JPS6395227A - Novel polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain a novel polymer having low photoelastic coefficient, melt viscosity, molding strain and birefringence and excellent optical properties, heat-resistance and strength and useful for optical disk, etc., by reacting a specific dihydric phenol with a carbonate-forming compound. CONSTITUTION:The objective polymer having the recurring unit of formula II and having an intrinsic viscosity [eta] of >=0.3dl/g in methylene chloride solution at 20 deg.C is produced by reacting (A) a dihydric phenol of formula I (R is H or 1-10C alkyl; X<1> and X<2> are H, halogen, 1-5C alkyl or phenyl; Y is benzyl, benzhydryl or trityl; n is 0-5) [e.g. 2,2-bis(4-hydroxyphenyl)-4-phenyl- butane] with (B) a carbonate-forming compound (preferably diphenyl carbonate or phosgene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new polymer and a method for producing the same, and more particularly to a new polycarbonate polymer and an efficient method for producing the same.

[Prior art and points to be solved by the invention] Conventionally, 2,2-bis(4-hydroxyphenol)propane (commonly known as bisphenol A) has been combined with carbonate ester-forming compounds such as phosgene and diphenyl carbonate. Polycarbonate resins produced by the reaction have excellent transparency, heat resistance, and mechanical strength, and are therefore used in a wide range of applications.

However, with the expansion of various uses, the requirements for polycarbonate resins have become stricter, and there is a demand for polycarbonate resins with even better performance.

In particular, when a molded article is obtained by injection molding using conventional polycarbonate resin, the molded article has a large stress optical strain and therefore a large birefringence, making it unsuitable as a material for optical equipment.

Therefore, the present inventors maintained the excellent properties of conventional polycarbonate resin such as transparency, heat resistance, and mechanical strength, while improving fluidity and photoelastic coefficient to reduce optical distortion and birefringence of molded products. We conducted intensive research to develop a new polycarbonate-based polymer that has a smaller size and improved optical properties.

[Means for Solving the Problems] As a result, the inventors discovered that a new polycarbonate-based polymer having a specific repeating unit is suitable for the above purpose, and completed the present invention.

That is, the present invention is based on the general formula (wherein R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and XI and X2 each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group) , Y is a benzyl group.

Indicates a benzhydryl group or trityl group.

In addition, n represents an integer of O to 5), and the intrinsic viscosity [η] of the chloride and methylene solution at 20°C is 0.3 di)/g
In addition to providing the above novel polymer.

By reacting the dihydric phenol represented by the general formula (wherein R, XI, A method of manufacturing is also provided.

The green return unit represented by the general formula (I) constituting the novel polymer of the present invention includes 7. I, the type and bonding position of x2,
Furthermore, there are various types depending on the type of Y and the number indicated by n, but the specific structure of the repeating unit is shown below.

etc. can be given.

Further, the degree of polymerization (molecular weight) of the novel polymer of the present invention may be determined as appropriate depending on the application, etc., but the intrinsic viscosity [η] at 20°C of a solution using methylene chloride as a solvent is 0.3 di.
l/g or more, preferably in the range of 0.3 to 1.0 di)/g. If the above-mentioned intrinsic viscosity is less than 0.3 di)/g, the obtained polymer has poor mechanical strength. It will be a small one.

The novel polymer of the present invention can be produced by various methods, but according to the production method of the present invention described above, a high-quality polymer can be produced efficiently.

In the production method of the present invention, a dihydric phenol represented by the general formula (II) and a carbonate-forming compound are introduced into a reaction system and allowed to react.

Here, the dihydric phenol of the general formula (II) is polycondensed with a carbonate ester-forming compound to constitute the green return unit of the general formula (I). We can give examples that correspond to specific examples of units.

Note that the dihydric phenol of the general formula (■) can be combined with the phenol of the general formula (where xl and x2 are the same as above) in the presence of an acidic catalyst without a solvent or in a solvent, for example. It can be produced by reacting an aldehyde or ketone represented by RC→CH2←Y (R, Y, and n are the same as above).

On the other hand, the type of carbonate-forming compound may be appropriately selected depending on the use of the polymer to be produced, but generally diphenyl carbonate, di-p-tolyl carbonate, phenyl-P-)lyl carbonate, etc. Diaryl carbonates such as carbonate, di-p-chlorophenyl carbonate or dinaphthyl carbonate, and halides of carbonic acid such as phosgene and bromphosgene are used, of which diphenyl carbonate or phosgene is preferred.

In the production method of the present invention, the above-mentioned dihydric phenol and carbonate ester-forming compound are polycondensed, but the conditions and operating methods at this time are the so-called phosgene method and the transesterification method, which have been conventionally used in the production of polycarbonate. Normally, a suitable catalyst, alkali,
A molecular weight regulator or the like may be used. Here, various m-phenols can be used as the molecular weight regulator, but preferred ones include phenol, tert-butylphenol, phenylphenol, and cumylphenol.

According to the method described above, the novel polymer of the present invention can be obtained, but when molding various molded products using it,
Additives such as antioxidants and ultraviolet absorbers may be added depending on the intended use.

[Examples] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of dihydric phenol 14 Benzyl acetone was added to a reactor equipped with a gas blowing pipe.
8 g (1,0 mol) and 282 g (3,0 mol) of phenol.
0 mol) and mercaptoacetic acid 5 mj) as a cocatalyst were added, and dry hydrogen chloride gas was blown in at 40°C with stirring for 5 hours. After pulverizing the obtained reaction product, 6
It was washed three times with 500 layers of water at 0° C. and then recrystallized from xylene to obtain 258 g of 2,2-bis(4-hydroxyphenyl)-4-phenyl-butane. Yield is 8
It was 1%.

(2) Production of copolymer 90 g (0,283 a
500% sodium hydroxide aqueous solution with a concentration of 8% by weight
ml of methylene chloride, and to the resulting solution, add 400 methylene chloride.
mA+, P-tert-butylphenol3. O
g and a 10% by weight aqueous solution 1IIi+ of triethylamine as a catalyst were added, and phosgene gas was blown into the reaction system while stirring vigorously until the pH of the reaction system reached 9.0.
After diluting the organic layer by adding 500 a+j) of methylene chloride to the obtained product, 1 ρ of water was added.

0, O1 normal sodium hydroxide aqueous solution 50hi),
water 500+sJ), 0.01N dilute hydrochloric acid 500m
1) and water 500IIli+, respectively, in this order. Then, the organic layer was poured into methanol to precipitate and collect the polymer. Yield was 91g.

This polymer was prepared at 20°C in a solution with methylene chloride as a solvent.
The intrinsic viscosity [η] was 0.18 dR/g.

In addition, the infrared absorption spectrum of this polymer contains 1 [1
Absorption due to a carbonyl group was observed at the 50c+s-1 position, and absorption due to an ether bond was observed at the 1240 cm-1 position, indicating that a carbonate bond was present.

From this, it was found that this polymer had the following repeating units.

Furthermore, the glass transition temperature of this polymer is 144℃/
1Jynε, and the photoelastic coefficient is 41.5X 10-13←Threat stand-
Met.

Example 2 (1) 210g of diphenylmethylmethylketone as raw material for preparing dihydric phenol
(1.0 mol) and 282 g (3.0 mol) of phenol were used in the same manner as in Example 1 (1).
．． 198 g of 1-diphenyl-2,2-bis(4-hydroxyphenyl)propane was obtained. The yield was 52%.

(2) As a dihydric phenol as a raw material for producing a polymer, 1 obtained in (1) above is used.
, 1-diphenyl-2,2-bis(4-hydroxyphenyl)propane (2
), 89 g of a polymer was obtained.

The intrinsic viscosity [η] of this polymer was 0.81 dj)/g. Moreover, this polymer had the following repeating unit.

there were.

Example 3 (1) Preparation of dihydric phenol Same as (1) of Example 1 except that 148 g (1.0 mol) of benzyl acetone and 324 g (3.0 mol) of orthomethylphenol were used as raw materials. and 2
．． 2-bis(3-methyl-4-hydroxyphenyl)-
270 g of 4-phenylbutane was obtained.

The yield was 78%.

(2) As a dihydric phenol as a raw material for producing a polymer, the 2 obtained in (1) above is used.
, 2-bis(3-methyl-4-hydroxyphenyl)-
87 g of a polymer having the following repeating unit was obtained in the same manner as in Example 1 (2) except that 90 g of 4-phenylbutane was used.

The intrinsic viscosity [η] of this polymer was 0.45 dβ/g. Comparative Example 1 Except for using 2,2-bis(4-hydroxyphenyl)propane as the raw material dihydric phenol, A polycarbonate consisting of the following repeating unit was obtained by carrying out the same operation as in 2).

The intrinsic viscosity [η] of this polycarbonate is 0.55dj
)/g, the glass transition temperature is 143°C, and the photoelastic coefficient is 76X 10-13! This was a large value.

[Effects of the Invention] The polymer of the present invention obtained in this way has a smaller photoelastic coefficient than conventional polycarbonate resins, has a low melt viscosity, and has little molding strain, so it has low birefringence and good optical properties. It is extremely excellent. Moreover, it has sufficient heat resistance and mechanical strength.

Therefore, the polymer of the present invention can be effectively used as a material for various industrial devices, including a material for optical devices such as optical disks.

Claims (2)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X^1 and X^2 are a hydrogen atom, a halogen atom, represents an alkyl group or phenyl group having 1 to 5 carbon atoms, Y represents a benzyl group, benzhydryl group, or trityl group; n represents an integer of 0 to 5), and A novel polymer whose intrinsic viscosity [η] of a methylene chloride solution at 20°C is 0.3 dl/g or more. (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. represents an alkyl group or phenyl group having 1 to 5 carbon atoms, Y represents a benzyl group, benzhydryl group, or trityl group; n represents an integer of 0 to 5) and carbonic acid ester formation A repeating unit represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R, X^1, X^2, Y and n are the same as above) A method for producing a novel polymer having a methylene chloride solution having an intrinsic viscosity [η] of 0.3 dl/g or more at 20°C.