JPS63108024A - Novel polycarbonate copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate polymer excellent in optical properties, having an adjustable refractive index and useful as a material for optical instruments, by reacting a specified bisphenol with a carbonic ester-forming compound. CONSTITUTION:Bisphenols of formula I and II are reacted with a carbonic ester-forming compound to obtain a polycarbonate polymer having repeating units of formulas III and IV and a reduced viscosity >=0.2dl/g (as measured in a 0.5g/dl concentration solution in methylene chloride at 20 deg.C). In the formulae, X and Y are each a single bond, an ether bond, a thioether bond, -SO2-, a group of formula V (wherein R<3> and R<4> are each H, a 1-5C alkyl or phenyl) or a group of formula VI (wherein n' is 4-8), X=Y or Xnot equal to Y, R<1> and R<2> are each H, a halogen, a 1-5C alkyl or phenyl and l and m are each 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polycarbonate copolymer and a method for producing the same. More specifically, the present invention provides a novel polycarbonate-based copolymer that has excellent optical properties such as a particularly high refractive index, which is useful as a material for optical equipment, and can also adjust the value of the refractive index; It concerns the manufacturing method.

[Conventional technology]

Traditionally, typical polycarbonate resins are 2.2
A product obtained by reacting -bis-(4-hydroxyphenyl)propane (bisphenol A) with phosgene or diphenyl carbonate is known.
Because it has excellent properties such as excellent transparency, heat resistance, and mechanical properties, as well as good molding accuracy, it is widely used as an engineering plastic in many fields.

By the way, plastic optical elements have been gaining popularity in recent years because they have advantages such as being lighter than glass ones, having excellent impact resistance, no polishing required, easy mass production, and the ability to mass produce aspherical lenses. The demand for it is increasing.

It is known that polycarbonate polymers are useful as materials for plastic optical elements because they have excellent optical properties such as excellent transparency and high refractive index (Japanese Patent Laid-Open No. 58-126119). Publication, JP-A-58-1
79224), and as the uses of the optical element expand, there has been a desire to develop a new material with even better optical properties.

[Problem that the invention seeks to solve]

Under these circumstances, an object of the present invention is to provide a novel polycarbonate copolymer having excellent optical properties and useful as a material for optical devices.

[Means for solving problems]

As a result of extensive research into new polycarbonate copolymers, the present inventors have discovered a novel polycarbonate copolymer obtained by reacting a dihydric phenol with a specific structure with a carbonate-forming compound. However, it was discovered that it has a particularly high refractive index and has excellent optical properties such as being able to adjust the value of the refractive index, and based on this knowledge, the present invention was completed.

That is, the present invention relates to the general formula [wherein X and Y are a single bond, an ether bond, or an onythyl bond, or -5O7-1-C- (where R3 and R4 are each a hydrogen atom and 1 to 5 alkyl group or phenyl group), -←C1+ x=y
or Xt-Y, R1 and R2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and β and m are each an integer of 1 to 4.] A repeating unit represented by The temperature of a solution with a concentration of 0.5 g/dβ using methylene chloride as a solvent is 20
Reduced viscosity [ηsp/c) at °C is 0.2 d j!
/ g or more, and this polycarbonate copolymer is expressed as: It can be produced by reacting a dihydric phenol with a carbonate-forming compound.

In the copolymer of the present invention, specific examples of the compound having the structure represented by the general formula (III) used as a raw material include bis(3-phenyl-4-hydroxyphenyl)methane, 1,1-bis( 3-phenyl-4-hydroxyphenyl)ethane, 1゜2-bis(3-phenyl-4
-hydroxyphenyl)ethane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1.3-
Bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)butane, 1,4-bis(3-phenyl-4-hydroxyphenyl)butane, 2,2 -bis(3-phenyl-4-hydroxyphenyl)octane, 1,8-bis(
3-phenyl-4-hydroxyphenyl)octane, 1
-Phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)ethane, diphenyl-bis(3-phenyl-4-hydroxyphenyl)methane, 1,1-bis(
3-phenyl-4-hydroxyphenyl)cyclopenkune, 1. l-Bis(3-phenyl-4-hydroxyphenyl)cyclohexane, bis(3-phenyl-4-hydroxyphenyl)sulfone, 3,3'-diphenyl-4
, 4'-dihydroxybiphenyl, 3,3'-diphenyl-414'-dihydroxydiphenyl ether, and 3°3'-diphenyl-4,4'-dihydroxydiphenyl sulfide.

In addition, as a compound represented by the general formula (■), 2.2
-bis(4-hydroxyphenyl)propane, 2,2-
Bis(3-methyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(
4-hydroxyphenyl)octane, 4,4-bis(4
-hydroxyphenyl)hebutane, 2,2- (3,5
,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane, (3,3'-dichloro-4,4
'-dihydroxydiphenyl)methane, bis-(3,5
-dimethyl-4-hydroxyphenyl) ether, bis-(3,5-dimethyl-4-hydroxyphenyl) sulfone, bis-(3゜5-dimethyl-4-hydroxyphenyl) sulfide, bis-(3,5-dimethyl) -4-hydroxydiphenyl)cyclohexane and the like.

On the other hand, examples of carbonate-forming compounds include phosgene, diphenyl carbonate, g-p-)lyl carbonate, phenyl-p-tolyl carbonate, and di-p-tolyl carbonate.
- bisaryl carbonates such as chlorophenyl carbonate and dinaphthyl carbonate.

The copolymer of the present invention can be produced by known methods used to produce polycarbonate from bisphenol A, such as direct reaction of dihydric phenol and phosgene, or ester reaction of dihydric phenol and bisaryl carbonate. Methods such as exchange reaction can be employed.

In the former direct reaction method of dihydric phenol and phosgene, the dihydric phenol represented by the general formulas (III) and (IV) is reacted with phosgene, usually in the presence of an acid binder and a solvent.

Examples of acid binders used include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of solvents include methylene chloride,
Chlorobenzene, xylene, etc. are used. moreover,
To accelerate the polycondensation reaction, catalysts such as tertiary amines such as triethylamine or quaternary ammonium salts are used, and molecular weight regulators such as pt-butylphenol and phenylphenol are used to adjust the degree of polymerization. It is desirable to carry out the reaction by adding an agent. Further, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added as desired.

The blending ratio of dihydric phenol (I[l) and (IV) is arbitrary; if you want to obtain a copolymer with a high refractive index, you can increase the ratio of the compound (II[>) used. .The refractive index can be changed from 1.58 to 1.67 depending on the blending ratio.When the ratio of repeating unit (1) in the obtained copolymer is 20 mol% or more, the refractive index is 1.60.
A copolymer having a refractive index higher than that can be obtained.

The reaction is usually carried out at a temperature ranging from 0 to 150°C, preferably from 5 to 40°C. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours.
It's time. Further, during the reaction, it is desirable to maintain pl+ of the reaction system at 10 or more.

On the other hand, in the latter transesterification method, the general formula (I
) and (IV) and bisaryl carbonate are mixed and reacted under reduced pressure at high temperature. The reaction is usually carried out at 150-350°C, preferably at 2
The reaction is carried out at a temperature in the range of 00 to 300° C., and the degree of vacuum is preferably set to 1 fin Hg or less at the end, so that the phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. The reaction time depends on the reaction temperature, degree of pressure reduction, etc., but is usually 1~
It takes about 4 hours. The reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon, and if desired, the above-mentioned molecular weight regulator, antioxidant, etc. may be added to carry out the reaction.

The thus obtained copolymer of the present invention is a novel polycarbonate-based copolymer having repeating units represented by the above general formula, and is composed of 0, 5
Reduced viscosity (7
7Sp/C) is 0.2d7! /g or more. If the reduced viscosity is less than 0.2 dβ/g, the degree of polymerization is too low and the object of the present invention cannot be fully achieved.

The copolymer of the present invention has a particularly high refractive index, and the value of the refractive index can be adjusted.

The copolymer of the present invention may be molded by methods normally used for molding polycarbonate resins, such as injection molding, compression molding, the low-links method, which is a combination of injection molding and compression molding, and micromolding. Any method can be used.

In the above molding method, the copolymer of the present invention may be molded as it is, but if desired, various components,
For example, phosphorous esters to prevent coloration and deterioration of transparency, plasticizers to increase the melt index value, etc. may be blended and molded, and the characteristics of the copolymer of the present invention may be Other resins may be blended and molded within a range that does not impair the properties.

Examples of the sulfite esters used in this case include tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trisstearyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (nonylphenyl)phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di-2-
Examples include ethylhexyl phosphite, phenyldidecyl phosphite, tricyclohexyl phosphite, distearylpentaerythrityl diphosphite, diphenylpentanyl strityl diphosphite, and the like.

Examples of plasticizers include alkyl phthalates such as 2-ethylhexyl phthalate, n-butyl phthalate, isodecanyl phthalate, tridecanyl phthalate, heptyl tucrate, and nonyl phthalate, 2-ethylhexyl adipate, and 2-ethylhexyl adipate. - Alkyl esters of dibasic acids such as ethylhexyl sebacate, phosphate alkyl esters such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate, epoxidized octyl oleate, epoxidized butyl oleate, etc. Examples include epoxidized fatty acid esters, polyester plasticizers, and chlorinated fatty acid esters.

〔Example〕

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way.

510 g (3 mol) of 0-phenylphenol and 58 g (1 mol) of acetone were mixed, heated to 60°C and dissolved, then mercaptoacetic acid Log was added as a catalyst, and hydrochloric acid gas was blown in for 36 hours while stirring. . After washing the obtained reaction product three times with warm water, the organic phase was heated to 190 ml under reduced pressure.
heated to ℃.

Then, the residue was dissolved in 400 mA of methylene chloride, and 2
After adding 500 mj+ of a normal aqueous sodium hydroxide solution and stirring, it was cooled on ice to precipitate crystals, which was then washed, and then added to 1N hydrochloric acid 2β, after stirring, the crystals were filtered and washed several times with water. Afterwards, it was dried under reduced pressure.

In this way, 154 g of crystals (yield 40%) were obtained. The melting point of this compound is 58-60°C, and the purity is 99°C.
．． It was 3%. According to proton NMR analysis, this compound has the following structure 2.

Production of 2-bis(3-phenyl-4-hydroxyphenylon) The following structure was prepared by performing the same operation as in Production Example 1, except that 120 g (1 mol) of acetophenone was used instead of acetone in Production Example 1. 1-phenyl-1,
110 g (yield 25%) of 1-bis(3-phenyl-4-hydroxyphenyl)ethane was obtained. The melting point of this compound was 67-68°C, and the purity was 99.1%.

Production Example 3 Bis(3-phenyl-4-hydroxy0-
391 g (2.3 mol) of phenylphenol, 100 g (1.0 mol) of 98% sulfuric acid and 100 g of chlorobenzene
9.5 g of benzenesulfonic acid (0.05 g)
mol) was added and heated while stirring. Produced water azeotropically distilled out together with chlorobenzene at around 135°C. The distillate was condensed and separated into two phases, and the organic phase was continuously returned to the reactor. Indoor bath 165 10 hours after the start of distillation
℃ and the aqueous phase reached 35 mA. Add 50% xylene to this
0 mβ was added and cooled to precipitate crystals. The crystals were washed with methylene chloride and then recrystallized from a mixed solution of acetone and cyclohexane to obtain 340 g (yield: 85%) of a product. The melting point of this compound is 'H-
NMR (acetone a6) δ (pp+n) is 7
．． 16 (2H, d), 7.31-7.47 (6
H, m), 7.58 (4H, d), 7.83 (2
H, dd), 7.91 (2H, d), the molecular weight (m+) is 402, and the purity is 99.7% (HPLC
).

From this, it was confirmed that this compound has the following structure.

510 g (3 mol) of O-phenylphenol and 98 g (1 mol) of cyclohexanone were mixed, heated to 60°C to dissolve, then 150 g of 90% by weight sulfuric acid was added, and heated at 70°C with stirring. The reaction was carried out at C for 24 hours. The obtained reaction product was diluted with monochlorobenzene at 1°C and washed three times with warm water, and then the organic phase was heated to 190°C under reduced pressure to remove the solvent and unreacted raw materials. Then, the residue was treated with 400mj of methylene chloride! Dissolved in 500mj of 5N sodium hydroxide aqueous solution! was added and stirred, cooled on ice to precipitate crystals, and the crystals were mixed with 500mj of methylene chloride! After washing twice with
After washing with A, the crystals were added to 2N hydrochloric acid (2Il) and stirred, the crystals were filtered, washed several times with water, and then added with acetone.
It was recrystallized from a cyclohexane mixed solution.

In this way, 189 g of crystals (yield 45%) were obtained. The melting point of this compound is 143-145℃, H-NMR
(Acetone d6) δ (ppm) is 1°6 to 1
．． 8 (10H, m), 6. 89 (2H, d),
7.10 (2H, dd), 7.2~7.4 (8H
, m), 7.56 (4H, dd), and the molecular weight is (
m+) was 420.

From this, it was confirmed that this compound has the following structure.

Example 1 Internal volume II! 2.2-screws (
70 g (0.25 mol) of 4-hydroxyphenyl)propane in 480 mj of a 6% aqueous solution of sodium hydroxide!
and 250 mj+ of methylene chloride were added, and while stirring, phosgene gas was added at a rate of 900 mβ/min.
It blew for a minute. Then, the product was separated by standing to obtain a methylene chloride solution of a polycarbonate oligomer having a polymerization degree of 2 to 3 and having a chloroformate group terminal.

Finally, dilute 90 mA of this solution with methylene chloride to
20mj! binding, 0.8 g of pt-butylphenol as a molecular weight regulator, and 2,2-bis(3-phenyl-4-hydroxyphenyl)propane 1 obtained in Production Example 1 above.
4.5 g was added. Next, 1 ml of a triethylamine aqueous solution with a concentration of 5 wt% as a catalyst and 40 ml of water were added, and while stirring, 90 mj2 of a 2N aqueous sodium hydroxide solution was added.
was added dropwise over 30 minutes, followed by 1 hour under stirring.
Allowed time to react. After the reaction is complete, methylene chloride 5 is added to the product.
The mixture was diluted by adding 0.0 m It, washed sequentially with water, 0.01 N aqueous sodium hydroxide solution, 0.01 N hydrochloric acid, and water, and poured into 51 methanol.

As a result, 28 g of copolymer (yield: 86%) was obtained.

This copolymer was prepared at 0.5 g in methylene chloride as a solvent.
/ d 7! The reduced viscosity [ηsp/c) (the same applies hereinafter) at 20°C of the far degree solution was 0.48d7+/g, and the glass transition temperature was 140°C. Further, from infrared absorption spectrum analysis, absorption due to a carbonyl group was observed at a position of 1650 cm-' and absorption due to an ether bond was observed at a position of 1240 c+n-', indicating that the material had a carbonate bond. Further, from NMR spectrum analysis, the mole fraction of the repeating unit represented by the above formula (1) is 33
It was mol%. From these facts, this copolymer is
It was recognized as having the following repeating unit.

The refractive index of this polycarbonate copolymer at 20°C was 1.6350.

Example 2 Example 1 except that the amount of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane used was 7.2 g.
Similarly to (2), reduced viscosity (ηs p/c) 0
．． 43 dj! /g and a glass transition temperature of 143° C. was obtained.

This copolymer has the following repeating units and is prepared by diluting 45 ml of the methylene chloride solution of the polycarbonate oligomer obtained in Example 1 with methylene chloride to obtain a
1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)ethane obtained in Production Example 1 above while stirring. .9 g was dissolved in a mixed solution of 10 ml of pyridine and 10 ml of methylene chloride and added dropwise. The reaction was continued for 1 hour at room temperature while stirring. After the reaction is complete,
The product was diluted with 300 ml of methylene chloride and washed with 2N hydrochloric acid and then with water. The product was then poured into 272 methanol to precipitate and collect the copolymer.

The obtained copolymer has a reduced viscosity [ηs p/c) of 0.
38dl! , /g, the glass transition temperature is 154°C,
From infrared absorption spectrum analysis and NMR spectrum analysis, it was confirmed that it had the following repeating unit.

The refractive index of this copolymer is 1.6558 at 20°C.
Met.

Example 4 A solution of the polycarbonate oligomer obtained in Example 1 in methylene chloride (300 m12) was diluted with methylene chloride to 450 m2.
mj! 0.5 g of pt-butylphenol as a molecular weight regulator and 30 g of bis(3-phenyl-4-hydroxyphenyl) sulfone prepared in Production Example 3 were dissolved in 140 ml of a 2N sodium hydroxide aqueous solution. The solution was added, and 3 ml of a 12N sodium hydroxide aqueous solution and 1.0 ml of a 5% by weight triethylamine aqueous solution as a catalyst were added, and the mixture was reacted for 1 hour with vigorous stirring. After the reaction was completed, the same procedure as in Example 1 was carried out.

As a result, 112 g (yield: 92%) of a copolymer was obtained.

This copolymer has a reduced viscosity [ηs p/c) of 0°63
d1. /g, and the glass transition temperature was 158°C. Furthermore, infrared absorption spectroscopy and NMR spectroscopy revealed that the molar fraction of the repeating unit represented by formula (1) was 13 mol%.

From these facts, this copolymer was recognized to have the following repeating units.

The refractive index of this polycarbonate copolymer at 20°C was 1.625.

Example 5 Methylene chloride of polycarbonate oligomer was prepared in the same manner as in Example 1 except that 2,2-bis(3-methyl-4-hydroxyphenylpropane was used instead of 2.2-bis(4-hydroxyphenyl)propane) A solution was obtained.

Next, the same operation as in Example 4 was performed except for using this oligomer methylene chloride solution, and 108 g of the copolymer was obtained.
(yield 89%).

This copolymer has a reduced viscosity [ηSI/c) of 0°45 dA/g and a glass transition temperature of 131
It was ℃. In addition, infrared absorption spectroscopy and NM
From R spectrum analysis, the molar fraction of the repeating unit represented by the formula (1) was 13 mol%.

From these facts, this copolymer was recognized to have the following repeating units.

The refractive index of this polycarbonate copolymer at 20°C was 1.608.

Example 6 3.3'-diphenyl-4,4'- instead of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane
The same operation as in Example 1 was performed except that dihydroxybiphenyl was used to obtain 27 g (yield: 88%) of a copolymer.

This copolymer has a reduced viscosity [ηsp/c] of O952d.
j! /g, and the glass transition temperature was 144°C. Furthermore, infrared absorption spectroscopy and NMR spectroscopy revealed that the molar fraction of the repeating unit represented by the formula CI) was 22 mol%.

From these facts, this copolymer was recognized to have the following repeating units.

The refractive index of this polycarbonate copolymer at 20°C was 1.602.

Example 7 1.1-bis(3-phenyl-4-
The same operation as in Example 1 was performed except for using (hydroxyphenyl)cyclohexane, and 29 g of copolymer (yield: 9) was obtained.
2%).

This copolymer has a reduced viscosity [ηs p/c) of 0°57
d lI/g, and the glass transition temperature was 151°C. Furthermore, infrared absorption spectroscopy and NMR spectroscopy revealed that the molar fraction of the repeating unit represented by the formula CI) was 23 mol%.

From these facts, this copolymer was recognized to have the following repeating units.

The refractive index of this polycarbonate copolymer at 20°C was 1.603.

A reference example is a polycarbonate (reduced viscosity 0.51 dA/g) obtained by a normal phosgene method using 2,2-bis(4-hydroxyphenyl)propane as the phenol.
As a result of measuring the refractive index at 20°C, it was 1.5850.
Met.

〔Effect of the invention〕

The polycarbonate copolymer of the present invention is novel and has excellent optical properties such as a particularly high refractive index, and the value of the refractive index can be adjusted, so it can be used as a material for various optical devices. , such as still cameras, video cameras, telescopes, glasses, contact lenses, prisms, etc.
It can be used for optical fibers, video discs, audio discs, optical memory discs, etc.

It is also useful as an engineering plastic and as a material for various molded products.

Claims (1)

[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, X and Y are single bonds, ether bonds, thioether bonds, or - SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^3 and R^4 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (however, n is an integer from 2 to 10) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (however, n' is an integer from 4 to 8), and X=Y
However, X≠Y may be satisfied, R^1 and R^2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and l and m are each an integer of 1 to 4. A novel polycarbonate-based copolymer having a repeating unit of . 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [X and Y in the formula are single bonds, ether bonds, thioether bonds, or -SO2-, ▲ mathematical formulas, There are chemical formulas, tables, etc. ▼ (However, R^3 and R^4 are hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or phenyl groups, respectively), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, is an integer from 2 to 10) or ▲There is a mathematical formula, chemical formula, table, etc.▼ (however, n is an integer from 4 to 8), and X=Y or X≠Y may be R^1 and R^2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and m is an integer of 1 to 4, respectively]. General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X, Y, R^1, R^2, l, m have the same meanings as above), and the reduced viscosity [ηsp/c] of a solution with a concentration of 0.5 g/dl using methylene chloride as a solvent is 0 at a temperature of 20°C. .2 dl/g or more of a polycarbonate copolymer manufacturing method.