JPS5817224B2 - Hydrolysis-resistant polycarbonate composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to clear aromatic polycarbonate compositions, in particular clear compositions based on aromatic polycarbonates that have good hydrolysis and embrittlement resistance even when exposed to high temperatures and moisture. It is.

Clear aromatic polycarbonate resins are widely used in many applications such as window glass and baby bottles, but they suffer from clouding and brittleness when sterilized at high temperatures in water or moisture, especially the latter. unsuitable for this purpose.

It has been found that these drawbacks can be eliminated by mixing small amounts of aliphatic or aromatic epoxy compounds with polycarbonate.

This word contains only cycloaliphatic epoxy compounds,
A clear polycarbonate containing a cycloaliphatic epoxy compound together with a phosphite (the former is disclosed in U.S. Pat. No. 3489).
7 ], No. 66 Specification K1 The latter is U.S. Patent No. 363431
This is surprising considering that the products (described in Patent No. 2, respectively) become cloudy after steam autoclave treatment.

In the present invention, the aromatic epoxy may be either monodoxy or polyepoxy.

The amount of epoxy used is 0 based on the weight of polycarbonate.
．． 0.01 to about 0.50% by weight.

Next, examples of the present invention will be shown.

All "parts" and "parts" in the examples refer to parts by weight unless otherwise specified.

Example 1 A reactor equipped with a reflux condenser and a mechanical stirrer was charged with 100 parts of methylene chloride, 150 parts of 2,2-bis(
4-oxyphenyl)propane, 150 parts of calcium hydroxide, 3 parts of phenol and 0.018 parts of triethylamine.

The slurry is stirred and phosgene is added to it at a rate of about 90 parts/hour.

Phosgene addition is stopped after 50 minutes.

The solid polycarbonate is recovered by filtration to remove any residual solvent.

The product is dried at 125° C. overnight. The product is then fed into an extruder at a temperature of about 525°F to pelletize.

Example 2 The polymer produced in Example 1 was treated with 0, 1
% by weight of bisphenol A diglycidyl ether is mixed and the mixture is pelletized as in Example 1.

Example 3 Example 2 was carried out using 0.05 weight of glycidol in place of bisphenol A sidalicidyl ether in Example 2.
Repeat the operation.

Example 4 The procedure of Example 2 is repeated using 0.2 parts by weight of epoxidized canine oil in place of the bisphenol A diglycidyl ether of Example 2.

Example 5 The procedure of Example 2 is repeated using 01 wt epoxidized polybutadiene in place of the bisphenol A diglycidyl ether of Example 2.

Example 6 Example 2 is repeated using 0.025 wt. 1.2,3,4-jepoxybutane in place of the bisphenol A diglycidyl ether of Example 2.

Example 7 A reactor equipped with a reflux condenser and a mechanical stirrer was charged with 1100 parts of methylene chloride, 150 parts of 2,2-bis(4-oxyphenyl)propane, 150 parts of calcium hydroxide, 3 parts of phenol, and 0.0] and 8 parts of triethylamine.

The slurry is stirred and to it is added 0.075 parts of phosphorous trichloride based on the weight of 2,2-bis(4-oxyphenyl)propane.

Phosgene addition is stopped after about 50 minutes.

The polymer is recovered in the same manner as in Example 1.

The elemental phosphorus content of this product was determined by the Schoniger combustion method as described in Slam and Leillis, Identification and Analysis of Plastics, Illitus Books, London, 1965, page 8. , about 0.003 parts 4% by weight.

Example 8 The polymers prepared in Example 7 were treated with 0, 0,
Xylmethyl 3,4-epoxycyclohexanecarboxylate is mixed into 1% by weight of 3,4-epoxycyclo, and the mixture is then pelletized as in Example 1.

Example 9 The polymer compositions of Examples 1-8 were each injection molded at about 6500F to have dimensions of 3 inches by 2 inches and a thickness of 1
/8 inch test specimen.

Samples were subjected to the ASTM Dl 003 test at 260°F.
Measure the light transmittance of the sample before and after steam autoclaving.

The higher the light transmittance, the better the clarity of the sample.

The test results are shown in Table 1.

Example 9 For each of the polymer compositions of Examples 1 to 8, the molecular weight degradation due to hydrolysis is compared by measuring the intrinsic viscosity before and after steam autoclave treatment.

The larger the difference between before and after autoclaving, the more significant is the disassembly of the polycarbonate.

Intrinsic viscosity is the value measured in dioxane at 30°C.

The test results are shown in Table 2.

Aromatic epoxies that can be used in the composition of the present invention include:
Aromatic glycidyl or diglycidyl ethers having 1 to 3 aromatic rings and polyepoxides having 1 to 3 aromatic rings are suitable.

Suitable aliphatic epoxies include compounds of the formula: where R1 and R2 each represent an alkyl group having from 1 to 24 carbon atoms, and n is an integer from 1 to about 10. be.

Specific epoxies that may be used include, for example, glycidol, bisphenol A diglycidyl ether, tetrabrominated bisphenol A diglycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, epoxidized soybean oil, butadiene Epoxides include tetraphenylethylene epoxide octyl epoxytalate and epoxidized polybutadiene.

Among these, bisphenol A diglycidyl ether is preferred.

Dihydric phenols that can be used to prepare the aromatic polycarbonates used in the compositions of the invention include bisphenols, e.g. phenol ethers, commonly known as his(4-oxyphenyl)-ether, dioxydiphenyl, commonly known as P,P-dioxydiphenyl, dioxyarylsulfones, e.g. evahis(4-oxyphenyl)-
sulfones, dioxybenzenes, e.g. resorcinol,
Halogen- and alkyl-substituted dioxybenzenes, reportedly 1,4-dioxy-2=chlorobenzene, and dioxydiphenyl sulfoxides, such as bis(4-oxyphenyl)-sulfoxide carbs.

A number of dihydric phenols suitable for making carbonate polymers are disclosed in U.S. Pat.
No. 365 and No. 3153008.

If a carbonate copolymer or an interpolymer is more desirable than a homopolymer for preparing the aromatic carbonate polymers of the present invention, two or more different dihydric phenols, preferably dihydric phenols and glycol or hydroxyl groups or It is of course possible to use acid-terminated polynisdale polymers or copolymers with dibasic acids.

The embodiments of the present invention are as follows.

(1) As an aliphatic epoxy compound, the following formula: (R1 in the formula
and R2 each represent an alkyl group having from 1 to 24 carbon atoms, n is an integer from 1 to 10.

(2) The composition according to the claims, wherein the aliphatic epoxy is selected from monoglycidyl ethers, diglycidyl ethers, and polyglycidyl ethers.

(3) The composition according to the claims, which is an aliphatic epoxidized soybean oil.

(4-) The composition according to the claims, wherein the aromatic epoxy is bisphenol A diglycidyl ether.

Claims (1)

[Claims] 1 Aromatic polycarbonate resin, 0.01 to 0.50% by weight based on the weight of the polycarbonate resin, selected from aromatic epoxy, aliphatic epoxy (excluding epoxidized soybean oil), and mixtures thereof. A water-resistant clear aromatic polycarbonate composition comprising a mixture with an epoxy compound.