses, or once the reaction has progressed to an appropriate extent, the temperature is increased and the reaction temperature is increased. A method of distilling off excess solvent such as chlorobenzene can be suitably employed.

The reaction time cannot be uniformly specified because it varies depending on the reaction temperature, its operation mode, and various other factors, but it is usually about 2 to 20 hours, preferably 4 to 1 hour.
It may be about 0 hours.

To give a specific example, when using a mixed solvent of N-methylpyrrolidone and chlorobenzene as a solvent for bis(4-chlorophenyl)sulfone, the reaction temperature is raised to about 140 to 160°C for a while. A preferred method is to continue the reaction at around 160° C. for about 2 hours after distilling off chlorobenzene.

In addition, for the above condensation polymerization reaction, appropriate molecules may be used as necessary!
Additives such as regulators, crosslinkers, polymerization promoters, etc. may also be used.

As the molecular weight regulator, known ones can be used, and specific examples include monohydric phenols such as phenol, tert-butylphenol, nonylphenol, octylphonol, dodecylphenol, cumylphenol, and phenylphenol. Can be done. Among these, phenol etc. can be particularly preferably used.

In the manner described above, a reaction product liquid containing the polysulfone of the present invention can be obtained.

This polysulfone can be recovered in various purities by conventional separation and purification methods.

As a method for separating and recovering polysulfone from the reaction product liquid, for example, a method of cooling the reaction product liquid and then injecting it into water to precipitate it can be suitably employed.

This precipitated polymer is usually pulverized to the desired particle size, washed with a water-methanol mixture to remove residual alkali halides and other impurities, and then dried to obtain a product with the desired purity. It can be finished as.

The polysulfone resin of the present invention thus obtained is
It has excellent properties such as heat resistance, rigidity, and toughness that ordinary polysulfone resins have, and it also has excellent oxidation resistance and hydrolysis resistance, and in particular, has significantly improved fluidity during molding. Therefore, it is easy to mold under relatively mild conditions, and since the photoelastic coefficient is moderately small, distortion during molding, especially optical distortion, is difficult to occur.
It is an engineering plastic with excellent properties such as being able to be finished as a molded product with extremely low optical anisotropy, and is especially suitable for use as a variety of industrial materials, including materials for optical equipment. Can be done.

〔Example〕

(Example 1) 76.10 g (0.20 mol) of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane was added to 50 mj of N-methylpyrrolidone! , chlorobenzene 200m1!
, at 60-80°C. Add to this 28.2mj of 14.2N aqueous sodium hydroxide solution! (0°40 mol)
was added, stirred and heated. Chlorobenzene was distilled at 120 to 140°C to drive out water in the system. To this was added 57.43 g of bis(4-chlorophenyl)sulfone (0,2
mol), N-methylpyroIJF 50 mff1 and chlorobenzene 100 mj! It was dissolved in a mixed solvent with and added.

After that, chlorobenzene was distilled off and the reaction temperature was adjusted to 160~160℃.
After the temperature rose to 170°C and reacted for 5 hours, the mixture was cooled.
The polymer was recovered by injection into water. This polymer was pulverized using a Waring blender, washed several times with water and methanol, and then dried at 100° C. under reduced pressure. The properties of the obtained polymer were as follows.

Intrinsic viscosity -0.52 dl/g (in chloroform, 20°C
Glass transition temperature = 191°C Photoelastic coefficient -63X 10 I! cm! /dyne water vapor permeability = 1.6 g -m/rd ・24 hrs In addition, this polymer has an IH-NMR (acetone dh) δ (
ppm) is 2.1 (6H), 7.5~8゜2 (24
H), and in infrared absorption spectrum analysis, 12
An ether bond was confirmed at 50 cm-', and from these, it was found that the following repeating unit was present.

(Example 2) In place of 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1-phenyl-1°1-bis(3
-Phenyl-4-hydroxyphenyl)ethane was used in the same manner as in Example 1. The physical properties of the obtained polymer were as follows.

Intrinsic viscosity = 0.48a/g Glass transition temperature = 215°C Photoelastic coefficient = 55 x 10-13CI11”/d
yne moisture permeability=1.1g-mm/%24hrs'H-N
The results of MR analysis and infrared absorption spectrum analysis are shown in Example 1.
It was found that this polymer has the following repeating unit.

(Example 3) It was carried out in the same manner as in Example 1 except that bis(3-phenyl-4-hydroxyphenyl) sulfone was used instead of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane. . The physical properties of the obtained polymer were as follows.

Intrinsic viscosity = 0.55a/g Glass transition temperature = 208°C Photoelastic coefficient = 60 x 10-” cm2/dyne
Moisture permeability -1.7g-mn+/rr?・24hrs'H-
The results of NMR analysis and infrared absorption spectrum analysis were the same as in Example 1, and this polymer was (Comparative Example 1) in place of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane. It was carried out in the same manner as in Example 1 except that bis(4-hydroxyphenyl)propane was used. The physical properties of the obtained polymer were as follows.

Intrinsic viscosity = 0.62d1/g Glass transition temperature = 193°C Photoelastic coefficient = 93 X 10-+3CI11”/d
yne moisture permeability = 3.2 g -arn/rrr ・24
h r sThis polymer consists of the following repeating units.

[Effects of the Invention] The polysulfone resin of the present invention is a novel polysulfone resin having a specific repeating monomer unit and a specific intrinsic viscosity, and has excellent heat resistance, rigidity, toughness, heat resistance, hydrolysis resistance, etc. It has excellent elastic properties, improved fluidity during molding, and a moderately reduced photoelastic coefficient.
Therefore, it has the advantage that it can be easily molded under relatively mild conditions, and that it is possible to obtain a molded product with extremely small optical anisotropy and significantly suppressed optical distortion due to molding. be.

The second aspect of the present invention is to use specific bisphenols, bis(4-halophenyl) sulfone such as bis(4-chlorophenyl) sulfone, and strong alkaline compounds such as sodium hydroxide as reaction raw materials during the production of the above polysulfone resin. Since the process is simple, the reaction efficiency is high, it is economical, and the conventional polysulfone resin manufacturing process can be easily applied.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [However, in formula (I), Y is a single bond, ether bond, thioether bond, -SO_2-, ▲ Mathematical formula ,Chemical formula,
There are tables, etc. ▼ (However, R^1 and R^2 represent hydrogen atoms, alkyl groups of C_1 to C_6, or phenyl groups.), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, n is , represents an integer from 2 to 10), or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, m represents an integer from 4 to 8.). ] A polysulfone resin having a repeating unit represented by the following and having an intrinsic viscosity of 0.4 dl/g or more at 20°C in chloroform. 2. General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [However, in formula (I), Y is a single bond, ether bond, thioether bond, -SO_2-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (However, R^1 and R^2 represent hydrogen atoms, alkyl groups of C_1 to C_6, or phenyl groups.), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, n is , represents an integer from 2 to 10), or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, m represents an integer from 4 to 8.). ] Bisphenols represented by the general formula (III) ▲ mathematical formula,
There are chemical formulas, tables, etc. ▼ (III) [However, in the formula, X^1 and X^2 each represent a halogen atom. Note that X^1 and X^2 may be of the same type or may be of different types. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (I) which are characterized by reacting with the compound represented by (I) [However, in formula (I), Y has the same meaning as above. ] A method for producing a polysulfone resin having a repeating unit represented by the following and having an intrinsic viscosity of 0.4 dl/g or more at 20°C in chloroform. 3. The compound represented by the general formula (III) is bis(4
-chlorophenyl) sulfone
Method for producing polysulfone resin described in Section 1.