WO2016188474A1 - 一种聚碳酸酯组合物及其制备方法 - Google Patents

一种聚碳酸酯组合物及其制备方法 Download PDF

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WO2016188474A1
WO2016188474A1 PCT/CN2016/083620 CN2016083620W WO2016188474A1 WO 2016188474 A1 WO2016188474 A1 WO 2016188474A1 CN 2016083620 W CN2016083620 W CN 2016083620W WO 2016188474 A1 WO2016188474 A1 WO 2016188474A1
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parts
polycarbonate
group
polycarbonate composition
flame retardant
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PCT/CN2016/083620
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English (en)
French (fr)
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岑茵
孙东海
佟伟
谢湘
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金发科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
  • 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 combine the excellent performance of both, and improve the physical properties and processing performance.
  • ABS due to the addition of ABS, the double bond in the system will bring long-term Hot oxygen aging performance and weathering performance hazards, especially when the use environment is relatively high, the surface is easy to form defects and its color is easy to change.
  • Patent CN102292393 discloses that the use of salt inclusions can improve the surface quality after hot wet storage and is therefore suitable for the preparation of molded articles having an ageing resistant defect-free A-grade surface;
  • Patent CN104271610 discloses the use of sodium, magnesium and calcium impurities to prepare a polymer having improved surface after moist heat storage; however, the above light metal impurities are easily alkaline in a hot and humid environment, promoting degradation of the polycarbonate, thereby causing degradation of properties before and after use. And the color difference is large, and the stability is poor in practical applications.
  • the inventors have surprisingly found through a large number of experiments that the total amount of the phenolic substance and the metal manganese element added in the polycarbonate composition formulation is not more than 500 ppm based on the total weight of the polycarbonate composition, so that the polycarbonate is made.
  • the ester composition has good fluidity and color stability and high gloss before and after long-term thermal oxygen aging, and is particularly suitable for occasions where the use environment is relatively high.
  • Still another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.
  • a polycarbonate composition comprising, by weight, the following composition:
  • the sum of the weight components of the four components a, b, c, and d is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the four components a, b, c, d is 100 parts;
  • the total amount of the phenolic substance and the metal manganese element in the total weight of the polycarbonate composition is 10 ppm or more and 500 ppm or less; wherein the structural formula of the phenolic substance is as shown in the formula (1):
  • R 1 and R 5 represent a hydrogen group other than a hindered group, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or a carbonyl group, and an ester group
  • R 2 , R 3 and R 4 represent a substituent having a hydrogen atom, preferably hydrogen. atom.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the four components a, b, c, d is 100 parts;
  • the total amount of the phenolic substance and the metal manganese element in the total weight of the polycarbonate composition is 10 ppm or more and 500 ppm or less; wherein the structural formula of the phenolic substance is as shown in the formula (1):
  • R 1 and R 5 represent a hydrogen group other than a hindered group, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or a carbonyl group, and an ester group
  • R 2 , R 3 and R 4 represent a substituent having a hydrogen atom, preferably hydrogen. atom.
  • the test method for the content of the phenolic substance after weighing 2 g of the polycarbonate composition with an electronic balance, the sample is placed in a constant temperature oven at a preset temperature of 120 ° C and the temperature is uniformly stabilized, and then placed in Soxhlet.
  • the extraction device was subjected to methanol extraction, the extraction temperature was 85 ° C, and the time was 48 h.
  • the extract is injected into the adsorption column of C18 for separation and quantification.
  • the specific outflow time of the standard and the extrapolation method can be calculated.
  • the content of phenolic substances is obtained.
  • Test method for the content of manganese metal elements ICP-MS mixed standard method.
  • the total amount of the phenolic substance and the metal manganese element is 20 ppm or more and 400 ppm or less; preferably 30 ppm or more and 300 ppm or less; more preferably 50 ppm or more and 200 ppm or less.
  • the compounding weight ratio of the phenolic substance and the metal manganese element is 2:3-4:3.
  • the polycarbonate is selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-fat One or more of a family polycarbonate, a branched polycarbonate, a siloxane copolycarbonate; preferably an aromatic polycarbonate.
  • the polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, more preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000.
  • the viscosity average molecular weight was calculated by using a solution of dichloromethane as a solvent at a test temperature of 25 ° C.
  • the above polycarbonate can be produced by an interfacial polymerization method and a transesterification method, and the terminal hydroxyl group content can be controlled in the process.
  • the graft copolymer is selected from one or more of a graft copolymer prepared by bulk polymerization, emulsion polymerization, bulk-suspension polymerization.
  • Bulk polymerization method including sol, prepolymerization, polymerization, devolatilization and granulation.
  • the rubber is dissolved in ethylbenzene and styrene, and the monomer is mixed into a raw material liquid according to the formula amount, and the prepared raw material liquid is input.
  • the prepolymerization is carried out in a prepolymerization kettle.
  • the rubber grafting monomer while the monomer is copolymerized, is separated from the solution to form a discontinuous phase dispersed in the continuous phase of the raw material liquid, when there are enough single
  • the discontinuous phase of the copolymer becomes a continuous phase
  • the grafted rubber forms a discontinuous phase dispersed in the continuous copolymer phase, completes the phase transition, and finally undergoes further polymerization, vacuum degassing, extrusion, cooling and Pelletizing to obtain the final product;
  • Bulk-suspension polymerization method adjust the rubber and monomer solution according to the formulation, and notify the addition of a polymerization regulator and a radical initiator, and carry out bulk polymerization of the monomer mixture at 80 ° C - 120 ° C, stirring constantly during the polymerization, and going Ionic water and a suspending agent are added to the mixture to disperse the mixture, and then suspension polymerization is carried out by using a radical catalyst to obtain a certain degree of polymerization, followed by agglomeration, filtration, washing, dehydration and drying, and then granulating to obtain a product;
  • Emulsion polymerization method the rubber is grafted by adding the monomer mixture to the rubber latex at a polymerization temperature of 50 ° C to 80 ° C in an initiator, deionized water, an emulsifier and a crosslinking agent, and finally washing, dehydrating and drying. After granulation, the product is obtained.
  • graft copolymer is selected from the group consisting of the following graft copolymers comprising b.1 on b.2:
  • B.1.1 50 parts - 95 parts of styrene, styrene derivatives such as ⁇ -methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid C1-C8-alkyl ester, dimethyl
  • styrene styrene derivatives such as ⁇ -methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid C1-C8-alkyl ester, dimethyl
  • a siloxane a phenylsiloxane, a polyalkylsiloxane
  • rubber graft base such as polybutadiene, polyisoprene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene random Copolymers and block copolymers, polybutadiene and polyisoprene copolymers, ethylene and a-olefin copolymers, ethylene and a-unsaturated carboxylic acid ester copolymers, ethylene-propylene-non-conjugated dienes
  • a terpolymer an acryl rubber, and an organosiloxane rubber.
  • the graft copolymer is selected from the group consisting of acrylonitrile-styrene copolymer AS, acrylonitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-acrylonitrile-butadiene styrene
  • copolymer MABS acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene graft copolymer MBS;
  • ABS acrylonitrile-butadiene-styrene graft copolymer ABS in which the butadiene rubber polymer has a weight fraction of 5 wt% to 50 wt% in ABS, and the particle size distribution may be uniform or have two Or multiple distributions of the above peaks.
  • the graft copolymer is selected from the group consisting of graft polymers comprising b.1 on b.2 as follows:
  • B.1.1 50 parts - 95 parts of styrene, styrene derivatives such as ⁇ -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;
  • rubber-containing graft base such as polybutadiene, polyisoprene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene Copolymers and block copolymers, polybutadiene and polyisoprene copolymers, ethylene and a-olefin copolymers, ethylene and a-unsaturated carboxylic acid ester copolymers, ethylene-propylene-nonconjugated One or more of an olefinic terpolymer, an acryl rubber, and an organosiloxane rubber.
  • rubber-containing graft base such as polybutadiene, polyisoprene, styrene-butadiene random copolymer and block copolymer, acrylonitrile-butadiene Copolymers and block copolymers, polybutadiene and polyisoprene copolymers, ethylene and a
  • the graft copolymer is selected from the group consisting of acrylonitrile-styrene copolymer AS, acrylonitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-acrylonitrile-butadiene styrene Copolymer MABS, acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene grafting
  • the polymers MBS wherein the particle size of the MBS is preferably 0.1 um to 0.5 um, the bulk polymerization method ABS particle diameter 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.
  • ABS acrylonitrile-butadiene-styrene graft copolymer ABS in which the butadiene rubber polymer has a weight fraction of 5 wt% to 50 wt% in ABS, and the particle size distribution may be uniform or have two Or multiple distributions of the above peaks.
  • 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
  • the phosphorus-containing flame retardant is selected from the group consisting of triphenyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, trimethylphenyl phosphate, and tris(2,4,6-trimethyl phosphate).
  • Phenyl) ester tris(2,4-di-tert-butylphenyl) phosphate, tris(2,6-di-tert-butylphenyl) phosphate, resorcinol bis(diphenyl phosphate) , hydroquinone bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate), p-phenylene One or more of phenol bis(2,6-dimethylphenyl phosphate).
  • the polyester composition may further comprise other auxiliary agents, such as one or more selected from the group consisting of stabilizers, flame retardant synergists, anti-drip agents, lubricants, mold release agents, plasticizers, fillers, and colorants.
  • auxiliary agents such as one or more selected from the group consisting of stabilizers, flame retardant synergists, anti-drip agents, lubricants, mold release agents, plasticizers, fillers, and colorants.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphonic acid Ester, trimethyl phosphate, etc., organic phosphite, alkylated monohydric or polyhydric phenol, alkylation reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene , alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones Or a variety of combinations.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl
  • a suitable plasticizer is a phthalate.
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable colorants include various pigments, dyes.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the polycarbonate composition of the invention has excellent long-term thermal stability and weather resistance, no defects in appearance and excellent mechanical properties, and can be used in outdoor and indoor applications, such as various types and sizes of outer casing parts, household appliances. Such as televisions, printers, modem enclosures, display enclosures, etc., or automotive components for outdoor use, enclosures or covers for architectural applications, and electrical appliance enclosures and bezels.
  • the invention has the following beneficial effects:
  • the present invention pretreats polycarbonate by using a phenolic substance and a metal manganese element, and the metal manganese element acts as a reduction in the system, and can balance the degradation of the iron atom or its compound on the polymer, and at the same time in trace amounts.
  • the retained phenolic substances can capture the synergistic action of the active sites formed by the thermal oxygen shearing of polycarbonate during post-processing and molding, and can better stabilize the phenolic hydroxyl groups in the system, so that the polycarbonate maintains excellent fluidity.
  • a phenolic substance is used as a blocking agent in the synthesis process to form a phenolic hydroxyl group, and a trace amount of a phenolic substance cannot be left.
  • the present invention allows the flow of the polycarbonate composition by using a total amount of the phenolic substance and the metal manganese element added to the polycarbonate composition formulation in an amount of not more than 500 ppm based on the total weight of the polycarbonate composition. It has good properties and has long-term thermal stability before and after aging, and it is especially suitable for occasions where the use environment is relatively high.
  • Test method for manganese content of metal ICP-MS mixed standard method
  • Newton's index method the die length to diameter ratio is 20, the shear stability temperature is 260 ° C, the shear rate is 100 s -1 -10000 s -1 , the preheating time is 300 s, and the shear rate and shear stress curve are obtained. After the exponentiation n, the Newtonian index is obtained.
  • Gloss measurement method After the swatch is kept at constant temperature and humidity for 48 hours, the glossiness of the 60° angle is measured by a gloss meter, and the surface gloss level is the best, without any defects, and the level 2 has a slight water pitting, 3 The grade is poor surface gloss, obvious splash and pitting;
  • Component a-1 PC 1300-10 (LG, Korea);
  • Component a-2 PC 1225 (Japanese Teijin);
  • Phenolic substances used in the present invention are used in the present invention:
  • Phenolic substances used in the present invention are used in the present invention:
  • the graft copolymer used in the present invention is graft copolymer used in the present invention:
  • Component b-1 ABS1 Emulsion Method 757 (Taiwan Chi Mei);
  • Component b-2 ABS2 Ontology Method 8391 (Shanghai Gaoqiao);
  • Component b-3 MBS EM500 (LG, Korea);
  • Component c BDP, bisphenol A-bis(diphenyl phosphate) (Idico);
  • Component d-1 PEP-36 (bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate) as a stabilizer;
  • Component d-2 C wax as a lubricant
  • Component d-3 PTFE (polytetrafluoroethylene) as an anti-drip agent
  • Component d-4 colorant carbon black M717.
  • Phenolic materials and standard manganese solution and phenylsiloxane are formulated into a phenylsiloxane solution with a mass fraction of 12.5 ppm to 2000 ppm; blending the phenylsiloxane solution with polycarbonate in a high mixer
  • the pretreated polycarbonate is obtained; the pretreated polycarbonate, the graft copolymer, the flame retardant, and other auxiliary agents are weighed according to the formula of Table 1, and then blended by a high mixer or a mixer.
  • the total amount of the phenolic substance and the metal manganese element added in the polycarbonate composition formulation is not more than 500 ppm based on the total weight of the polycarbonate composition.
  • the polycarbonate composition has good fluidity and has long-term thermal stability before and after thermal aging And high gloss, especially suitable for occasions where the use environment is relatively high.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明公开了一种聚碳酸酯组合物，按重量份计，包括以下组成： a、30份-80份的聚碳酸酯； b、8份-50份的接枝共聚物； c、5份-25份的阻燃剂； d、0-10份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份。本发明通过选用在聚碳酸酯组合物配方中添加苯酚类物质和金属锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过500ppm时，使得聚碳酸酯组合物的流动性好，且具有长期热氧老化前后颜色稳定性和高光泽度，特别适用于使用环境要求比较高的场合；其中苯酚类物质的结构式如式(1)：其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子。

Description

一种聚碳酸酯组合物及其制备方法 技术领域
本发明涉及工程塑料技术领域，特别涉及一种聚碳酸酯组合物及其制备方法。
背景技术
聚碳酸酯PC具有较高耐冲击性及耐热性等特性，为改善其加工性能及对缺口冲击敏感的缺点，通常可加入橡胶类改性聚合物，如ABS、MBS等，特别是以PC和ABS为主要原料的PC/ABS合金是一种重要的工程塑料，可综合两者的优良性能，做到物理性能以及加工性能得到提高，但是由于ABS的加入，体系中双键会带来长期热氧老化性能以及耐候性能的隐患，特别是对使用环境要求比较高的场合，其表面容易形成缺陷以及其颜色容易发生变化。
专利CN102292393公开了使用盐夹杂物能改善在热湿储存之后的表面质量，因此适合于制备具有耐老化的无缺陷A级表面的模塑品；
专利CN104271610公开了选用钠、镁、钙杂质制备具有湿热储存后改善表面的聚合物；但是以上轻金属杂质容易在湿热环境下形成碱性，促进聚碳酸酯的降解，从而导致其在使用前后性能衰减以及颜色差异较大，在实际应用中稳定性较差。
到目前为止，关于苯酚类物质和金属锰元素的复配总量对所述聚碳酸酯组合物的流动性、高光泽度，以及颜色稳定性的影响未见报道。
本发明人经过大量实验惊讶地发现，选用在聚碳酸酯组合物配方中添加苯酚类物质和金属锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过500ppm时，使得聚碳酸酯组合物的流动性好，且具有长期热氧老化前后颜色稳定性和高光泽度，特别适用于使用环境要求比较高的场合。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种具有优异的流动性，且具有长期热氧老化前后颜色稳定性和高光泽度的聚碳酸酯组合物。
本发明的再一目的是提供上述聚碳酸酯组合物的制备方法。
本发明是通过以下技术方案实现的：
一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-80份的聚碳酸酯；
b、8份-50份的接枝共聚物；
c、5份-25份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份。
优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-75份的聚碳酸酯；
b、8份-35份的接枝共聚物；
c、5份-23份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份；
基于聚碳酸酯组合物的总重量中苯酚类物质和金属锰元素的复配总量大于等于10ppm和小于等于500ppm；其中苯酚类物质的结构式如式(1)：
Figure PCTCN2016083620-appb-000001
式(1)
其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子。
更优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-70份的聚碳酸酯；
b、8份-30份的接枝共聚物；
c、5份-18份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份；
基于聚碳酸酯组合物的总重量中苯酚类物质和金属锰元素的复配总量大于等于10ppm和小于等于500ppm；其中苯酚类物质的结构式如式(1)：
Figure PCTCN2016083620-appb-000002
式(1)
其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子。
其中，苯酚类物质的含量的测试方法：用电子天平称量2g的聚碳酸酯组合物后，将样品放入预设温度120℃并且温度均一稳定的恒温烘箱中2h后，放入索氏抽提装置进行甲醇抽提，抽提温度为85℃，时间为48h，将抽提液放置到恒温后，通过过滤网抽出20ul，以10ml/min的流速，借助流动相(甲醇:纯净水＝90:10)将抽提液进样到C18的吸附柱里进行分离以及定量，通过建立1ppm，5ppm，10ppm以及20ppm的标准溶液建立标准曲线后，可以通过标样的特定流出时间以及外推法计算得出苯酚类物质的含量。
金属锰元素的含量的测试方法：ICP-MS混标法。
当基于聚碳酸酯组合物的总重量中苯酚类物质和金属锰元素的复配总量超过500ppm，由于体系中过盈的小分子，会导致流动不稳定以及明显的表面麻点水花，从而存在加工稳定性和表面缺陷的隐患。
优选地，所述苯酚类物质和金属锰元素的复配总量为大于等于20ppm和小于等于400ppm；优选为大于等于30ppm和小于等于300ppm；更优选为大于等于50ppm和小于等于200ppm。
其中，所述苯酚类物质和金属锰元素的复配重量比为2：3-4：3。
其中，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪 族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯。
所述聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，更优选为粘均分子量16000-28000的芳香族聚碳酸酯。当粘均分子量在上述范围内，机械强度良好并且能保持优异的成型性。其中，粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。
上述聚碳酸酯的制备方法可以通过界面聚合法和酯交换法制得，并且可以在过程中控制端羟基的含量。
其中，所述接枝共聚物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的接枝共聚物的一种或几种。
本体聚合法：包括溶胶，预聚合，聚合，脱挥和造粒五个步骤：将橡胶溶解在乙苯和苯乙烯中，按照配方量加入单体配成原料液，将配好的原料液输入预聚釜中进行预聚合，在聚合过程中，橡胶接枝单体，同时单体共聚，从溶液中分离出来，形成分散在原料液中连续相中的不连续相，当具有足够多的单体聚合后，不连续相的共聚物变成连续相，接枝的橡胶形成不连续相分散在连续的共聚物相中，完成相转变，最后经过进一步聚合，真空脱气，挤出，冷却和切粒得到最终制品；
本体-悬浮聚合法：按照配方调节橡胶和单体溶液，并通知加入聚合调节剂和自由基引发剂，将单体混合物在80℃-120℃进行本体聚合，聚合过程中不断搅拌，并将去离子水和悬浮剂加入到混合物中，使混合物得到分散，然后利用自由基催化剂进行悬浮聚合，得到一定聚合度后经过凝聚，过滤，洗涤，脱水和干燥后造粒获得制品；
乳液聚合法：橡胶通过在引发剂，去离子水，乳化剂和交联剂，聚合温度控制在50℃-80℃，将单体混合物加到橡胶乳胶进行接枝，最后进行洗涤，脱水和干燥后造粒获得制品。
其中，所述接枝共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物：
b.1、5份-95份的b.1.1和b.1.2的混合物：
b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲 基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
b.2、5份-95份的橡胶接枝基础如聚丁二烯、聚异戊二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物、丙烯酰橡胶、有机硅氧烷橡胶的一种或几种。
更优选地，所述接枝共聚物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；
进一步优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS，其中丁二烯橡胶质聚合物在ABS中的重量分数为5wt％-50wt％，粒径分布可以是均匀的或者具有两个或者以上峰值的多分布。
优选地，所述接枝共聚物，按重量份计，选自包含如下b.1在b.2上的接枝聚合物：
b.1、30份-80份的b.1.1和b.1.2的混合物：
b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
b.2、20份-70份的含橡胶接枝基础如聚丁二烯、聚异戊二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物、丙烯酰橡胶、有机硅氧烷橡胶的一种或几种。
更优选地，所述接枝共聚物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共 聚物MBS中的一种或几种；其中MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
进一步优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS，其中丁二烯橡胶质聚合物在ABS中的重量分数为5wt％-50wt％，粒径分布可以是均匀的或者具有两个或者以上峰值的多分布。
其中，所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
优选地，所述含磷阻燃剂选自磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A-双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
该聚酯组合物中还可以包含其它助剂，如选自稳定剂、阻燃增效剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、着色剂的一种或几种。
合适的稳定剂包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等，有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类，苯并三唑类，二苯甲酮类的一种或者多种组合。
合适的增塑剂为邻苯二甲酸酯。
合适的脱模剂包括硬脂酸金属盐类，硬脂酸烷基酯类，硬脂酸季戊四醇酯类，石蜡，褐煤蜡等等。
合适的着色剂包括各种颜料，染料。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)将苯酚类物质以及标准锰溶液与苯基硅氧烷按照配比质量分数为 12.5ppm-2000ppm的苯基硅氧烷溶液；
2)将苯基硅氧烷溶液与聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；
3)将预处理的聚碳酸酯、接枝共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
本发明的聚碳酸酯组合物由于具有优异的长期热稳定性和耐候性，外观无缺陷以及优异的力学性能，可用于户外以及室内的应用领域，例如各种类型和尺寸的外壳部件，家用电器如电视机，打印机，modem外壳，显示器外壳等，或者在户外使用的汽车部件，建筑领域的外壳或者盖子，以及电器用具外壳和边框。
本发明与现有技术相比，具有如下有益效果：
1)本发明通过用苯酚类物质以及金属锰元素对聚碳酸酯进行预处理，金属锰元素在体系中起到还原作用，能够平衡铁原子或者其化合物对聚合物的降解作用，同时在痕量级留存的苯酚类物质能够捕捉聚碳酸酯在后加工以及成型中热氧剪切形成的活性点的协同作用下，能够更好地稳定体系中的酚羟基，使得聚碳酸酯保持优异的流动性，避免现有技术中一般采用苯酚类物质在合成过程中作为封端剂形成酚羟基而无法残留痕量的苯酚类物质的缺陷。
2)本发明通过选用在聚碳酸酯组合物配方中添加苯酚类物质和金属锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过500ppm时，使得聚碳酸酯组合物的流动性好，且具有长期热氧老化前后颜色稳定性和高光泽度，特别适用于使用环境要求比较高的场合。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
各性能的测试标准或方法：
苯酚类物质含量的测定方法：用电子天平称量2g的聚碳酸酯组合物后，将样品放入预设温度120℃并且温度均一稳定的恒温烘箱中2h后，放入索氏抽提装置进行甲醇抽提，抽提温度为85℃，时间为48h，将抽提液放置到恒温后，通过过滤网抽出20ul，以10ml/min的流速，借助流动相(甲醇:纯净水＝90:10)将 抽提液进样到C18的吸附柱里进行分离以及定量，通过建立1ppm，5ppm，10ppm以及20ppm的标准溶液建立标准曲线后，可以通过标样的特定流出时间以及外推法计算得出苯酚类物质的含量；
金属锰元素含量的测试方法：ICP-MS混标法；
牛顿指数的测定方法：模口长径比为20，剪切稳温度为260℃，剪切速率为100s-1-10000s-1，预热时间300s，后得到剪切速率以及剪切应力的曲线后求幂n得到牛顿指数。其中，牛顿指数的计算方法：通过剪切速率和剪切应力做幂拟合，得到拟合公式y＝a xn，拟合公式的方差R2要大于0.99；其中，n为牛顿指数，牛顿指数越小，其加工性能越好，并且，牛顿指数降低0.01，其加工性能有明显改善。
长期热氧老化颜色稳定性的测定方法：80℃烘箱热氧色板颜色变化等级，1级为最好，5级为最差；
光泽度的测定方法：色板恒温恒湿放置48h后用光泽度仪测定60°角的光泽度，表面光泽度等级，1级为最好，没有任何缺陷，2级有轻微水花麻点，3级为表面光泽度差，明显水花和麻点；
本发明中使用的聚碳酸酯：
组分a-1：PC 1300-10(韩国LG)；
组分a-2：PC 1225(日本帝人)；
本发明中使用的苯酚类物质：
本发明中使用的苯酚类物质：
对甲基苯酚类物质：(阿拉丁)；
二甲基苯酚类物质：(阿拉丁)；
标准锰溶液：(国家钢铁研究院)
本发明中使用的接枝共聚物：
组分b-1：ABS1 乳液法757(台湾奇美)；
组分b-2：ABS2 本体法8391(上海高桥)；
组分b-3：MBS  EM500(韩国LG)；
本发明中使用的阻燃剂：
组分c：BDP，双酚A-双(磷酸二苯基酯)(艾迪科)；
本发明中使用的其它助剂：
组分d-1：PEP-36(双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)作为稳定剂；
组分d-2：C蜡作为润滑剂；
组分d-3：PTFE(聚四氟乙烯)作为抗滴落剂；
组分d-4：着色剂炭黑M717。
实施例1-12及对比例1-8：聚碳酸酯组合物的制备
将苯酚类物质以及标准锰溶液与苯基硅氧烷配成质量分数为12.5ppm-2000ppm的苯基硅氧烷溶液；将苯基硅氧烷溶液与聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；按表1的配方将预处理的聚碳酸酯、接枝共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物；对聚碳酸酯组合物的流动性(牛顿指数)、长期热氧老化颜色稳定性(色差)和光泽度进行测试，数据见表1。
表1 实施例1-12及对比例1-8的具体配比(重量份)及其测试性能结果
Figure PCTCN2016083620-appb-000003
Figure PCTCN2016083620-appb-000004
续表1
Figure PCTCN2016083620-appb-000005
从表1的实施例和对比例的比较可以看出：选用在聚碳酸酯组合物配方中添加苯酚类物质和金属锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过500ppm时，聚碳酸酯组合物的流动性好，且具有长期热氧老化前后颜色稳定性 和高光泽度，特别适用于使用环境要求比较高的场合。

Claims (14)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-80份的聚碳酸酯；
    b、8份-50份的接枝共聚物；
    c、5份-25份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份。
  2. 一种如权利要求1所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-75份的聚碳酸酯；
    b、8份-35份的接枝共聚物；
    c、5份-23份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份；
    基于聚碳酸酯组合物的总重量中苯酚类物质和金属锰元素的复配总量大于等于10ppm和小于等于500ppm；其中苯酚类物质的结构式如式(1)：
    Figure PCTCN2016083620-appb-100001
    其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子。
  3. 一种如权利要求1所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-70份的聚碳酸酯；
    b、8份-30份的接枝共聚物；
    c、5份-18份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份；
    基于聚碳酸酯组合物的总重量中苯酚类物质和金属锰元素的复配总量大于等于10ppm和小于等于500ppm；其中苯酚类物质的结构式如式(1)：
    Figure PCTCN2016083620-appb-100002
    其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子。
  4. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述苯酚类物质和金属锰元素的复配总量为大于等于20ppm和小于等于400ppm；优选为大于等于30ppm和小于等于300ppm；更优选为大于等于50ppm和小于等于200ppm。
  5. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述苯酚类物质和金属锰元素的复配重量比为2：3-4：3。
  6. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或一种；优选为芳香族聚碳酸酯。
  7. 根据权利要求6所述的聚碳酸酯组合物，其特征在于，所述芳香族聚碳酸酯选自粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均分子量16000-28000的芳香族聚碳酸酯。
  8. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述接枝共聚物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的接枝共聚物的一种或几种。
  9. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述接枝共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物
    b.1、5份-95份的b.1.1和b.1.2的混合物：
    b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
    b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
    b.2、5份-95份的聚丁二烯、聚异戊二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物、丙烯酰橡胶、有机硅氧烷橡胶的一种或几种。
  10. 根据权利要求9所述的聚碳酸酯组合物，所述接枝共聚物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS；其中MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
  11. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂、含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
  12. 根据权利要求11所述的聚碳酸酯组合物，其特征在于，所述含磷阻燃剂选自磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A- 双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
  13. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述组分d的其它助剂选自稳定剂、阻燃增效剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、着色剂的一种或几种。
  14. 一种如权利要求1-13任一项所述的聚碳酸酯组合物的制备方法，其特征在于，包括如下步骤：
    1)将苯酚类物质以及标准锰溶液与苯基硅氧烷配成质量分数为12.5ppm-2000ppm的苯基硅氧烷溶液；
    2)将苯基硅氧烷溶液与聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；
    3)将预处理的聚碳酸酯、接枝共聚物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
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