JPS63108023A - Novel polycarbonate polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate polymer having excellent optical properties and being useful as, e.g., a material for optical instruments, by reacting a specified bisphenol with a carbonic ester-forming compound. CONSTITUTION:A bisphenol of formula I is reacted with a carbonic ester- forming compound to obtain a polycarbonate polymer comprising repeating units of formula II and having 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 is a single bond, an ether bond, a thioether bond, -SO2-, a group of formula III (wherein R<1> and R<2> are each H, a 1-5C alkyl or phenyl), a group of formula IV (wherein n is 2-20) or a group of formula V (wherein n' is 4-8). This polymer has a particularly high refractive index and, for example, a polycarbonate obtained from 2,2-bis(3-phenyl-4-hydroxyphenyl)propane has a refractive index of 1.6662 at 20 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polycarbonate polymer and a method for producing the same. More specifically, the present invention relates to a novel polycarbonate polymer with excellent optical properties, such as a particularly high refractive index, which is useful as a material for optical equipment, and a method for producing the same.

[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 polymer having excellent optical properties and useful as a material for optical devices.

[Means for solving problems]

As a result of intensive research into new polycarbonate-based polymers, the present inventors have discovered that a new polycarbonate-based polymer obtained by reacting a dihydric phenol with a specific structure with a carbonate-forming compound, It was discovered that it has excellent optical properties such as a particularly high refractive index, and based on this knowledge, the present invention was completed.

That is, the present invention relates to the general formula [wherein is an alkyl group or phenyl group), ÷CH,su' (where n
is 2 to 1\l (where n' is an integer of 4 to 8)] 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 0.21! /g or more,
This polycarbonate polymer can be produced, for example, by reacting a dihydric phenol represented by the general formula (in which X has the same meaning as above) with a carbonate-forming compound.

In the polymer of the present invention, the dihydric phenol used as a raw material is a compound having a structure represented by the general formula (If), and specifically, 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
．． I-bis(3-phenyl-4-hydroxyphenyl)
Cyclopencune, 1.1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane, bis(3-phenyl-4-hydroxyphenyl)sulfone, 3.3'-diphenyl-4°4'-dihydroxybiphenyl, 3,3
'-diphenyl-4,4'-); Hydroxydiphenyl ether, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide, and the like.

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

The polymer of the present invention can be produced by known methods used to produce polycarbonate from bisphenol A, such as direct reaction between dihydric phenol and phosgene, or transesterification reaction between dihydric phenol and bisaryl carbonate. Methods such as the following can be adopted.

In the former direct reaction method of dihydric phenol and phosgene, the dihydric phenol represented by the general formula (I[) and phosgene are reacted, usually in the presence of an acid binder and a solvent. Examples of acid binders include pyridine,
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used, and as the solvent, for example, methylene chloride, chlorobenzene, xylene, etc. are used. Furthermore, to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt, and a p-
It is desirable to carry out the reaction by adding a molecular weight regulator such as t-butylphenol or phenylphenol. Also,
If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added. The reaction is usually O~
It is carried out at a temperature of 150°C, preferably in the range 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.

Further, during the reaction, it is desirable to maintain p)l of the reaction system at 10 or more.

On the other hand, in the latter transesterification method, the general formula (I
The dihydric phenol represented by [) and bisaryl carbonate are mixed and reacted under reduced pressure at high temperature. The reaction is usually carried out at 150 to 350°C, preferably 200 to 300°C.
The reaction is carried out at a temperature in the range of 0.degree. C., and the degree of vacuum is preferably 1 mHg 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 about 1 to 4 hours. The reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be carried out with the addition of the above-mentioned molecular N regulator, antioxidant, etc., if desired.

The thus obtained polymer of the present invention is a novel polycarbonate-based polymer consisting of repeating units represented by the general formula (X in the formula has the same meaning as above), and uses methylene chloride as a solvent. Yes0, 5
The reduced viscosity [ηsp/c) of a solution with a concentration of 14 g/d at a temperature of 20° C. is 0.2 dlI/g or more.

Those with a reduced viscosity of less than 0.2 dl/g are
The degree of polymerization is too low to fully achieve the purpose of the present invention.

The polymer of the present invention has a particularly high refractive index, for example, 2,2-bis(3-phenyl-4
-Hydroxyphenyl)propane has a refractive index of 1.66 at a temperature of 20°C.
62, and 1-phenyl-1,1-bis(3-
The refractive index of the polycarbonate obtained from phenyl 74-hydroxyphenyl)ethane was 1.6750.

In contrast, the refractive index of polycarbonate obtained from bisphenol A was 1.5850.

The method for molding the polymer of the present invention includes methods normally used for molding polycarbonate resins, such as injection molding,
Any method can be used, such as a compression molding method, a low-links method that is a combination of injection molding and compression molding, and micromolding.

In the above molding method, the polymer of the present invention may be molded as it is, but if desired, the polymer may be added with various components, such as phosphorous esters to prevent coloring and deterioration of transparency, melt It may be molded by adding a plasticizer to increase the index value, or it may be molded by adding other resins to the extent that the properties of the polymer of the present invention are not impaired.

Examples of the phosphite esters used in this case include tributyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trisstearyl phosphite, triphenyl phosphite, tricresyl phosphite, and tris(2-ethylhexyl) phosphite. nonylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di-2-
Examples include ethylhexylbosphite, phenyldidecylphosphite, tricyclohexylphosphite, distearylpentaerythrityl diphosphite, diphenylpentanylsthrityl diphosphite, and the like.

Examples of plasticizers include alkyl phthalates such as 2-ethylhexyl phthalate, n-butyl phthalate, isodecanyl phthalate, tridecanyl phthalate, heptyl phthalate, 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 ml of methylene chloride,
2N sodium hydroxide aqueous solution 500m7! was added and stirred, cooled on ice to precipitate crystals, washed twice with 400 ml of methylene chloride, then washed with 500 ml of 2N aqueous sodium solution, then added to 1N hydrochloric acid 21 and stirred. The crystals were filtered, washed several times with water, and then dried under reduced pressure.

In this way, 154 g of crystals (yield: 40%) were obtained. The melting point of this compound was 58-60''C, and the purity was 99.3%. Analysis by proton NMR revealed that this compound was 2゜2-bis(3-phenyl-4-hydroxy) having the following structure. Production of phenylon 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%.

0-phenylphenol 391g (2.3 mol), 98
% sulfuric acid 100 g (1,0 mol) and chlorobenzene 1
00 g of the mixture, add 9.5 g of benzenesulfonic acid (0,
05 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.

Ten hours after the start of distillation, the internal temperature reached 165°C and the aqueous phase reached 36 m#. 500 ml of xylene was added to this and cooled to precipitate crystals. After washing the crystals with methylene chloride, they were 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 251-252°C, and the 'H-NMR (acetone d6) δ (ppm) is 7.16 (2H, d
), 7.31-7.47 (6H, m), 7.58
(4H, d) , 7.83 (2H, dd) , 7.9
1 (2H, d), the molecular weight (m+) was 402, and the purity was 99.7% (by HPLC).

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

510 g (3 mol) of droxyphenyl O-phenylphenol and 98 g (1 mol) of cyclohexanone were mixed, heated to 60°C to dissolve, and then 150 g of sulfuric acid with a concentration of 90% by weight was added, and 70 g of cyclohexanone was mixed with stirring. The reaction was carried out at ℃ for 24 hours. The obtained reaction product was diluted with 11 parts of monochlorohenzene and diluted with 3 parts of warm water.
After washing twice, the organic phase was heated to 190°C under reduced pressure.
The solvent and unreacted raw materials were distilled off. Then, the residue was mixed with 400 mj of methylene chloride! Add 500 m# of aqueous sodium hydroxide solution with a 5N concentration, stir, cool on ice to precipitate crystals, and add 500 m of methylene chloride to the crystals.
After washing twice with 0mj2, washing with 2N aqueous sodium solution 300mA, and then washing with 2N hydrochloric acid 2
1 and stirred, the crystals were filtered, washed several times with water, and then recrystallized from an acetone-cyclohexane mixed solution.

In this way, 189 g of crystals (yield 45%) were obtained. The melting point of this compound is 143-145°C and 'H-NM
R (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) and 7.56 (4H, dd), and the molecular weight (m+) was 420.

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

Example 1 A flask with a baffle plate having an internal volume of 11 was filled with 2 obtained in Production Example 1.
, 2-bis(3-phenyl-4-hydroxyphenyl)
Add 60 g of propane, 1 g of pt-butylphenol as a molecular weight regulator, and 500 n12 methylene chloride and dissolve them, then add 300 mβ of water and 1 ml of triethylamine as a catalyst, and heat 30 g of phosgene gas at 20 to 30°C while stirring.
While blowing notes 0 to 4, a 12N aqueous sodium hydroxide solution was added dropwise so that the pu of the reaction system did not fall below 10. After blowing phosgene gas for 25 minutes,
The reaction was allowed to proceed at ~25° C. for 1 hour with stirring.

After the reaction, the product was diluted with 700ml of methylene chloride, water, 0.01N sodium hydroxide, water, 0.
．． The polymer was washed with 01N hydrochloric acid and water in that order and poured into 51 methanol to precipitate and collect the polymer. Finished polymer was 64 g (97% yield).

The polymer obtained here was prepared using methylene chloride as a solvent.
．． Reduced viscosity of a solution of 5 g/d l-fM degrees [ηs
p/C] (the same applies hereinafter) is 0. 4. 2 d it /
g, and the glass transition temperature was 138°C. In addition, this polymer was found to have 165% by infrared absorption spectrum analysis.
Absorption due to carbonyl group at 0 cm-' position, 1240
Absorption due to an ether bond was observed at the cm-' position, and it was recognized that the polycarbonate had a carbonate bond, indicating that it was a polycarbonate consisting of the following repeating unit.

Furthermore, the refractive index of this polycarbonate at 20° C. was as large as 1.6662.

Example 2 A polymer was produced in the same manner as in Example 1, except that 65 g of 1-phenyl-1,1-bis(3-phenyl-4-hydroxyphenyl)ethane obtained in Production Example 2 was used.

The reduced viscosity [η sp/c) of the obtained polymer was 0.45 d.
ll/g, the glass transition temperature was 174°C and the refractive index was 1.6750. From infrared absorption spectrum analysis, it was confirmed that the polymer had carbonate bonds, and this polymer had the following repeating units.

Example 3 Bis(3-
Phenyl-4-hydroxyphenyl) sulfone 95g (
0.236 mol) was dissolved in 650 ml of a 1.2N aqueous sodium hydroxide solution, and 250 ml of methylene chloride was added.
Add j2 and add 100% phosgene gas while stirring vigorously.
Blow was carried out at a rate of 0 m for 67 minutes until the pH in the system reached 10. Thereafter, the mixture was separated by standing to obtain an oligomer having a chloroformate group terminal.

Add 300 ml of this oligomer to 450 ml of methylene chloride.
mA, and 0.6 g of pt-butylphenol was added as a molecular weight regulator. bis(3-phenyl-4
-Hydroxyphenyl) sulfone (25 g) was dissolved in 150 mj+ of a 2N sodium hydroxide aqueous solution, added to the oligomer, and 1.0 ml of a 2.5% by weight triethylamine aqueous solution was added as a catalyst! The mixture was added and reacted for 1 hour with vigorous stirring.

After the reaction, methylene chloride 1.57! diluted with water, 0.0
The polymer was washed with 1N hydrochloric acid and water in that order, and the methylene chloride phase was poured into methanol to precipitate and collect the polymer.
'C for 24 hours. The reduced viscosity (ηsp/c) of this polymer is 0.49dj! /g, and the glass transition temperature was 172°C. Further, in the infrared absorption spectrum of this polymer, the same absorption as in Example 1 was observed, and it was recognized as a polycarbonate having the following repeating unit. The yield of this product was 104 g, and the refractive index was 1.6690.

Example 4 As a dihydric phenol, 1-phenyl- obtained in Production Example 4
A polymer having a reduced viscosity [ηsp/c) of 0.59d and 127g and a glass transition temperature of 161°C was prepared in the same manner as in Example 3 except that 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane was used. I got it.

The infrared absorption spectrum of this polymer showed the same absorption as in Example 1, and it was recognized as a polycarbonate having the following repeating unit. The refractive index of this material at 20°C was 1.657.

Example 5 3,3'-diphenyl-4,4 as dihydric phenol
Reduced viscosity Cyzsp/c) 0.54 d lt/
g, a polymer having a glass transition temperature of 138°C was obtained.

The infrared absorption spectrum of this polymer showed the same absorption as in Example 1, and it was recognized as a polycarbonate having the following repeating unit. The refractive index of this material was 1.670.

Example 6 85 g (0,224 mol) of 2,2-bis(3-phenyl-4-hydroxyphenyl)propane obtained in Production Example 1 was dissolved in 650 ml of a 1.5N potassium hydroxide aqueous solution, and diluted with methylene chloride. Add 250 mA and pl of phosgene gas at a rate of 10,100 O/min while stirring vigorously.
(Blowed in until it reached 1o. After the reaction, it was left to stand and separated.
A methylene chloride solution of an oligomer having a chloroformate group end was obtained.

This solution is 300mj! 4.50 ml with methylene chloride
0.5 g of pt-butylphenol as a molecular weight regulator and 24.0 g (0,063 mol) of 2.2-bis(3-phenyl-4-hydroxyphenyl)propane were hydroxylated to a 2N concentration. Potassium solution 140m7! 1.0 ml of a 5% by weight triethylamine aqueous solution was added as a catalyst while stirring vigorously, and the mixture was allowed to react for 1 hour. Post-treatment of the reaction was carried out in the same manner as in Example 3.

The yield of polymer was 112 g.

The polymer obtained here has a reduced viscosity [η sp/c) of 0.
．． 52d7! /g. In addition, this polymer was found to have carbonate bonds by infrared absorption spectrum analysis, with absorption due to a carbonyl group at the 1650c+n-' position and absorption due to an ether bond at the 1240cm-' position. It was a polycarbonate consisting of the following repeating units.

Furthermore, the refractive index of this polycarbonate at 20°C was 1.6662.

Comparative Example A polycarbonate having the following repeating unit was obtained in the same manner as in Example 1, except that 2,2-bis(4-hydroxyphenyl)propane was used as the dihydric phenol. This polycarbonate has a reduced viscosity [ηsp/c) of 0.51dj! /g, and the refractive index at 20°C is
It was 1.5850.

〔Effect of the invention〕

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

It is also used 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. ▼ [X in the formula is a single bond, ether bond, thioether bond, or -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 and R^2 are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However,
n 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)] A novel polycarbonate polymer having a reduced viscosity [η sp/c] of 0.2 dl/g or more at a temperature of 20° C. in a solution having a concentration of 0.5 g/dl using methylene as a solvent. 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [X in the formula is a single bond, ether bond, thioether bond, or -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R^1 and R^2 are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, respectively), ▲There are mathematical 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)] Dihydric phenol and carbonate ester There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼ (X in the formula has the same meaning as above) that are characterized by reacting with forming compounds, and are composed of repeating units represented by methylene chloride. A method for producing a polycarbonate polymer in which the reduced viscosity [ηsp/c] of a solution having a concentration of 0.5 g/dl using a solvent as a solvent at a temperature of 20° C. is 0.2 dl/g or more.