WO2016197914A1 - Polycarbonate composition and preparation method therefor - Google Patents

Abstract

Disclosed is a polycarbonate composition, comprising the following components in parts by weight: a. 30.3 parts to 80.3 parts of polycarbonate; b. 7.7 parts to 49.7 parts of a rubber-modified graft polymer; c. 4.5 parts to 24.5 parts of a flame retardant; and d. 0 parts to 9.8 parts of other additives, where the sum of the parts by weight of the four components, a, b, c, and d, is 100 parts. By means of such selection in the present invention, when the mass percent content of a flow promoter in the total mass of the polycarbonate composition of the polycarbonate composition formula is less than or equal to 2 wt%, a specific range of contents of the flow promoter facilitates increased compatibility and miscibility of the rubber-modified graft polymer and a polycarbonate resin, and the rubber-modified graft polymer of increased gloss migrates easily to the surface of a product, thus ultimately increasing the melt stability and surface gloss of the polycarbonate composition, which is especially suitable in scenarios of increased requirements on the use environment.

Description

Polycarbonate composition and preparation method thereof Technical field

The invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.

Background technique

Polycarbonate PC has high impact resistance and heat resistance. In order to improve its processing properties and sensitivity to notch impact, it is usually added to rubber-modified polymers such as ABS, MBS, etc., especially PC. PC/ABS alloy with ABS as the main raw material is an important engineering plastic, which can improve the heat resistance and tensile strength of ABS, on the other hand, it can reduce the viscosity of PC melt, improve the processing performance and reduce the stress inside the product. And the sensitivity of the impact strength to the thickness of the product. However, the fluidity in the cavity during the molten polycarbonate PC forming process directly affects the quality of the molded PC/ABS alloy.

Patent 103,772,942 A discloses an abrasion resistant PC/ABS composition incorporating 0.2 parts by weight to 0.3 parts of polyethylene wax having excellent impact resistance and abrasion resistance, but the polyethylene wax is merely used as a dispersing agent for other properties. The impact of the aspect has not been explained.

Patent 103772942A discloses an ABS modified polycarbonate alloy material which has the characteristics of good heat resistance, high impact strength and good environmental crack resistance. Polyethylene wax is used as a lubricant therein, and has no effect on other properties. Description.

Patent CN103391970 discloses a low molecular weight flame retardant and UV resistant polycarbonate molding compound, and it is proposed that a sulfonate flame retardant having a low free sulfate content and a free fluoride ion content has little influence on the melt index of PC, and can be fluctuated. Smaller molding compounds, but sulfonate-based flame retardants are difficult to disperse, and poor hydrolysis stability limits their widespread use.

Up to now, the influence of the content of the flow modifier on the melt stability and surface gloss of the polycarbonate composition has not been reported.

The inventors have surprisingly found through a large number of experiments that a specific range of flow promoters is selected when the mass percentage of the flow promoter is less than or equal to 2% by weight based on the total mass of the polycarbonate composition of the polycarbonate composition formulation. It is beneficial to improve the compatibility and mutual solubility of the rubber modified graft polymer and the polycarbonate resin, and the rubber modified graft polymer with high glossiness is easy to migrate to the surface of the product, thereby finally mentioning The melt stability and surface gloss of the polycarbonate composition are increased, and it is particularly suitable for applications where the use environment is relatively high.

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art, it is an object of the present invention to provide a polycarbonate composition having excellent melt stability and surface gloss.

Another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.

The invention is achieved by the following technical solutions:

A polycarbonate composition comprising, by weight, the following composition:

a, 30.3 parts to 80.3 parts of polycarbonate;

b, 7.7 parts to 49.7 parts of the rubber modified graft polymer;

c, 4.5 parts - 24.5 parts of flame retardant;

d, 0-9.8 parts of other auxiliaries;

Wherein, the sum of the weight components of the four components a, b, c, and d is 100 parts.

Preferably, a polycarbonate composition, by weight, comprises the following composition:

a, 35 parts - 75 parts of polycarbonate;

b, 8 parts - 35 parts of rubber modified graft polymer;

c, 5 parts - 24.5 parts of flame retardant;

d, 0-9.8 parts of other auxiliaries;

Wherein, the sum of the weight components of the four components a, b, c, d is 100 parts,

The flow promoter has a mass percentage of 2% by weight or more and 0.01% by weight or more based on the total mass of the polycarbonate composition.

Preferably, the flow promoter is contained in an amount of not less than 1% by weight and 0.05% by weight or more based on the total mass of the polycarbonate composition; preferably 0.8% by weight or less and 0.1% by weight or more.

Wherein, the flow promoter may also be selected from the group consisting of a combination of a polyethylene wax and an amide wax, a compound of an amide wax and a stearate, a compound of a polyethylene wax and a stearate, a polyethylene wax and an amide wax. And the compounding of stearates.

Wherein, based on the total mass of the flow promoter, the compounding ratio of the polyethylene wax to the amide wax is 3:1-1:3; the compounding ratio of the amide wax to the stearate is 2:1-1:5; The compounding ratio of the polyethylene wax to the stearate is 2:1 to 1:5; the compounding of the polyethylene wax with the amide wax and the stearate is 1:1:10-1:1:1.

Preferably, the compounding ratio of the polyethylene wax to the amide wax is 2:1 to 1:2 based on the total mass of the flow promoter; the compounding ratio of the amide wax to the stearate is 1:2-1:3 The compounding ratio of the polyethylene wax to the stearate is 1:2-1:3; the compounding of the polyethylene wax with the amide wax and the stearate is 3:3:20-1:1:4.

Evaluation method for improving the melt fluidity of plastic materials by flow promoter: The polymer composition is melted into a plastic fluid under a certain time (10 minutes), a certain temperature and pressure (different materials standards), and then passed through a The number of grams of a 2.1 mm diameter tube. The greater the value, the better the melt flowability of the polymer composition, and vice versa; the test standard used herein is ASTM D1238, unit: g/10 min. The test conditions were as follows: melt flow rate (MFR) at 230 ° C under a load of 2.16 kg.

After melt blending a certain amount of flow promoter with the polycarbonate composition, the melt flow rate is tested to significantly increase the melt flow rate of the polycarbonate composition, i.e., increase the melt flowability of the composition.

Preferably, the polyethylene wax has a molecular weight of 1500-5000, and is a polyethylene homopolymer/interpolymer having a molecular weight of 1000-2000 obtained by depolymerization of polyethylene having a molecular weight of 10 ⁴ to 10 ⁷ . One or more of low density polyethylene wax, high density polyethylene wax, modified high density polyethylene wax, partially oxidized polyethylene wax, and oxidized polyethylene wax;

The amide wax has a molecular weight of 400-1000 and is a low molecular weight wax obtained by a polycondensation reaction of a dibasic acid and a diamine, and is selected from the group consisting of oleic acid amides and/or fatty acid amides, more preferably ethylene double hard fat. Acid amide

The stearate is selected from one or more of zinc stearate, magnesium stearate, and calcium stearate.

The polycarbonate is selected from one or more of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, a branched polycarbonate, and a siloxane copolycarbonate, preferably Aromatic polycarbonate.

Preferably, the aromatic polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000, more preferably an aromatic having a viscosity average molecular weight of 17,000 to 24,000. Family polycarbonate.

Wherein the polycarbonate is selected from the group consisting of a polycarbonate prepared by an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Or several. A particularly preferred method thereof will be described in detail below.

First, a method of producing a polycarbonate resin by an interfacial polymerization method will be described: in the interfacial polymerization method, First, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an inert organic solvent and an aqueous alkali solution while usually maintaining a pH of 9 or more, and then interfacial polymerization is carried out in the presence of a polymerization catalyst to obtain a polycarbonate. Resin. A molecular weight modifier (chain terminator) and an antioxidant which prevents oxidation of the dihydroxy compound may also be present in the reaction system as needed.

Dihydroxy compounds and carbonate precursors have been listed above. The use of phosgene as a carbonate precursor is particularly preferred, and such a method in which phosgene is used is particularly referred to as a phosgene method.

Examples of the inert organic solvent include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene. An organic solvent may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

Examples of the alkali compound contained in the aqueous alkali solution include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogencarbonate; and alkaline earth metal compounds. Sodium hydroxide and potassium hydroxide are preferred. An alkali compound may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

Although the concentration of the alkali compound in the aqueous alkali solution is not limited herein, it is usually used in an amount of from 5 wt% to 10 wt% to control the pH of the aqueous alkali solution during the reaction to be 10-12. Further, for example, when phosgene is bubbled, the molar ratio of the bisphenol compound to the alkali compound is usually set to 1:1.9 or more, and preferably 1:2.0 or more, but 1:3.2 or less, and preferably 1:2.5 or less. Thereby, the pH of the aqueous phase is controlled to be 10-12, preferably 10-11.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; and alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N , N'-diethylcyclohexylamine, etc.; aromatic tertiary amines such as N, N'-dimethylaniline and N, N'-diethylaniline; quaternary ammonium salts such as trimethylbenzyl chloride Ammonium, tetramethylammonium chloride and triethylbenzylammonium chloride; pyridine; guanine; A polymerization catalyst may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

Examples of the molecular weight modifier include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; and phthalimides; and the like, and among these, aromatic A phenol is preferred. Specific examples of such aromatic phenols include alkyl-substituted phenols such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long-chain alkyl-substituted phenol. Etc.; a vinyl group-containing phenol such as isopropenyl phenol; an epoxy group-containing phenol; and a carboxyl group-containing phenol such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid. One type of molecular weight modifier may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

The amount of the molecular weight modifier is usually 0.5 mol or more per 100 mol of the dihydroxy compound. It is preferably 1 mol or more, but is usually 50 mol or less, and preferably 30 mol or less. Setting the amount of the molecular weight modifier to this range can improve the thermal stability and hydrolysis resistance of the polycarbonate resin composition.

The reaction substrate, reaction medium, catalyst, additives, and the like may be mixed together in any desired order during the reaction as long as the desired polycarbonate resin can be obtained, and a suitable order can be established as needed. For example, when phosgene is used as the carbonate precursor, the molecular weight modifier can be added at any desired timing between the reaction of the dihydroxy compound with phosgene (phosgenation) and at the beginning of the polymerization reaction.

The reaction temperature is usually set to 0 to 40 ° C, and the reaction time is usually in the range of several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

Next, a method of producing a polycarbonate resin by a melt transesterification method in which, for example, a transesterification reaction is carried out between a carbonic acid diester and a dihydroxy compound, will be explained.

Meanwhile, examples of the carbonic acid diester include a dialkyl carbonate compound such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonate such as ditolyl carbonate. Wait. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferred, and in particular, diphenyl carbonate is even more preferable. One type of carbonic acid diester may be used, or two or more types thereof may be used together in a desired combination and ratio.

A desired ratio of the dihydroxy compound to the carbonic acid diester may be used, provided that the target polycarbonate resin can be obtained, but it is preferred to use 1 or more molar equivalents of diester carbonate per 1 mole of the dihydroxy compound, and 1.01 is used. The above molar equivalents are even more preferred. However, the upper limit is usually a molar equivalent of 1.30 or less. The amount of terminal hydroxyl groups can be adjusted to a preferred range by setting the ratio of the two compounds within such a range.

The amount of terminal hydroxyl groups in the polycarbonate resin tends to greatly affect thermal stability, hydrolysis resistance, color tone, and the like. Thus, the amount of terminal hydroxyl groups can be adjusted as desired by any well-known desired method. In the transesterification reaction, a polycarbonate resin in which the amount of the terminal hydroxyl group is adjusted can be usually obtained by adjusting the mixing ratio between the carbonic acid diester and the aromatic dihydroxy compound, the degree of pressure reduction, and the like during the reaction. Further, the molecular weight of the obtained polycarbonate resin can usually also be adjusted by this process.

The above mixing ratio is used in the case where the amount of the terminal hydroxyl group is adjusted by adjusting the mixing ratio of the dicarbonate and the dihydroxy compound.

A method in which a chain terminator is separately added during the reaction can be mentioned as a more aggressive adjustment method. Examples of the chain terminator during the process include, for example, a monovalent phenol, a monovalent carboxylic acid, a carbonic acid diester, and the like. A chain terminator may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

When a polycarbonate resin is produced by a melt transesterification method, a transesterification catalyst is usually used. Any desired transesterification catalyst can be used. Among these, for example, the use of an alkali metal compound and/or an alkaline earth metal compound is preferred. Further, as the auxiliary compound, for example, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, a basic amine compound or the like can be used. A transesterification catalyst may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

The reaction temperature in the melt transesterification method is usually from 100 ° C to 320 ° C. Further, the reaction is usually carried out under reduced pressure of 2 mmHg or less. The detailed procedure should be a process in which the melt polycondensation reaction is carried out under the above conditions while removing by-products such as aromatic hydroxy compounds and the like.

The melt polycondensation reaction can be carried out by a batch process or a continuous process. When the batch method is carried out, the reaction substrate, the reaction medium, the catalyst, the additives and the like may be mixed together in any desired order as long as the target aromatic polycarbonate resin can be obtained, and a suitable order can be established as needed. Among these, however, it is preferable to carry out melt polycondensation by a continuous process in consideration of stability of, for example, a polycarbonate and a polycarbonate resin composition.

The catalyst deactivator can be used as needed in the melt transesterification process. Any desired compound that neutralizes the transesterification catalyst can be used as a catalyst deactivating agent. Examples include sulfur-containing organic compounds and derivatives thereof and the like. A catalyst deactivator may be used, or two or more kinds thereof may be used together in a desired combination and ratio.

The amount of the catalyst deactivator to be used is usually 0.5 parts by weight or more and preferably 1 part by weight or more, based on the alkali metal or alkaline earth metal contained in the transesterification catalyst, but should be usually 10 parts by weight or less, and preferably 5 parts by weight or less. Further, the concentration thereof is usually 1 ppm or more with respect to the aromatic polycarbonate resin, but is usually 100 ppm or less, and preferably 20 ppm or less.

Wherein, the molecular weight of the polycarbonate resin is arbitrary, and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] calculated from the viscosity of the liquid is usually from 13,000 to 40,000, preferably from 16,000 to 28,000, more preferably 17,000. -24000. The mechanical strength of the polycarbonate resin composition of the present invention can be further improved by setting the viscosity average molecular weight to be at least the lower limit of the above range, and this is even more desirable when the composition is used for applications requiring high mechanical strength. Meanwhile, by setting the viscosity average molecular weight to be lower than the upper limit of the above range, the decrease in fluidity of the polycarbonate resin composition of the present invention can be controlled or improved, which improves moldability and promotes the thin wall molding method. Two or more polycarbonate resins having different viscosity average molecular weights may be mixed and used together, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may also be included in the mixture.

The term viscosity average molecular weight [M _v ] means a Schnell viscosity equation in which the intrinsic viscosity [η] (unit: dl/g) is determined by measurement using an Ubbelohde viscometer at 20 ° C as a solvent, that is, η = 1.23. ×10 ^-4 Mv ^0.83 Calculated value. Further, the intrinsic viscosity [η] is a value calculated by the following equation after measuring the specific viscosity [η _sp ] in a solution of various concentrations [C] (g/dl).

The concentration of the terminal hydroxyl group in the polycarbonate resin is arbitrary, and can be selected and determined as needed, but is usually 1,000 ppm or less, preferably 800 ppm or less, and more preferably 600 ppm or less. Therefore, the residual thermal stability and color tone of the polycarbonate resin composition of the present invention can be further improved. The lower limit of the concentration, in particular, in the case of a polycarbonate resin produced by a melt transesterification method, is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more. The decrease in molecular weight can be prevented, whereby the mechanical properties of the polycarbonate resin composition can be further improved.

The unit of the terminal hydroxyl group concentration is expressed herein as ppm based on the mass of the terminal hydroxyl group relative to the mass of the polycarbonate resin. Colorimetric analysis by a carbon tetrachloride/acetic acid process was used as a measurement method (see Macromol. Chem., 88, 215, 1965).

The polycarbonate resin can be used as a sole polycarbonate resin (wherein the term "single polycarbonate resin" is not limited to a mode including only one polycarbonate resin, for example, including a plurality of different monomer formulations and The mode of the polycarbonate resin of molecular weight), or it may be combined and used as an alloy (mixture) of a polycarbonate resin and different thermoplastic resins. Further, the polycarbonate resin may constitute a copolymer having a polycarbonate resin as its main component, such as an oligomer or polymer including a siloxane structure for the purpose of further improving flame retardancy and impact resistance. a copolymer; a copolymer comprising a monomer, oligomer or polymer comprising a phosphorus atom for the purpose of further improving thermal oxidative stability and flame retardancy; comprising dihydroxyanthracene for the purpose of improving thermal oxidative stability a monomer, oligomer or polymer of the structure; a copolymer comprising an oligomer or polymer comprising an olefinic structure as represented by polystyrene for the purpose of improving optical properties; and for improving chemical resistance The purpose includes a copolymer of a polyester resin oligomer or a polymer; and the like.

The polycarbonate resin may also contain a polycarbonate oligomer for the purpose of improving the appearance of the molded article and improving fluidity. The polycarbonate oligomer has a viscosity average molecular weight [Mv] of usually 1,500 or more, and preferably 2,000 or more, but is usually 9,500 or less, and preferably 9,000 or less. In addition, preferably, The content of the polycarbonate oligomer contained is set to 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be a polycarbonate resin (so-called recycled material polycarbonate resin) which is regenerated from a used manufactured product rather than an unused raw material. Examples of used manufactured products include optical recording media such as optical disks, etc.; light guide plates; transparent automotive parts such as automobile window glass, automobile headlight glass and windshield, etc.; containers such as water bottles, etc.; spectacle lenses; and building materials such as baffles , glass windows, corrugated sheets; and so on. Further, a pulverized product or a molten pellet obtained from a defective product, a slag, a runner, or the like can also be used.

However, it should be noted that the recycled polycarbonate resin is preferably 80% by weight or less, and more preferably 50% by weight or less, of the polycarbonate resin contained in the polycarbonate resin composition of the present invention. The recycled polycarbonate resin will most likely undergo deterioration due to heat or aging, and if such a polycarbonate resin is used in an amount larger than the above range, color tone and mechanical properties may be adversely affected.

Wherein, the rubber modified graft polymer is selected from one or more of rubber-modified graft polymers prepared by emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, bulk/suspension polymerization.

The acrylonitrile-butadiene-styrene copolymer (ABS resin) preferably used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a butadiene rubber component with acrylonitrile and styrene, and acrylonitrile. a mixture of styrene copolymers. The content of the butadiene rubber component in the ABS resin is preferably from 5 wt% to 40 wt%, more preferably from 10 wt% to 35 wt%, still more preferably from 13 wt% to 25 wt%, based on 100 wt% of the ABS resin component.

Wherein the rubber-modified graft polymer is selected from the group consisting of the following graft polymers comprising b.1 on b.2:

B.1, 5 parts - 95 parts of a mixture of b.1.1 and b.1.2:

B.1.1, 50 parts - 95 parts of styrene, styrene derivatives such as α-methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid One or more of a C1-C8-alkyl ester, a dimethylsiloxane, a phenylsiloxane, a polyalkylsiloxane;

B. 1.2, 5 parts - 50 parts of acrylonitrile, methacrylonitrile, C1-C8-alkyl methacrylate, one or more of C1-C8-alkyl acrylate;

b. 2, 5 parts - 95 parts of polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene random copolymer and block copolymer, polybutylene Alkene and polyisoprene copolymer, ethylene and a-olefin copolymer, ethylene and a-unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene terpolymer One or several of them.

More preferably, the rubber modified graft polymer is selected from the group consisting of acrylonitrile-butadiene-styrene graft copolymer ABS, acrylonitrile-styrene-acrylic terpolymer ASA or methyl methacrylate- One or more of the butadiene-styrene graft copolymer MBS, more preferably an acrylonitrile-butadiene-styrene graft copolymer ABS; wherein the particle size of the MBS is preferably 0.1 um to 0.5 um, The bulk polymerization method ABS particle size is preferably 0.1 um to 2 um, and the emulsion polymerization method ABS particle diameter is preferably 0.05 um to 0.2 um.

Wherein the flame retardant is selected from the group consisting of a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant; the halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, and bromine Bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate Or one or more of perfluorotricyclopentadecane or brominated aromatic crosslinked polymer, preferably brominated polystyrene; the halogen-free flame retardant is selected from the group consisting of nitrogen-containing flame retardants and phosphorus-containing resistors One or more of a flammant or a flame retardant containing nitrogen and phosphorus is preferably a phosphorus-containing flame retardant.

Preferably, the phosphorus-containing flame retardant is selected from the group consisting of monomers and oligomeric phosphates and phosphonates, phosphonate amines and phosphazenes, wherein one or more groups selected from the group may also be used. a mixture of various compounds; preferably triphenyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, trimethylphenyl phosphate, tris(2,4,6-trimethylphenyl phosphate) ) ester, tris(2,4-di-tert-butylphenyl) phosphate, tris(2,6-di-tert-butylphenyl) phosphate, resorcinol bis(diphenyl phosphate), p-benzene Diphenol bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate), hydroquinone bis ( One or more of 2,6-dimethylphenyl phosphate.

Other additives may also be included in the polycarbonate composition, such as one or more selected from the group consisting of heat stabilizers, antioxidants, anti-drip agents, light stabilizers, plasticizers, fillers, and colorants.

Suitable heat stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphine. Acid ester, trimethyl phosphate, and the like.

Suitable antioxidants include organic phosphites, alkylated monohydric or polyhydric phenols, alkylation products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkane Alkalized hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, and the like.

Suitable anti-drip agents are preferably fluorinated polyolefins, which are well known (see for example EP-A 640 655). Commercially available products such as those from DuPont

30N.

Suitable light stabilizers include one or more combinations of benzotriazoles, benzophenones.

A suitable plasticizer is a phthalate.

Suitable fillers include titanium dioxide, talc, mica and barium sulfate.

Suitable colorants include various pigments, dyes.

The preparation method of the above polycarbonate composition comprises the following steps:

1) selecting a rubber-modified graft polymer having a mass percentage of the flow promoter based on the total mass of the polycarbonate composition of 2% by weight or less and 0.01% by weight or more;

2) The above-mentioned rubber-modified graft polymer containing a flow promoter, polycarbonate, flame retardant, and other auxiliary agents are weighed in proportion, and then blended, extruded, and passed through a high-mixer or a mixer. The mixture was cooled with water and granulated to obtain a polycarbonate composition of columnar particles.

All ingredients may be added to the processing system first, or some additives may be premixed with one or more of the major components.

In one embodiment, the flame retardant composition can be dry blended to form a mixture in a device such as a Henschel mixer or a Waring blender prior to feeding to the extruder, wherein the mixture is molten Blended. In another embodiment, a portion of the polycarbonate composition can be premixed with a flame retardant to form a dry premix. The dry premix is then melt blended with the remaining polycarbonate composition in an extruder. In one embodiment, some of the flame retardant composition may be fed first at the mouth of the extruder while the remainder of the flame retardant composition is fed downstream through the port of the mouth.

Blending of the flame retardant composition includes using a combination of shear, tensile, compressive, ultrasonic, electromagnetic, thermal, or at least one of the above-described forces or forms of energy, and is performed in a processing facility , by single screw, multi-screw, meshing co-rotating or counter-rotating screw, non-intermeshing co-rotating or counter-rotating screw, reciprocating screw, screw with pin, barrel with pin, roller, ram The spiral force, or a combination comprising at least one of the foregoing, applies the force.

Blending involving the above forces can be carried out in machines such as single or multi-screw extruders, Buss kneaders, Henschel mixers, spiral mixers, Ross mixers, internal mixers (Banbury), roll mills, molding The machine (such as an injection molding machine, a vacuum molding machine, a blow molding machine) or the like, or a combination comprising at least one of the above machines.

The flame retardant composition can be introduced into the melt blending unit as a masterbatch. For example, a portion of the polycarbonate composition can be pre-blended with a phosphate flame retardant to form a masterbatch, and then the masterbatch is blended with the remaining ingredients to form a flame retardant composition. In this process, the masterbatch can be introduced into a blending device downstream of the location where the remaining components of the flame retardant composition are introduced.

The polycarbonate compositions of the present invention are useful in the preparation of molded articles such as, for example, durable articles, electrical and electronic components, automotive parts, and the like. The composition can be converted into articles using common thermoplastic processes such as film and sheet extrusion, injection molding, gas assisted injection molding, extrusion molding, compression molding, and blow molding.

The polycarbonate composition of the present invention can be used for outdoor and indoor applications, such as mobile phones, since it can significantly improve the impact strength of the polycarbonate composition without affecting its flame retardancy, fluidity, and heat resistance. MP3 players, computers, laptops, cameras, video recorders, tablets, hand-held receivers, kitchen appliances or parts of electrical enclosures, or automotive components for outdoor use, enclosures or covers for architectural applications, and enclosures and enclosures for electrical appliances .

Compared with the prior art, the invention has the following beneficial effects:

1) In the polycarbonate composition formulation, when the mass percentage of the flow promoter is less than or equal to 2% by weight based on the total mass of the polycarbonate composition, the rubber modified graft polymer and the polycarbonate are greatly improved. The compatibility and miscibility of the resin give the polycarbonate composition excellent melt stability.

2) When the mass percentage of the flow promoter in the total mass of the polycarbonate composition is less than or equal to 2% by weight, the rubber-modified graft polymer having a higher glossiness is easily migrated to the surface of the product, thereby improving The surface gloss of the polycarbonate composition is particularly suitable for applications where the use environment is relatively high.

detailed description

The invention is further illustrated by the following detailed description of the preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.

Test criteria or methods for each performance:

Melt Flow Rate (MFR) Stability Factor: Allows plastic pellets to melt into a plastic fluid over a period of time (10 minutes), at a certain temperature and pressure (different material standards), and then pass through a diameter of 2.1. The number of grams of the mm tube. The larger the value, the better the processing fluidity of the plastic material, and vice versa; the test standard used herein is ASTM D1238, unit: g/10 min. The test conditions were as follows: melt flow rate (MFR) at 230 ° C under a load of 2.16 kg.

During the production process, 7-10 g of cylindrical pellets were taken randomly, and dried at 100 ° C for more than 4 hours. The difference between the MFR _n measured by the above method and the mean value MFR _mean of 50 melt flow rates (MFR) was The mean of the square is defined as the melt flow rate (MFR) stability coefficient herein, ie the melt flow rate (MFR) stability coefficient = ((MFR _1- MFR _mean ) ² + (MFR ₂ -MFR _mean ) ² + (MFR ₃ -MFR _mean ) ² +········+(MFR ₅₀ -MFR _mean ) ² )/50; Obviously, the smaller the value, the higher the melt flow stability of the polycarbonate composition The opposite is the worse.

Method for determining surface gloss: Gloss was measured at 60 degrees using a 2.5 mm thick color card in accordance with ASTM D2457. Tested with the OU4200 gloss meter.

Polycarbonate used in the present invention:

Component a-1: PC 1300-10 (LG, Korea);

Component a-2: PC 1225 (Japanese Teijin);

Rubber modified graft polymer used in the present invention:

Component b-1: ABS1 emulsion method 757 (Taiwan Chi Mei);

Component b-2: ABS2 ontology 8391 (Shanghai Gaoqiao);

Component b-3: MBS EM500 (LG, Korea);

Polyethylene wax: (Clariant, Switzerland);

Amide wax: (Clarian, Switzerland);

Stearate: (Zhongshan Huamingtai Chemical Co., Ltd.);

Flame retardant used in the present invention:

Component c: BDP, bisphenol A-bis(diphenyl phosphate) (Idico);

Other auxiliaries used in the present invention:

Component d-1: AO1076: β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl alcohol ester CAS NO.: [2082-79-3]) as an antioxidant ;

Component d-2: PTFE (polytetrafluoroethylene) as an anti-drip agent.

Examples 1-12 and Comparative Examples 1-12: Preparation of Polycarbonate Compositions

Selecting a rubber-modified graft polymer having a mass percentage of the flow promoter in a total mass of the polycarbonate composition of 2% by weight or less and 0.01% by weight or more based on the total mass of the polycarbonate composition; the above-mentioned flow promoter is formulated according to the formulation of Table 1. The rubber-modified graft polymer, polycarbonate, flame retardant, and other auxiliary agents are weighed according to the ratio, and then blended by high-mixer or mixer, extruded, cooled by water, and granulated to obtain columnar particles. The polycarbonate composition; the melt flow rate (MFR) stability coefficient and surface gloss of the polycarbonate composition were tested. The data is shown in Table 1.

Table 1 Specific ratios (parts by weight) of Examples 1-12 and Comparative Examples 1-12 and test performance results thereof

Continued Table 1

From the comparison of the examples of Table 1 and the comparative examples, it can be seen that the present invention selects the mass percentage of the flow promoter in the total mass of the polycarbonate composition based on the polycarbonate composition formulation to be less than or equal to 2% by weight. The specific range of flow promoters is beneficial to improve the compatibility and mutual solubility of the rubber modified graft polymer with the polycarbonate resin, and the rubber modified graft polymer with higher gloss is easy to migrate to the product. The surface, which ultimately improves the melt stability and surface gloss of the polycarbonate composition, is particularly suitable for applications where the use environment is relatively high.

Claims (16)

1. A polycarbonate composition comprising, by weight, the following composition:

   a, 30.3 parts to 80.3 parts of polycarbonate;

   b, 7.7 parts to 49.7 parts of the rubber modified graft polymer;

   c, 4.5 parts - 24.5 parts of flame retardant;

   d, 0-9.8 parts of other auxiliaries;

   Wherein, the sum of the weight components of the four components a, b, c, and d is 100 parts.
2. A polycarbonate composition according to claim 1 comprising, by weight, the following composition:

   a, 35 parts - 75 parts of polycarbonate;

   b, 8 parts - 35 parts of rubber modified graft polymer;

   c, 5 parts - 24.5 parts of flame retardant;

   d, 0-9.8 parts of other auxiliaries;

   Wherein, the sum of the weight components of the four components a, b, c, d is 100 parts,

   The flow promoter has a mass percentage of 2% by weight or more and 0.01% by weight or more based on the total mass of the polycarbonate composition.
3. The polycarbonate composition according to claim 2, wherein the flow promoter is contained in an amount of not less than 1% by weight and 0.05% by weight or more based on the total mass of the polycarbonate composition; preferably less than or equal to 0.8. Wt% and greater than or equal to 0.1 wt%.
4. The polycarbonate composition according to claim 2 or 3, wherein the flow promoter is selected from the group consisting of a combination of a polyethylene wax and an amide wax, a compound of an amide wax and a stearate, and a polyethylene wax. Compounding with stearate, blending of polyethylene wax with amide wax and stearate.
5. The polycarbonate composition according to claim 4, wherein the compounding ratio of the polyethylene wax to the amide wax is from 3:1 to 1:3 based on the total mass of the flow promoter; the amide wax and the hard fat The compounding ratio of the acid salt is 2:1-1:5; the compounding ratio of the polyethylene wax to the stearate is 2:1-1:5; the compounding of the polyethylene wax with the amide wax and the stearate It is 1:1:10-1:1:1.
6. The polycarbonate composition according to claim 5, wherein the compounding ratio of the polyethylene wax to the amide wax is 2:1 to 1:2 based on the total mass of the flow promoter; the amide wax and the hard fat The compounding ratio of the acid salt is 1:2-1:3; the compounding ratio of polyethylene wax to stearate is 1:2-1:3; the compounding of polyethylene wax with amide wax and stearate is 3:3:20- 1:1:4.
7. The polycarbonate composition according to any one of claims 4 to 6, wherein the polyethylene wax has a molecular weight of 1,500 to 5,000 and is produced by depolymerization of polyethylene having a molecular weight of 10 ⁴ to 10 ⁷ . A polyethylene homopolymer/interpolymer having a molecular weight of 1000 to 2000, selected from the group consisting of low density polyethylene wax, high density polyethylene wax, modified high density polyethylene wax, partially oxidized polyethylene wax, and oxidized polyethylene wax. One or more of the above; the amide wax has a molecular weight of 400-1000, is a low molecular weight wax obtained by polycondensation reaction of a dibasic acid and a diamine, and is selected from the group consisting of oleic acid amides and/or fatty acid amides, more preferably It is ethylene bis stearic acid amide; the stearate is one or more selected from the group consisting of zinc stearate, magnesium stearate, and calcium stearate.
8. The polycarbonate composition according to claim 1 or 2, wherein the polycarbonate is selected from the group consisting of an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and One or more of the polycarbonates prepared by the solid phase transesterification of the prepolymer.
9. The polycarbonate composition according to claim 1 or 2, wherein the polycarbonate is selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, and a branched poly One or more of a carbonate or a siloxane copolycarbonate, preferably an aromatic polycarbonate; the aromatic polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, preferably a viscosity average The aromatic polycarbonate having a molecular weight of 16,000 to 28,000 is more preferably an aromatic polycarbonate having a viscosity average molecular weight of 17,000 to 24,000.
10. The polycarbonate composition according to claim 1 or 2, wherein the rubber-modified graft polymer is selected from the group consisting of emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, and bulk/suspension polymerization. One or more of the modified graft polymers.
11. The polycarbonate composition according to claim 1 or 2, wherein the rubber-modified graft polymer is selected from the group consisting of the following b.1 grafting on b.2. polymer:

    B.1, 5 parts - 95 parts of a mixture of b.1.1 and b.1.2:

    B.1.1, 50 parts - 95 parts of styrene, styrene derivatives such as α-methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid One or more of a C1-C8-alkyl ester, a dimethylsiloxane, a phenylsiloxane, a polyalkylsiloxane;

    B. 1.2, 5 parts - 50 parts of acrylonitrile, methacrylonitrile, C1-C8-alkyl methacrylate, one or more of C1-C8-alkyl acrylate;

    b. 2, 5 parts - 95 parts of polybutadiene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene random copolymer and block copolymer, polybutylene Alkene and polyisoprene copolymers, ethylene and a- One or more of an olefin copolymer, an ethylene and a-unsaturated carboxylic acid ester copolymer, and an ethylene-propylene-nonconjugated diene terpolymer.
12. The polycarbonate composition according to claim 10, wherein the rubber-modified graft polymer is selected from the group consisting of styrene-butadiene-styrene block copolymer SBS, acrylonitrile-butadiene. One or several of styrene graft copolymer ABS, methyl methacrylate-acrylonitrile-butadiene styrene copolymer MABS, methyl methacrylate-butadiene-styrene graft copolymer MBS Preferred; acrylonitrile-butadiene-styrene graft copolymer ABS; wherein MBS particle size is preferably 0.1 um-0.5 um, bulk polymerization ABS particle size is preferably 0.1 um-2 um, emulsion polymerization ABS particle size It is preferably 0.05 um to 0.2 um.
13. The polycarbonate composition according to claim 1 or 2, wherein the flame retardant is selected from a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant; The flammable agent is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, One or more of decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane or brominated aromatic crosslinked polymer, preferably brominated polystyrene; The halogen-free flame retardant is selected from one or more of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant or a nitrogen and phosphorus-containing flame retardant, preferably a phosphorus-containing flame retardant.
14. The polycarbonate composition according to claim 12, wherein the phosphorus-containing flame retardant is characterized in that the phosphorus-containing flame retardant is selected from the group consisting of triphenyl phosphate, tricresyl phosphate, and phosphoric acid. Tolyl diphenyl ester, trimethylphenyl phosphate, tris(2,4,6-trimethylphenyl) phosphate, tris(2,4-di-tert-butylphenyl) phosphate, tris(phosphate) 2,6-di-tert-butylphenyl) ester, resorcinol bis(diphenyl phosphate), hydroquinone bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate) And one or more of resorcinol bis(2,6-di-tert-butylphenyl phosphate) and hydroquinone bis(2,6-dimethylphenyl phosphate).
15. The polycarbonate composition according to claim 1 or 2, wherein the other auxiliary agent of component d is selected from the group consisting of a heat stabilizer, an antioxidant, an anti-drip agent, a light stabilizer, and a plasticizer. One or several of fillers, colorants.
16. A method of preparing a polycarbonate composition according to any one of claims 1 to 14, comprising the steps of:

    1) selecting a rubber-modified graft polymer having a mass percentage of the flow promoter based on the total mass of the polycarbonate composition of 2% by weight or less and 0.01% by weight or more;

    2) The above-mentioned rubber-modified graft polymer containing a flow promoter, polycarbonate, flame retardant, and other auxiliary agents are weighed in proportion, and then blended, extruded, and passed through a high-mixer or a mixer. Water cooling The granules give a polycarbonate composition of columnar granules.