JPH0641290A - Production of polycarbonate concendensate and polycarbonate composition comprising said cocondensate and glass fiber - Google Patents

Abstract

PURPOSE:To obtain the cocondensate improved in impact resistance and processability by reacting a mixture of bisphenol A with a specified bisphenol compound with a carbonate precursor. CONSTITUTION:The cocondensate is obtained by reacting a mixture of 1-90wt.% 2,2-bis(4-hydroxyphenyl)propane with 99-10wt.% bisphenol of the formula (wherein R1 is H or methyl; and R2 is H, methyl, ethyl, propyl or butyl) [e.g. 1,1-bis(4-hydroxyphenyl)ethane] with a carbonate precursor (e.g. phosgene). This cocondensate is excellent in heat resistance, transparency, impact resistance, processability, etc., and a molding of a polycarbonate composition comprising this cocondensate and glass fibers has excellent surface appearance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel polycarbonate cocondensate and a polycarbonate composition comprising the cocondensate and glass fibers.

[0002]

2. Description of the Related Art Polycarbonate (hereinafter, simply referred to as bisphenol A PC) made from 2,2-bis (4-hydroxyphenyl) propane (hereinafter, referred to as bisphenol A) and a carbonate precursor has heat resistance and resistance. Widely used as an engineering plastic with excellent impact and transparency.

However, since bisphenol A PC is inferior in processability, a method of blending polyethylene terephthalate or polybutylene terephthalate polyester has been proposed, but bisphenol A PC has been proposed.
The transparency, which is the original feature of PCs, is sacrificed. Further, although the workability is improved by suppressing the molecular weight of bisphenol A PC to be low, the impact resistance is remarkably lowered.

On the other hand, improvement of processability from the structural aspect of bisphenol APC itself has also been investigated, and a new bisphenol other than 2,2-bis (4-hydroxyphenyl) propane is reacted with a carbonate precursor. Polycarbonates and blends of such new polycarbonates with bisphenol A PC have also been proposed, but they feature the original characteristics of bisphenol A PC.
As a workability-improved product, there are still problems.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a result of intensive studies on the above points, the present inventor has found that a novel polycarbonate cocondensate obtained by reacting bisphenol A and a bisphenol having a specific structure with a carbonate precursor is bisphenol A.
It has been found that PC has excellent heat resistance and transparency inherent to PC and also has a significantly improved impact resistance / workability balance, and a composition comprising the cocondensate and glass fiber has an excellent surface appearance. The present invention has been achieved and has reached the present invention.

What is particularly surprising is that the cocondensate provides a completely different effect (improvement in appearance) in a composite system with glass fibers than a mixture of bisphenol A PC and a bisphenol homopolymer of a specific structure.

[0007]

[Means for Solving the Problems] That is, the present invention is
2,2-bis (4-hydroxyphenyl) propane 1-
Bisphenol 99 represented by the following general formula with 90% by weight
Provided is a method for producing a polycarbonate cocondensate having excellent processability, which comprises reacting 10% by weight with a carbonate precursor, and a polycarbonate composition having excellent surface appearance, which comprises the cocondensate and glass fibers. To do.

[0008]

[Chemical 1] (R ₁ is hydrogen and R ₂ is hydrogen, a methyl, propyl or butyl group, or R ₁ is a methyl group, and R
₂ is an ethyl, propyl or butyl group. )

The present invention will be described in detail below.

In the polycarbonate cocondensate of the present invention, the proportion of bisphenol A and bisphenol having a specific structure is 1 to 90 of bisphenol A based on the total amount of both bisphenols.
% By weight, 99-10% by weight of specific structure bisphenol. When the amount of bisphenol A is less than 1% by weight, the heat resistance is lowered, and when it exceeds 90% by weight, the workability cannot be improved. Bisphenol A is preferably 10 to 80% by weight, and bisphenol A having a specific structure is 90 to 20% by weight.

The specific structure bisphenol is a bisphenol represented by the following general formula, preferably bis (4-hydroxyphenyl) in which R ₁ and R ₂ are hydrogen.
Methane, bis (3-hydroxyphenyl) methane and mixtures thereof R ₁ is hydrogen and R ₂ is methyl group 1,1-bis (4-hydroxyphenyl) ethane and R ₁ is methyl group, and R ₂ is an ethyl group 2,2-
Bis (4-hydroxyphenyl) butane is preferred.

[0012]

[Chemical 1] (R ₁ is hydrogen and R ₂ is hydrogen, a methyl, propyl or butyl group, or R ₁ is a methyl group, and R
₂ is an ethyl, propyl or butyl group. )

As the carbonate precursor, phosgene,
Examples thereof include diphenyl carbonate and dialkyl carbonate.

The method for producing a polycarbonate cocondensate from bisphenol A, a bisphenol having a specific structure and a carbonate precursor is not particularly limited, but the following phosgene method, transesterification method and the like are exemplified.

(Phosgene method) Methylene chloride, 1,
In this method, an aqueous alkali solution or pyridine is added as an acid acceptor to bisphenols in the presence of an inert solvent such as 2-dichloroethane, and the reaction is carried out while blowing phosgene gas.

When an aqueous alkali solution is used as the acid acceptor, the reaction rate is increased by using a quaternary ammonium salt or a tertiary amine as the catalyst. Reaction temperature is 0-10
It is 0 ° C.

Both bisphenols may be reacted with the carbonate precursor simultaneously from the beginning, or either one of the bisphenols may be reacted with the carbonate precursor,
It is also possible to carry out the condensation reaction to some extent and then add the other and continue the reaction.

Further, the catalyst may be added from the beginning,
Any method may be used, such as preparing a prepolymer and then adding a catalyst to obtain a high molecular weight.

There is also no particular limitation on the method for recovering the polymer component after the reaction, and the polymer solution is thoroughly washed, and then pulverized while removing the solvent with a kneader having a pulverizing mechanism, steam stripping, and multi-stage venting. A known method such as a method of treating with an attached extruder can be used.

(Transesterification method-1) A method of reacting bisphenols with diphenyl carbonate. In the initial reaction of the first stage, the condensation reaction is rapidly carried out, the by-product phenol is distilled out, and the bisphenols are not distilled out (usually 130 to 220 ° C., 60 to 15 mmH).
g)) is preferred. Under these conditions, the initial condensation reaction is performed for 1 to 3 hours, and the theoretical amount of phenol is 80 to 9
It is considered that the initial condensation reaction is substantially completed after it becomes about 0% and it is difficult to distill it anymore, and as the second step, the reaction is continued at high temperature and high vacuum to reach a high polymerization degree. Is preferably performed in an inert atmosphere such as nitrogen or argon.

Alkali metals, alkaline earth metals,
Usual transesterification catalysts such as metal elements typified by zinc, aluminum, tin, titanium, and the compounds thereof can be used.

(Transesterification method-2) This is a method of reacting a bisphenol with a dialkyl carbonate. Specifically, in the presence of an ester exchange catalyst, a method for synthesizing a bisalkyl carbonate of a bisphenol having an alkyl carbonate group at the terminal and self-condensing to produce a high molecular weight polycarbonate cocondensate or the presence of an ester exchange catalyst Below, it is a method of synthesizing a prepolymer from bisphenols and dialkyl carbonate, and then producing a high molecular weight polycarbonate cocondensate.

Preferred transesterification catalysts include metallic elements and compounds thereof as in the transesterification method of bisphenols and diphenyl carbonate.

As a method for obtaining a high-molecular weight polycarbonate cocondensate from the prepolymer, the prepolymer synthesized in the tank-type reaction tank is supplied to a thin-film type evaporator or degassing tank, and then supplied to a tank-type stirring polymerization tank. The method of superposing | polymerizing is mentioned.

Further, the present invention provides a polycarbonate composition comprising a polycarbonate cocondensate obtained by the above-mentioned method and a glass fiber and having a good appearance.

The shape of the glass fiber is not particularly limited, but a glass fiber having a fiber length of 0.5 to 10 mm and a fiber system of 3 to 30 μm is preferable in view of the physical properties of the final composition. Further, the sizing agent is not limited at all, and glass fiber using an epoxy-based or silane-based sizing agent can be used.

The mixing ratio of the cocondensate and the glass fiber and the mixing method are not limited, but from the viewpoint of the physical properties of the final composition,
Cocondensates of 99 to 30% by weight, particularly 95 to 50% by weight, glass fibers of 1 to 70% by weight, particularly 5 to 50% by weight are preferred.

As a mixing method, a Banbury mixer,
Known methods such as a tumbler, a single screw extruder, and a twin screw extruder having a kneading block can be used.

The polycarbonate co-condensate obtained by the method of the present invention contains not only glass fibers but also other fillers, flame retardants, colorants, stabilizers, antistatic agents, release agents,
Known additives such as light diffusing agents, polystyrene, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), rubber-reinforced styrene resin (HIP
Other polymers such as S, ABS, AES, AAS, ACS, etc.) and polyamide can also be blended.

The method for producing the polycarbonate cocondensate of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. All parts are based on weight.

Examples 1 to 4 and Comparative Examples 1 and 2 (phosgene method) A total of 22.8 parts of bisphenol A and 1,1-bis (4-hydroxyphenyl) ethane, pt-butylphenol.
After dissolving 0.45 part in an aqueous solution of 200 parts of water and 11.2 parts of caustic soda, 167 parts of methylene chloride was added,
12.2 parts of phosgene was bubbled in over 1 hour while keeping the temperature below ℃.

Next, caustic soda 3 dissolved in 25 parts of water
Part, an aqueous solution containing 0.078 parts of triethylamine was added,
Polymerization was carried out at 25 ° C. for 4 hours with vigorous stirring.

Then, it was diluted with methylene chloride, washed sufficiently with acid and washed with water and solidified with methanol. The polymer yield was 97%.

The powder was dried at 120 ° C. for 6 hours under hot air and pressed at 290 ° C. at 100 kg / cm ² for 10 minutes. Table 1 shows the amounts of bisphenols used and the physical properties of the obtained polymer.

[0035]

[Table-1]

Impact resistance: Measured after injection molding an impact test piece of 64 × 12.7 × 6.35 mm with a notch of 0.25 mmR.

Workability: 2.16 according to JIS K-7210
Measured at 0kgf, 280 ℃, 10 minutes.

Transparency: According to JIS K-7105 Section 5.5 Measuring Method A.

Heat resistance: ASTM D-648 1/4 inch, 18.6 kg / cm ²

Example 4 and Comparative Example 3 (Transesterification Method-
1) 11.4 parts of bisphenol A and 10.7 parts of 1,1-bis (4-hydroxyphenyl) ethane or 22.8 parts of bisphenol A, 34.5 g of diphenyl carbonate, 0.07 manganese acetate
When heated to 190 ° C in a nitrogen stream with 50g and decompressed to 50mmHg, phenol begins to distill.

If the distillate of phenol is reduced, the temperature is increased to 205
When the temperature is raised to ℃, phenol will evaporate again. Further, the degree of vacuum is lowered to 15 mmHg to sufficiently distill off the free phenol produced in this initial stage. This initial transesterification is completed in about 4 hours.

Subsequently, the pressure in the reactor was reduced to 1 mmHg.
The temperature is gradually increased while maintaining the vacuum of 30 minutes at 225 ° C,
The reaction is carried out at 260 ° C for 2 hours and 295 ° C for 1 hour. The yield of the produced polymers is 95%, and the reduced viscosity is 0.67.
Met. Table 2 shows the physical properties of the obtained polymer.

[0043]

[Table-2]

Example 6 and Comparative Example 4 (Phosgene Method) Using 8 parts of bisphenol A and 12 parts of 2,2-bis (4-hydroxyphenol) butane or 20 parts of 2,2-bis (4-hydroxyphenol) butane. Polymerization was carried out according to Example 1. The physical properties of the obtained polymer are shown in Table-
3 shows.

[0045]

[Table-3]

Examples 7 to 8 and Comparative Example 5 (Transesterification Method) Bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane was added to an autoclave equipped with a distillation means.
Dimethyl carbonate (157 parts) and NaOCH _{3 (} 0.54 parts) were charged, and nitrogen substitution was carried out by pressurization and normal pressure operation. Then, the reaction temperature was raised to 180 ° C. and the pressure was adjusted to 8 with stirring.
The reaction was carried out for 1 hour while keeping it at kg / cm ² . At that time, the produced methyl alcohol and excess dimethyl carbonate were distilled off. The reaction rate of bisphenol A was 94%.

Next, the produced carbonate oligomer (average molecular weight of about 1600) was placed in a round-bottom reaction vessel at atmospheric pressure,
The mixture was gradually heated to 240 to 250 ° C. under reduced pressure and reacted for about 3 hours, then heated to a pressure of about 5 mmHg and 280 ° C. and treated for 15 minutes. The viscosity in the system increased as methyl alcohol was removed.

The amounts of bisphenol A and 1,1-bis (4-hydroxyphenyl) ethane used and the physical properties of the obtained polymer are shown in Table 4.

[0049]

[Table-4]

Example 9 and Comparative Example 6 (phosgene method) Bisphenol A and bisphenol F (bis (4
A mixture of -hydroxyphenyl) methane and bis (3-hydroxyphenyl) methane) was used to obtain a polymer by the phosgene method in the same manner as in Example 1.

The composition of the bisphenol used and the physical properties of the obtained polymer are shown in Table-5.

[0052]

[Table-5]

Examples 10 to 12 and Comparative Examples 7 to 10 60 parts of the various cocondensates or homopolymers obtained in the above Examples and Comparative Examples were mixed with 40 parts of glass fiber, and the mixture was mixed with an injection molding machine to obtain 70 parts. A test piece of × 100 × 3 mm was prepared and the appearance was evaluated. The results are shown in Table-6.

Comparative Example 11 60 parts of a processability-improving PC obtained by blending polyethylene phthalate (PET) with the bisphenol A PC obtained in Comparative Example 1 above was blended with 40 parts of glass fiber, and then 70 A test piece of × 100 × 3 mm was prepared and the appearance was evaluated. The results are shown in Table-6.

[0055]

[Table-6]

Claims (2)

[Claims] 1. A polycarbonate copolymer characterized in that 1 to 90% by weight of 2,2-bis (4-hydroxyphenyl) propane and 99 to 10% by weight of bisphenol represented by the following general formula are reacted with a carbonate precursor. Method for producing condensate. [Chemical 1] (R ₁ is hydrogen and R ₂ is hydrogen, a methyl, propyl or butyl group, or R ₁ is a methyl group, and R
₂ is an ethyl, propyl or butyl group. ) 2. A polycarbonate composition comprising a polycarbonate co-condensate obtained by the production method according to claim 1 and glass fiber.