JP2867085B2 - Polycarbonate composition comprising polycarbonate cocondensate and glass fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate composition comprising a novel polycarbonate co-condensate and glass fibers.

[0002]

2. Description of the Related Art 2,2-Bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and a polycarbonate (hereinafter simply referred to as bisphenol A PC) derived from a carbonate precursor are heat-resistant and resistant to heat. Widely used as engineering plastic with excellent impact and transparency.

However, bisphenol A PC because poor workability, a method of blending the polyester polyethylene terephthalate and polybutylene terephthalate have been proposed bisphenol A P
Transparency which is an original feature of C is sacrificed. Further, although the processability is improved by keeping the molecular weight of bisphenol A PC low, the impact resistance is significantly reduced.

[0004] On the other hand, improvement in processability of bisphenol A PC itself from the structural aspect is also being studied, and a novel process comprising reacting a bisphenol other than 2,2-bis (4-hydroxyphenyl) propane with a carbonate precursor has been studied. Mixtures of polycarbonate and such novel polycarbonates with bisphenol A PC have also been proposed, but at the expense of the inherent characteristics of bisphenol A PC.
There is still a problem as a product with improved processability.

[0005]

The inventors of the present invention have conducted intensive studies on the above points and 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 it has excellent heat resistance and transparency inherent to PC and has a significantly improved impact resistance / workability balance, and the composition comprising the co-condensate and glass fiber has excellent surface appearance. And reached the present invention.

[0006] It is particularly surprising that the co-condensate has a completely different effect (appearance improvement) in a composite system with glass fibers than a mixture of bisphenol APC and a specific structure bisphenol homopolymer.

[0007]

[Means for Solving the Problems] That is, the present invention provides:
2,2-bis (4-hydroxyphenyl) propane 1
90% by weight of bisphenol 99 represented by the following general formula
An object of the present invention is to provide a polycarbonate composition having excellent surface appearance, comprising a polycarbonate cocondensate having excellent processability and a glass fiber, obtained by reacting a polycarbonate precursor with 10 to 10% by weight of a carbonate precursor.

[0008]

Embedded image (R ₁ is hydrogen and R ₂ is hydrogen, methyl, propyl or butyl, or R ₁ is methyl and R
₂ is an ethyl, propyl or butyl group. )

Hereinafter, the present invention will be described in detail.

In the polycarbonate co-condensate of the present invention, the ratio of bisphenol A to the specific structure bisphenol is from 1 to 90 of bisphenol A per total of both bisphenols.
%, Specific structure bisphenol 99 to 10% by weight. If bisphenol A is less than 1% by weight, heat resistance is reduced, and if it exceeds 90% by weight, workability cannot be improved. Preferably, bisphenol A is 10 to 80% by weight and specific structure bisphenol is 90 to 20% by weight.

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

[0012]

Embedded image (R ₁ is hydrogen and R ₂ is hydrogen, methyl, propyl or butyl, or R ₁ is methyl and R
₂ is an ethyl, propyl or butyl group. )

As carbonate precursors, phosgene,
Examples include diphenyl carbonate, dialkyl carbonate and the like.

The method for producing a polycarbonate cocondensate from bisphenol A, a bisphenol having a specific structure and a carbonate precursor is not particularly limited, and examples thereof include the following phosgene method and transesterification method.

(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 use of a quaternary ammonium salt or tertiary amine as a catalyst increases the reaction rate. Reaction temperature is 0-10
0 ° C.

Both bisphenols may be reacted simultaneously with the carbonate precursor from the beginning, or one of the bisphenols may be reacted with the carbonate precursor,
After the condensation reaction has been performed to some extent, it is also possible to add the other and continue the reaction.

Further, the catalyst may be added from the beginning,
After the prepolymer is formed, an arbitrary method such as adding a catalyst to increase the molecular weight may be used.

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

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

Further, an alkali metal, an alkaline earth metal,
Usual transesterification catalysts such as metal elements represented by zinc, aluminum, tin, titanium and the like and 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 a transesterification catalyst, a method of producing a bisalkyl carbonate ester of a bisphenol having an alkyl carbonate group at a terminal and self-condensing to produce a high-molecular-weight polycarbonate co-condensate or the presence of a transesterification catalyst Below is a method of synthesizing a prepolymer from bisphenols and dialkyl carbonate, and then producing a high molecular weight polycarbonate co-condensate.

Preferred transesterification catalysts include metal elements and compounds thereof as used 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 evaporator or a degassing tank, and further supplied to a tank-type stirring polymerization tank. A method of polymerizing is exemplified.

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

Although the shape of the glass fiber is not particularly limited, it is preferable that the fiber length is 0.5 to 10 mm and the fiber type is 3 to 30 μm in view of the physical properties of the final composition. There is no limitation on the sizing agent, and glass fibers using an epoxy or silane sizing agent can also be used.

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

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 composition of the present invention contains not only glass fibers but also other known additives such as other fillers, flame retardants, coloring agents, stabilizers, antistatic agents, mold release agents, and light diffusing agents. And polystyrene, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.),
Rubber reinforced styrene resin (HIPS, ABS, AES,
AAS, ACS, etc.) and other polymers such as polyamides can also be blended.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
All copies 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
0.45 part was dissolved in an aqueous solution of 200 parts of water and 11.2 parts of caustic soda, and 167 parts of methylene chloride was added.
12.2 parts of phosgene were blown in over one hour while the temperature was kept at or below.

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

Next, the mixture was diluted with methylene chloride, pickled and sufficiently washed with water, and coagulated with methanol. The polymer yield was 97%.

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

[0035]

[Table-1]

Impact resistance: An impact test piece of 64 × 12.7 × 6.35 mm was injection-molded, and a notch of 0.25 mmR was provided, followed by measurement.

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

Transparency: in accordance with JIS K-7105, section 5.5, measurement method A.

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

Example 5 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 were mixed with diphenyl carbonate 34. .5g,
When heated to 190 ° C. in a nitrogen stream together with 0.07 g of manganese acetate and reduced to 50 mmHg, phenol distillation starts immediately.

If the distillation of phenol is reduced, the temperature is increased to 205
When the temperature is raised to ℃, phenol is distilled again. Further, the degree of reduced pressure is reduced to 15 mmHg, and the free phenol produced in this initial stage is sufficiently distilled off. This initial transesterification is completed in about 4 hours.

Subsequently, the pressure in the reactor was reduced, and 1 mmHg
Gradually raise the temperature while maintaining the vacuum of 225 ℃ 30 minutes,
React at 260 ° C for 2 hours and 295 ° C for 1 hour. The yield of each of the produced polymers was 95%, and the reduced viscosity was 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. Table 1 shows the physical properties of the obtained polymer.
3 is shown.

[0045]

[Table-3]

Examples 7 to 8 and Comparative Example 5 (Transesterification method) Bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane,
After charging 157 parts of dimethyl carbonate and 0.54 part of NaOCH ₃ and performing nitrogen replacement by pressurization and normal pressure operation, the reaction temperature was increased to 180 ° C., and the pressure was increased to 8 under stirring.
The reaction was performed for 1 hour while maintaining the pressure at kg / cm ² . At that time, generated methyl alcohol and excess dimethyl carbonate were distilled off. The conversion of bisphenol A was 94%.

Next, the produced carbonate oligomer (average molecular weight: about 1600) was placed in a round bottom reaction vessel at atmospheric pressure,
After gradually heating to 240 to 250 ° C. while reducing the pressure and reacting for about 3 hours, the pressure was raised to about 280 ° C. at a pressure of about 5 mmHg, and the treatment was performed for 15 minutes. As the methyl alcohol was removed, the viscosity in the system increased.

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

[0049]

[Table-4]

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

Table 5 shows the composition of the bisphenol used and the physical properties of the obtained polymer.

[0052]

[Table-5]

Examples 10 to 12 and Comparative Examples 7 to 10 60 parts of various cocondensates or homopolymers obtained in the above Examples and Comparative Examples were mixed with 40 parts of glass fiber, and mixed with an injection molding machine. 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 workability-improved PC obtained by blending polyethylene phthalate (PET) with the bisphenol A PC obtained in Comparative Example 1 described above was blended with 40 parts of glass fiber, and then mixed with an injection molding machine. A test piece of × 100 × 3 mm was prepared and the appearance was evaluated. The results are shown in Table-6.

[0055]

[Table-6]

The criteria for evaluation of appearance in Table 6 are as follows. ：: Good: The float of the glass fiber on the surface of the test piece is hardly noticeable to the naked eye, and the appearance is glossy. X: Poor ... float of the glass fiber was clearly observed on the surface of the test piece with the naked eye, and the appearance was not glossy. As is clear from Table 6, the compositions of Examples 10 to 12, which are the co-condensates of the present invention, were composed of polycarbonate (Comparative Example 1) composed of bisphenol A alone (Comparative Example 7). ), And the polycarbonate of Comparative Example 1 and other polymers shown below (Comparative Example 2, Comparative Example 4, Comparative Example 6, and polyethylene terephthalate (PET))
Has a better surface appearance than the compositions obtained using the mixture with (Comparative Examples 8 to 11). Comparative Example 8: Mixture of Comparative Example 2 (a homopolymer obtained from 1,1-bis (4-hydroxyphenyl) ethane by the phosgene method) and Comparative Example 1 (a homopolymer obtained from bisphenol A by the phosgene method) And glass fiber. The type of the constituent monomer of the co-condensate of Example 2 used in the composition of Example 10 is the same as that of the mixture. Comparative Example 9: Mixture of Comparative Example 4 (a homopolymer obtained from 2,2-bis (4-hydroxyphenyl) butane by the phosgene method) and Comparative Example 1 (a homopolymer obtained from bisphenol A by the phosgene method) And glass fiber. The type of the constituent monomer of the co-condensate of Example 6 used in the composition of Example 11 is the same as that of the mixture. Comparative Example 10: Comparative Example 6 (a copolymer obtained from bis (4-hydroxyphenyl) methane and bis (3-hydroxyphenyl) methane by the phosgene method) and Comparative Example 1
(Homopolymer obtained from bisphenol A by the phosgene method) and a glass fiber. The kind of the constituent monomer of the co-condensate of Example 9 used in the composition of Example 12 is the same as that of the mixture.

Claims (1)

(57) [Claims] (1) 2,2-bis (4-hydroxyphenyl)
Polycarbonate co-condensate (A) 99 obtained by reacting 1 to 90% by weight of propane and 99 to 10% by weight of bisphenol represented by the following general formula with a carbonate precursor
30 wt% and glass fiber (B) polycarbonate composition characterized by consisting of 1 to 70 wt%. Embedded image (R ₁ is hydrogen and R ₂ is hydrogen, methyl, propyl or butyl, or R ₁ is methyl and R 2
₂ is an ethyl, propyl or butyl group. )