WO2018095189A1 - 聚碳酸酯组合物及其制备方法 - Google Patents

聚碳酸酯组合物及其制备方法 Download PDF

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WO2018095189A1
WO2018095189A1 PCT/CN2017/107746 CN2017107746W WO2018095189A1 WO 2018095189 A1 WO2018095189 A1 WO 2018095189A1 CN 2017107746 W CN2017107746 W CN 2017107746W WO 2018095189 A1 WO2018095189 A1 WO 2018095189A1
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polycarbonate
polycarbonate composition
calcium
flame retardant
ppm
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PCT/CN2017/107746
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English (en)
French (fr)
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岑茵
田征宇
谢修好
佟伟
丁超
叶南飚
谢湘
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金发科技股份有限公司
上海金发科技发展有限公司
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    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/10—Metal compounds
    • 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
    • C08K3/16—Halogen-containing compounds
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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;
  • the inventors have surprisingly found through extensive experimentation that in a polycarbonate composition, calcium is added to the polycarbonate composition by adding a calcium-containing compound having a lower soluble calcium content and reducing or avoiding the addition of other calcium-containing compounds.
  • the content of the product is controlled in the range of 50-300 ppm, so that the obtained polycarbonate composition not only has high impact strength and good processing fluidity, but also satisfies the processing requirements of various molded parts, and has high gloss.
  • the degree of surface quality of the polycarbonate composition is significantly improved.
  • 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 components:
  • the calcium element has a weight content of 50 ppm to 300 ppm based on the total weight of the polycarbonate composition.
  • the weight content of the calcium element was determined by the following method: weighing 200 mg of the polycarbonate composition (accurate To 0.1mg) to 50ml volumetric flask, add 5ml nitric acid, 0.1-1ml hydrogen peroxide, add water to the specified scale, cover the cap and put it into the microwave to digest, open the cap, cool to room temperature, add 4ml HCL solution, cover The upper cap was placed in a microwave oven for secondary digestion, then cooled to room temperature, filtered, and 1 ml of the digestion solution was tested by ICP-MS mixing method of Agilent Tcechnologies 700series, and finally the calcium element in the polycarbonate composition was measured. The detection limit is 2 ppm.
  • the present inventors have found that by adding a calcium-containing compound having a lower soluble calcium content in a polycarbonate composition, and reducing or avoiding the addition of other calcium-containing compounds, and controlling the content of calcium in the polycarbonate composition.
  • a calcium-containing compound having a lower soluble calcium content in a polycarbonate composition, and reducing or avoiding the addition of other calcium-containing compounds, and controlling the content of calcium in the polycarbonate composition.
  • the content of calcium is higher than 300ppm, the system will be alkaline.
  • the polycarbonate resin In an alkaline environment, the polycarbonate resin will be broken, resulting in a decrease in the gloss of the part, and defects such as gas marks on the surface, which cannot be good.
  • the appearance provides quality assurance.
  • the content of calcium is less than 50ppm, the equilibrium effect is not obvious, the system is acidic, and the ester polymer will also induce the degradation reaction by the external force of heat and shear under acidic conditions. Surface quality Falling, the gloss is reduced.
  • the calcium element has a weight content of from 80 ppm to 250 ppm, more preferably from 100 ppm to 200 ppm, based on the total weight of the polycarbonate composition.
  • the calcium element is derived from a calcium-containing compound selected from the group consisting of calcium-containing compounds having a pH of not more than 8 in purified water at 60 ° C, such as calcium halides such as calcium chloride, calcium sulfonates Such as calcium sulfate, calcium sulfonate, etc., organic complexes of calcium and the like.
  • the calcium-containing compound is preferably added in an amount such that the content of the calcium element in the polycarbonate composition is in the range of 50 ppm to 300 ppm.
  • 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; It is 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 is within the above range, the mechanical strength is good and excellent moldability can be maintained.
  • the viscosity average molecular weight was tested by a viscosity method using 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 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, and when there are enough monomers to be polymerized, the discontinuous phase
  • 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.
  • 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, One or more of acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene graft copolymer MBS; wherein the particle size of MBS is preferably 0.1 um-0.5 um,
  • the bulk polymerization method ABS particle size is preferably 0.1 um to 2 um
  • 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 mineral filler may specifically be talc, kaolin, clay, whiskers, diatomaceous earth, etc., and the mineral filler may be without any surface treatment, or may be coated, for example, an alkyl surface coating.
  • Epoxy surface treatment Treatment with amide surface treatment, hydroxy silicone oil, alkyl silane, methoxy silane, sulfonic acid group, etc.
  • the polycarbonate composition of the present invention may further comprise 0-20 parts by weight of other auxiliaries, such as selected from the group consisting of stabilizers, anti-drip agents, lubricants, mold release agents, plasticizers, One or several of the colorants.
  • auxiliaries such as selected from the group consisting of stabilizers, anti-drip agents, lubricants, mold release agents, plasticizers, One or several of the colorants.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphonic acid Ester, trimethyl phosphate, etc., pentaerythritol diphosphate (such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate), organic phosphite, alkylated monohydric phenol or Polyphenols, alkylation products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, One or more combinations of alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones.
  • organic phosphites
  • Suitable anti-drip agents are preferably fluorinated polyolefins such as polytetrafluoroethylene.
  • a suitable plasticizer is a phthalate.
  • the lubricant is one or a mixture of two or more of ethylene bisstearamide EBS, erucamide, zinc stearate, silicone oil, PETS.
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable colorants include various pigments, dyes such as carbon black and the like.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the pretreated polycarbonate, graft copolymer, flame retardant, mineral filler, and other auxiliary agents are weighed according to the ratio, and then blended, extruded, and cooled by a high-mixer or a mixer.
  • the granules give a polycarbonate composition of columnar granules.
  • the invention has the following beneficial effects:
  • the content of calcium element in the polycarbonate composition is controlled in the range of 50-300 ppm by adding a calcium-containing compound having a lower soluble calcium content and reducing or avoiding the addition of other calcium-containing compounds.
  • the polycarbonate composition obtained can not only have higher impact strength and better processing fluidity, but also meet the processing requirements of various molded parts, and has high gloss and significantly improved polycarbonate. The surface quality of the composition.
  • PC has a molecular weight of 24,000 (Mitsubishi, Japan);
  • the graft copolymer used in the present invention is graft copolymer used in the present invention:
  • ABS emulsion polymerization method particle size 0.05um-0.2um, wherein the butadiene rubber polymer weight fraction in ABS is 25wt%, 757 (Taiwan Chi Mei);
  • BDP bisphenol A-bis(diphenyl phosphate) CR741 (Japan Big Eight);
  • the calcium-containing compounds used in the present invention are all commercially available:
  • PEP-36 bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate
  • Anti-drip agent PTFE (polytetrafluoroethylene) micro powder, Daikin
  • Colorant carbon black M717, Cabot.
  • Calcium content test method Weigh 200mg polycarbonate composition sample (accurate to 0.1mg) into a 50ml volumetric flask, add 5ml nitric acid, 0.1-1ml hydrogen peroxide, add water to the specified scale, cover the cap Dissolve in a microwave oven, open the cap, cool to room temperature, add 4ml of HCL solution, cover the cap, put it into the microwave for secondary digestion, then cool to room temperature, filter, take 1ml of digestion solution through ICP-MS of Agilent Tcechnologies 700series The mixed standard method was tested, and finally the calcium content in the composition was measured, and the detection limit was 2 ppm.
  • the polycarbonate composition was injection molded into a square plate having a thickness of 2 mm, a length of 100 mm and a width of 100 mm at 275 ° C, and the temperature was adjusted at 23 ° C for 48 hours, and then according to the test method of D3964.
  • the gloss meter arbitrarily measure 3 times in the square plate of 100mm*100mm*2mm, read the test value, and record, if any one of the 3 times is less than 80°, it will be unqualified, and the rest will be tested according to the test value. The real average is recorded, and the larger the test value, the higher the Guanze degree.
  • Test method for impact strength ASTM D256 notched impact test.
  • MI test method Take 5g of the composition particles, bake in a constant temperature oven for 8h at 80 ° C, and put it into the melter for testing. The thermal residence time is 600s and the weight is 2.16kg. It is cut every 10s and cut a total of 6 times. The weight is weighed in the analytical balance and converted by ISO1133. The average value of 6 times is the final MI value. .
  • the calcium-containing compound and the hydroxysiloxane are formulated into a hydroxysiloxane suspension having a mass fraction of 12.5 ppm to 2000 ppm; the hydroxysiloxane suspension is blended with the polycarbonate in a high-mixer to obtain a pre-preparation Treated polycarbonate; according to the formulation of Table 1, the pretreated polycarbonate, graft copolymer, flame retardant, mineral filler, other additives are weighed in proportion, and then blended by high mixer or mixer , extrusion, water cooling, granulation to obtain columnar granules of polycarbonate composition; the gloss of the polycarbonate composition was tested, and the data is shown in Table 1.

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Abstract

一种聚碳酸酯组合物及其制备方法，按重量份计，包括以下组份： 30份-80份的聚碳酸酯； 0份-50份的接枝共聚物； 1份-30份的阻燃剂； 1份-50份的矿物填料；其中，基于聚碳酸酯组合物的总重量，钙元素的重量含量为50ppm-300ppm。通过在聚碳酸酯组合物中添加具有较低可溶性钙含量的含钙化合物以及减少或者避免其它含钙化合物的加入，将聚碳酸酯组合物中钙元素的含量控制在50-300ppm范围内，可以使制得的聚碳酸酯组合物不仅具有较高的冲击强度和较好的加工流动性满足各种成型制件的加工需求，且具有较高的光泽度，明显改善了聚碳酸酯组合物的表面质量。

Description

[根据细则37.2由ISA制定的发明名称]　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；
本发明人经过大量实验惊讶地发现，在聚碳酸酯组合物中，通过添加具有较低可溶性钙含量的含钙化合物以及减少或者避免其它含钙化合物的加入，将聚碳酸酯组合物中钙元素的含量控制在50-300ppm范围内，可以使制得的聚碳酸酯组合物不仅具有较高的冲击强度和较好的加工流动性满足各种成型制件的加工需求，且具有较高的光泽度，明显改善了聚碳酸酯组合物的表面质量。
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高光泽度、明显改善表面质量的聚碳酸酯组合物。
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，包括以下组份：
30份-80份的聚碳酸酯；
0份-50份的接枝共聚物；
1份-30份的阻燃剂；
1份-50份的矿物填料；
其中，基于聚碳酸酯组合物的总重量，钙元素的重量含量为50ppm-300ppm。
所述钙元素的重量含量采用如下方法测定：称取聚碳酸酯组合物200mg样品(精确 到0.1mg)到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解，打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700series的ICP-MS混标法进行测试，最后测出聚碳酸酯组合物中的钙元素含量，检出限为2ppm。
本发明经过研究发现，在聚碳酸酯组合物中通过添加具有较低可溶性钙含量的含钙化合物，以及减少或者避免其它含钙化合物的加入，并将聚碳酸酯组合物中钙元素的含量控制在50ppm-300ppm范围内，由于含钙化合物自身有一定的pH，在注塑过程中可以稳定体系中的杂质对聚碳酸酯聚合物降解的隐患，可以使制得的聚碳酸酯组合物具有较高的光泽度，可明显改善聚碳酸酯组合物的表面质量。当钙元素的含量高于300ppm时，体系会偏碱性，在碱性的环境下，聚碳酸酯树脂会发生断链，导致制件光泽度下降，表面出现气痕水花等缺陷，无法为良好的外观提供质量保证，当钙元素的含量低于50ppm时，平衡作用不明显，体系偏酸性，酯类聚合物也会在酸性条件下通过热和剪切的外力诱导加剧降解反应发生，表面质量下降，光泽度下降。
优选的，基于聚碳酸酯组合物的总重量，钙元素的重量含量为80ppm-250ppm，更优选为100ppm-200ppm。
其中，所述钙元素来源于含钙化合物，所述含钙化合物选自60℃纯净水中的pH值不大于8的含钙的化合物，如钙的卤化物如氯化钙等，钙的磺化物如硫酸钙，磺酸钙等，钙的有机络合物等。含钙化合物的添加量以使聚碳酸酯组合物中钙元素的含量为50ppm-300ppm范围内为宜。
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，粘均分子量通过粘度法测试：以二氯甲烷作为溶剂，测试温度为25℃。
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。
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。
所述矿物填料，具体可以为滑石粉、高岭土、黏土、晶须、硅藻土等等，矿物填料可以是不进行任何表面处理的，也可以是涂覆处理的，例如烷基表面包覆，环氧表面处理， 酰胺表面处理，羟基硅油，烷基硅烷，甲氧基硅烷，磺酸基等处理。
根据不同的用途需要，本发明的聚碳酸酯组合物中还可以包含0-20重量份的其它助剂，如选自稳定剂、抗滴落剂、润滑剂、脱模剂、增塑剂、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，季戊四醇双磷酸酯(如双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)，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。
合适的抗滴落剂为优选为氟化聚烯烃，如聚四氟乙烯。
合适的增塑剂为邻苯二甲酸酯。
所述润滑剂为乙撑双硬脂酰胺EBS、芥酸酰胺、硬脂酸锌、硅油、PETS中的一种或者两种及以上的混合物。
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，如炭黑等。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)将含钙化合物与羟基硅氧烷配成质量分数为12.5ppm-2000ppm的羟基硅氧烷悬浊液；
2)将羟基硅氧烷悬浊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、矿物填料、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。
本发明与现有技术相比，具有如下有益效果：
本发明在聚碳酸酯组合物中，通过添加具有较低可溶性钙含量的含钙化合物以及减少或者避免其它含钙化合物的加入，将聚碳酸酯组合物中钙元素的含量控制在50-300ppm范围内，可以使制得的聚碳酸酯组合物不仅具有较高的冲击强度和较好的加工流动性满足各种成型制件的加工需求，且具有较高的光泽度，明显改善了聚碳酸酯组合物的表面质量。
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。
本发明中使用的聚碳酸酯：
PC 粘分子量为24000(日本三菱)；
本发明中使用的接枝共聚物：
ABS 乳液聚合法，粒径0.05um-0.2um，其中丁二烯橡胶质聚合物在ABS中的重量分数为25wt％，757(台湾奇美)；
MBS 粒径0.1um-0.5um，EM500(韩国LG)；
本发明中使用的阻燃剂：
BDP，双酚A-双(磷酸二苯基酯)CR741(日本大八)；
矿物填料：滑石粉H30(林化成)；
本发明中使用的含钙化合物均来源于市购：
氯化钙，60℃纯净水中的pH为5.5；
硫酸钙，60℃纯净水中的pH为5.0；
磺酸钙，60℃纯净水中的pH为4.5；
本发明中使用的其它助剂：
稳定剂：PEP-36(双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)；
润滑剂：PETS，龙沙；
抗滴落剂：PTFE(聚四氟乙烯)微粉，大金
着色剂：炭黑M717，卡博特。
各性能的测试标准或方法：
钙元素含量的测试方法：称取200mg聚碳酸酯组合物样品(精确到0.1mg)到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解，打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700series的ICP-MS混标法进行测试，最后测出组合物中的钙元素含量，检出限为2ppm。
光泽度的测定方法：在275℃将聚碳酸酯组合物进行注塑成厚度为2mm，长度为100mm以及宽度为100mm的方形板块，室温23℃，湿度50％调节48h后，按照D3964的测试方法，通过光泽度仪，在100mm*100mm*2mm的方板中任意测3次，读取测试值，并记录，如果3次中有任意1次光泽度小于80°，则不合格，其余按照测试值真实平均值进行记录，测试值越大，表明关泽度越高。
冲击强度的测试方法：ASTM D256缺口冲击测试。
MI的测试方法：取5g组合物粒子，在80℃恒温烘箱烘烤8h后，放入熔指仪中测试， 热停留时间为600s后加上砝码2.16kg，每隔10s剪取一次，一共剪取6次，在分析天平中称量质量，并通过ISO1133进行换算，求6次平均值为最终MI值记录。
实施例1-16及对比例1-2：聚碳酸酯组合物的制备
将含钙化合物与羟基硅氧烷配成质量分数为12.5ppm-2000ppm的羟基硅氧烷悬浊液；将羟基硅氧烷悬浊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、矿物填料、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光泽度进行测试，数据见表1。
表1 实施例1-16及对比例1-2的具体配比(重量份)及其测试性能结果
Figure PCTCN2017107746-appb-000001
续表1：
Figure PCTCN2017107746-appb-000002
从表1的实施例和对比例的比较可以看出：通过在聚碳酸酯组合物中添加具有较低可溶性钙含量的含钙化合物，将聚碳酸酯组合物中钙元素的含量控制在50-300ppm范围内，可以使制得的聚碳酸酯组合物不仅具有较高的冲击强度和较好的加工流动性满足各种成型制件的加工需求，且具有较高的光泽度，明显改善了聚碳酸酯组合物的表面质量，对比例1-2中，聚碳酸酯组合物中钙元素的含量低于50ppm或高于300ppm时，聚碳酸酯组合物的冲击强度、加工流动性及光泽度均较差。

Claims (12)

  1. 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组份：
    30份-80份的聚碳酸酯；
    0份-50份的接枝共聚物；
    1份-30份的阻燃剂；
    1份-50份的矿物填料。
  2. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，基于聚碳酸酯组合物的总重量，钙元素的重量含量为50ppm-300ppm。
  3. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述钙元素的重量含量采用如下方法测定：称取200mg聚碳酸酯组合物样品,精确到0.1mg,到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解,打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700 series的ICP-MS混标法进行测试，最后测出聚碳酸酯组合物中的钙元素含量，检出限为2ppm。
  4. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，基于聚碳酸酯复合材料的总重量，钙元素的重量含量为80ppm-250ppm，优选为100ppm-200ppm。
  5. 根据权利要求1-4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几种；优选为芳香族聚碳酸酯。
  6. 根据权利要求5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，粘均分子量通过粘度法测试：以二氯甲烷作为溶剂，测试温度为25℃，优选为粘均分子量16000-28000的芳香族聚碳酸酯。
  7. 根据权利要求1-4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。
  8. 根据权利要求1-4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。
  9. 根据权利要求8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。
  10. 根据权利要求2-4任一项所述的聚碳酸酯组合物，其特征在于，所述钙元素来源于含钙化合物，所述含钙化合物选自60℃纯净水中的pH值不大于8的含钙的化合物，具体选自钙的卤化物、钙的磺化物或钙的有机络合物中的一种或几种。
  11. 根据权利要求1-4任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯组合物还包括0-20重量份其它助剂，所述其它助剂选自稳定剂、抗滴落剂、润滑剂、脱模剂、增塑剂、着色剂的一种或几种。
  12. 根据权利要求1-11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)将含钙化合物与羟基硅氧烷配成质量分数为12.5ppm-2000ppm的羟基硅氧烷悬浊液；
    2)将羟基硅氧烷悬浊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、矿物填料、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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CN109912940B (zh) * 2019-03-15 2021-05-11 广东格瑞纳思薄膜科技有限公司 一种抗划伤低翘曲的透明bopet薄膜及其制备方法
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