CN106084718A - High heat-resistant flame-retardant polycarbonate composition and preparation method thereof - Google Patents

High heat-resistant flame-retardant polycarbonate composition and preparation method thereof Download PDF

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CN106084718A
CN106084718A CN 201610423112 CN201610423112A CN106084718A CN 106084718 A CN106084718 A CN 106084718A CN 201610423112 CN201610423112 CN 201610423112 CN 201610423112 A CN201610423112 A CN 201610423112A CN 106084718 A CN106084718 A CN 106084718A
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polycarbonate
flame retardant
high heat
flame
polycarbonate composition
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CN 201610423112
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董相茂
田征宇
刘贤文
张永
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江苏金发科技新材料有限公司
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention discloses a high heat-resistant flame-retardant polycarbonate composition and a preparation method thereof. The high heat-resistant flame-retardant polycarbonate composition is prepared from, by weight, 70-99 parts of polycarbonate, 0.01-25 parts of phosphate copolycarbonate, 0.01-5 parts of fire retardant and 0-10 parts of other auxiliaries, and the sum of weight proportions of all the components is 100. Compared with the prior art, phosphate copolycarbonate is added into a raw material formula, under the situation that toughness and heat resistance of polycarbonate are not affected, flame retardant rating and flame-retardant stability of the polycarbonate composition can be greatly improved, and the high heat-resistant flame-retardant polycarbonate composition is particularly suitable for occasions which have high operating requirements.

Description

高耐热阻燃聚碳酸酯组合物及其制备方法 High heat flame retardant polycarbonate composition and its preparation method

技术领域 FIELD

[0001] 本发明涉及工程塑料技术领域,尤其涉及一种高耐热阻燃聚碳酸酯组合物及其制备方法。 [0001] The present invention relates to plastics technology, particularly relates to a highly heat-resistant flame retardant polycarbonate composition and its preparation method.

背景技术 Background technique

[0002] 聚碳酸酯PC具有较高的耐冲击性、耐热性、良好的尺寸稳定性、电绝缘性能等特性,当其应用在电子、电器、建筑、办公设备等领域时,通常会对材料的阻燃性能提出特殊要求。 [0002] PC Polycarbonate has high impact resistance, heat resistance, good dimensional stability, electrical insulation properties, when it is applied in the field of electronics, appliances, construction, office equipment, will generally flame resistance of a special request. 聚碳酸酯PC自身具有一定的阻燃性(氧指数为25%),但为了满足某些应用领域对阻燃性的高要求,必须对其进行阻燃改性。 PC Polycarbonate itself has a certain degree of flame resistance (oxygen index of 25%), but in order to meet certain demanding applications of flame retardancy, the flame retardant must be modified.

[0003] 众所周知,芳族磷酸酯阻燃剂的加入能够满足材料阻燃性的高要求,但是它的加入通常会使混合物的分解温度降低,并且常常会腐蚀加工机械,有些还会影响聚碳酸酯树脂的冲击强度和耐热性。 [0003] It is well known that addition of aromatic phosphate flame retardant materials to meet the requirements of high flame retardancy, but it will usually be added to reduce the decomposition temperature of the mixture, and often erosion machining machine, some will affect the polycarbonate ester resin impact strength and heat resistance. 另外,卤系阻燃剂在燃烧过程中会产生二恶英等有毒有害物质,造成环境污染而逐渐被限制使用。 Further, halogen flame in the combustion process will produce dioxin and other toxic substances, causing environmental pollution is gradually restricted. 在工业应用中,二苯基砜有机磺酸金属盐(KSS)和全氟丁烷磺酸钾(PPFBS)也是主流的阻燃剂。 In industrial applications, diphenyl sulfone metal organic sulfonate (KSS) and potassium perfluorobutane sulfonate (PPFBS) is the main flame retardant. 有机磺酸金属盐类的阻燃剂可以在较厚制品(厚度多3.2mm)取得良好的阻燃效果,但在应用于较薄制品时(1.6mm<厚度<3.2mm),由于有机磺酸金属盐阻燃剂添加量通常较小(<1),较难混合均匀等因素影响,有机磺酸金属盐阻燃剂会很难保证比较稳定的阻燃效果。 Organic sulfonic acid metal salts may be flame retardant (1.6mm <thickness <3.2mm), the organic sulfonic acid at thicker article (Multi 3.2mm thickness) to obtain good flame retardant effect, but applied to the thin article effect of the flame retardant metal salt is added in an amount generally small (<1), is difficult to uniformly mix and other factors, organic sulfonic acid metal salt flame retardants is difficult to ensure a more stable flame retardant effect. 然而在实际应用中,制品超薄、耐热是市场需求的发展方向。 In practice, however, the ultra-thin products, heat is the development direction of the market demand. 因此,上述两种阻燃剂的应用受到了极大的限制。 Thus, the two flame retardants application has been severely limited.

[0004] 中国专利CN104403293公开了一种无卤阻燃聚碳酸酯的方法,采先将聚碳酸酯PC、 阻燃剂、抗氧剂、润滑剂共混、造粒制成阻燃母粒,再将阻燃母粒与其余组分进行挤出造粒制成最终产品,通过阻燃母粒提高微量阻燃剂分散效果的方法来保证产品稳定性,且阻燃级别可做到1.6mmV-0,但是这种"先制阻燃母粒,再制最终产品"的方法操作麻烦,并且还增加了生产成本,从而对其广泛应用产生了一定的局限。 [0004] Chinese patent CN104403293 discloses a process for the halogen-free flame retardant polycarbonate, Cai first polycarbonate PC, flame retardants, antioxidants, lubricants blended, flame retardant masterbatch pelletization, the method then subjected to extrusion pelletization retardant masterbatch with the remaining components of the final product, to improve the dispersion effect of the micro flame retardant masterbatch to ensure product stability and flame retardancy level can be achieved 1.6mmV- 0, but this "preemptive retardant masterbatch, and then made the final product" approach to operational problems, and also increased the cost of production, resulting in some limitations to its widespread use.

[0005] 有鉴于此,特提出本发明。 [0005] In view of this, the present invention proposed Japanese.

发明内容 SUMMARY

[0006] 为了克服上述缺陷,本发明提供了一种高耐热阻燃聚碳酸酯组合物及其制备方法,该制备方法简单、操作安全,并且经该制备方法制得的聚碳酸酯组合物具有优异的韧性、耐热性、薄壁阻燃等级及阻燃稳定性,特别适用于使用环境要求比较高的场合。 [0006] In order to overcome the above drawbacks, the present invention provides a flame retardant polycarbonate composition of high heat resistance and its preparation method, the preparation method is simple, safe operation, and obtained by the production method of the polycarbonate composition It has excellent toughness, heat resistance, thin-wall flame retardant grades and stability, especially suitable for use where environmental requirements are relatively high.

[0007] 本发明为了解决其技术问题所采用的技术方案是:一种高耐热阻燃聚碳酸酯组合物,按重量份计,具有如下原料配方:聚碳酸酯70~99份、磷酸共聚碳酸酯0.01~25份、阻燃剂0.01~5份、其它助剂0~10份;且各组分的重量份之和为100份。 [0007] aspect of the present invention is to solve the technical problem is that: a high-heat-resistant flame retardant polycarbonate composition, in parts by weight, the raw material having the following formulation: 70 to 99 parts of polycarbonate, copolymer acid 0.01 to 25 parts carbonate, 0.01 to 5 parts of flame retardant, other additives 0 to 10 parts; parts by weight and the sum of the components is 100 parts.

[0008] 作为本发明的进一步改进,所述聚碳酸酯选自通过界面聚合法、熔融酯交换法、吡啶法、环状碳酸酯化合物的开环聚合法、预聚物的固相酯交换法制备的聚碳酸酯中的至少一种。 [0008] As a further improvement of the present invention, the polycarbonate is selected by interfacial polymerization, ring-opening polymerization melt transesterification method, a pyridine method, a cyclic carbonate compound method, a solid phase transesterification method of prepolymers at least one polycarbonate in the prepared.

[0009] 作为本发明的进一步改进,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、支化聚碳酸酯中的至少一种。 [0009] As a further improvement of the present invention, the polycarbonate is selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic - aliphatic polycarbonate, at least one branched polycarbonate.

[0010] 作为本发明的进一步改进,所述聚碳酸酯选用粘均分子量为13000~40000的芳香族聚碳酸酯。 [0010] As a further improvement of the present invention, the selection of viscosity average molecular weight polycarbonate aromatic polycarbonate is 13,000 to 40,000.

[0011] 作为本发明的进一步改进,所述聚碳酸酯选用粘均分子量为17000~24000的芳香族聚碳酸酯。 [0011] As a further improvement of the present invention, the selection of viscosity average molecular weight polycarbonate aromatic polycarbonate is 17,000 to 24,000.

[0012] 作为本发明的进一步改进,所述磷酸共聚碳酸酯选用重均分子量为50000~70000 的磷酸酯-碳酸酯共聚物。 [0012] As a further improvement of the present invention, the phosphoric acid selected copolycarbonate weight average molecular weight of 50,000 to 70,000 in phosphate - carbonate copolymer.

[0013] 作为本发明的进一步改进,所述阻燃剂选自含氮阻燃剂、含磷阻燃剂、有机磺酸金属盐阻燃剂中的至少一种; [0013] As a further improvement of the present invention, the flame retardant is selected from nitrogen containing flame retardants, phosphorus flame retardant, at least one organic sulfonic acid metal salt flame retarder;

[0014] 或者,所述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、溴化芳香族交联聚合物中的至少一种。 [0014] Alternatively, the flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene - maleic anhydride copolymer, a brominated epoxy resin , brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, full-bromo tricyclic pentadecane, at least one brominated aromatic crosslinked polymer.

[0015] 作为本发明的进一步改进,所述阻燃剂选用为有机磺酸金属盐阻燃剂,且所述有机磺酸金属盐阻燃剂为二苯基砜有机磺酸金属盐、全氟丁烷磺酸钾、全苯基丁烷磺酸钾中的至少一种。 [0015] As a further improvement of the invention, the choice of the flame retardant is an organic sulfonic acid metal salt flame retardant, and said flame retardant is an organic sulfonic acid metal salt of organic sulfonic acid metal salt of diphenyl sulfone, perfluoro butane sulfonic acid potassium, at least one full-diphenyl butane sulfonic acid potassium in.

[0016] 作为本发明的进一步改进,所述其它助剂选自热稳定剂、抗氧剂、抗滴落剂、光稳定剂、增塑剂、填料、着色剂中的至少一种。 [0016] As a further improvement of the present invention, at least one of the other additives selected from heat stabilizers, antioxidants, anti-drip agents, light stabilizers, plasticizers, fillers, colorants.

[0017] 本发明还提供了一种制备所述高耐热阻燃聚碳酸酯组合物的制备方法,包括以下制备步骤:首先,称取配方量的聚碳酸酯、磷酸共聚碳酸酯、阻燃剂和其它助剂,并皆投入到混合机中进行共混,混合均匀后再投入至双螺杆挤出机中进行熔融混合,并挤出造粒,得到所述高耐热阻燃聚碳酸酯组合物;其中,所述双螺杆挤出机的螺杆直径为40:1,各段螺筒温度设置为250~260°C,螺杆转速为400~500rpm。 [0017] The present invention also provides a preparation method for preparing the high heat of the flame retardant polycarbonate composition, comprising the following production steps: First, the formulation weighed amount of the polycarbonate, copolycarbonates phosphate, flame retardant and other auxiliary agents, and are put into a mixer for mixing melt blending, mixing uniformly and then put into a twin-screw extruder, extruded and pelletized, to obtain the high heat flame retardant polycarbonate composition; wherein said twin-screw extruder having a screw diameter of 40: 1, barrel temperature of each section is set to 250 ~ 260 ° C, a screw speed of 400 ~ 500rpm.

[0018] 本发明的有益效果是:相较于现有技术,本发明于原料配方中加入了磷酸酯共聚碳酸酯,该磷酸酯共聚碳酸酯与有机磺酸盐阻燃剂复配使用后,可极大地提高有机磺酸盐阻燃性能的发挥,从而使聚碳酸酯组合物具有极佳的薄壁阻燃等级和阻燃稳定性;此外,由于磷酸共聚碳酸酯为高分子聚合物,其与聚碳酸酯的相容性极好,不会影响聚碳酸酯组合物的韧性和冲击强度,且对聚碳酸酯的耐热性影响很小;而且磷酸共聚碳酸酯在体系中的流动性相对较好,有利于有机磺酸金属盐的均匀分散;因此,本发明通过在原料配方中加入磷酸酯共聚碳酸酯,能够实现在不影响聚碳酸酯韧性和耐热性的情况下,还极大的提高了聚碳酸酯组合物的阻燃等级和阻燃稳定性,特别适用于使用环境要求比较高的场合。 [0018] Advantageous effects of the present invention are: compared to the prior art, the present invention is added to the feed formulation phosphate copolycarbonate, copolycarbonate after use of the phosphate salt with the organic flame retardant compound, can greatly improve flame retardant properties of organic sulfonates play, so that the polycarbonate composition has excellent thin-wall flame retardant levels and stability; in addition, since phosphoric acid co-polymer of polycarbonate, with poly excellent compatibility carbonate, does not affect the toughness and impact strength of the polycarbonate composition, and has little effect on the heat resistance of the polycarbonate; and copolycarbonates flowability phosphate system is relatively good , to facilitate uniform dispersion of the organic sulfonic acid metal salt; therefore, the present invention is by the addition of phosphate in feed formulations copolycarbonate, can be achieved without affecting the toughness and heat resistance of the polycarbonate, but also greatly improved level and stability of the flame retardant polycarbonate compositions, particularly suitable for use where environmental requirements are relatively high.

具体实施方式 Detailed ways

[0019] 下面结合具体的实施例对本发明做进一步详细说明,但本发明不限于这些实施例。 [0019] The following embodiments with reference to specific embodiments of the present invention is described in further detail, but the present invention is not limited to these embodiments.

[0020] 众所周知,选材用料、原料配方、制备工艺是决定产品品质的三大要素,三者互为影响。 [0020] As we all know, selection of materials, raw material formulation, preparation technology are the three factors determine the quality of the product, three affect each other. 因而,为了更好地说明本发明所得高耐热阻燃聚碳酸酯组合物产品的优点及创新性, 以下将对本发明所得高耐热阻燃聚碳酸酯组合物产品的选材用料、原料配方和制备方法进行详细说明。 Accordingly, in order to better illustrate the advantages of the present invention and the innovative high heat resulting flame retardant polycarbonate composition of the product obtained according to the present invention will hereinafter flame retardant polycarbonate compositions of high heat resistant product selection of materials, the raw material formulation and methods of preparation described in detail.

[0021] (1)本发明的选材用料情况: [0021] (1) the selection of materials of the present invention:

[0022] 本发明公开了一种高耐热阻燃聚碳酸酯组合物,其所用原材料主要包括有聚碳酸酯、磷酸共聚碳酸酯、阻燃剂、以及其它助剂,各原材料的选材情况说明如下: [0022] The present invention discloses a flame retardant polycarbonate composition of high heat resistance, its main raw materials include polycarbonates, copolycarbonates phosphoric acid, flame retardants, and other additives, where the selection of each material description as follows:

[0023] (la)聚碳酸酯:在本发明中,所述聚碳酸酯选自通过界面聚合法、熔融酯交换法、 吡啶法、环状碳酸酯化合物的开环聚合法、预聚物的固相酯交换法制备的聚碳酸酯中的至少一种。 [0023] (la) Polycarbonate: In the present invention, the polycarbonate is selected from the interfacial polymerization method, melt ester exchange method, a pyridine method, a ring-opening polymerization of cyclic carbonate compound method, the prepolymer at least one polycarbonate prepared by a solid phase transesterification in. 下面将详细说明其特别优选的方法: The following will explain in detail a method which is particularly preferred:

[0024] 首先,对通过界面聚合法来制备聚碳酸酯树脂的制备方法进行说明:在界面聚合法中,先使二羟基化合物和碳酸酯前体在惰性有机溶剂和碱水溶液的存在下反应同时通常维持pH为9以上,然后再在聚合催化剂的存在下进行界面聚合,从而获得聚碳酸酯树脂;分子量调节剂(链终止剂)、以及防止二羟基化合物氧化的抗氧剂也可以按需要存在于反应体系中。 [0024] First, prepared by an interfacial polymerization method of preparing a polycarbonate resin will be described: In the interfacial polymerization, the first dihydroxy compound and a carbonate precursor in the presence of an organic reaction while the aqueous alkali solution and an inert solvent generally maintained at a pH of 9 or more, and then interfacial polymerization in the presence of a polymerization catalyst, thereby obtaining a polycarbonate resin; molecular weight modifier (chain terminator), and to prevent the oxidation of the dihydroxy compound antioxidants can also be present as needed in the reaction system.

[0025] 此外,在上述采用界面聚合法来制备聚碳酸酯树脂的工艺中,所述碳酸酯前体可优选为光气,且使用光气的这种方法还特别称为光气法。 [0025] Further, in the interfacial polymerization process to prepare the polycarbonate resin employed in the above, the carbonate precursor may preferably phosgene, phosgene and using this method is also particularly called phosgene method. 所述惰性有机溶剂可优选为氯代烃,例如二氯甲烷、1,2_二氯乙烷、氯仿、单氯苯、二氯苯中的;和芳香族烃,例如苯、甲苯和二甲苯。 The inert organic solvent may preferably be chlorinated hydrocarbons, such as dichloromethane, 1,2_ dichloroethane, chloroform, monochlorobenzene, dichlorobenzene; and aromatic hydrocarbons such as benzene, toluene and xylene . 且在实际操作中,所述惰性有机溶剂可以使用一种有机溶剂,或者可以以期望的组合和比例一起使用其两种以上。 And, in practice, the inert organic solvent is an organic solvent may be used, or two or more types thereof may be used together in a desired combination and ratio.

[0026] 所述碱水溶液中包含的碱化合物的实例可包括:碱金属化合物,例如氢氧化钠、氢氧化钾、氢氧化锂和碳酸氢钠(其中氢氧化钠和氢氧化钾是优选的);以及碱土金属化合物。 [0026] Examples of the alkaline compound contained in the aqueous alkali solution may include: alkali metal compounds, such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium bicarbonate (wherein sodium and potassium are preferred) ; and alkaline earth metal compounds. 且在实际操作中,可以使用一种碱化合物,或者可以以期望的组合和比例一起使用其两种以上。 And, in practice, an alkali compound may be used, or two or more types thereof may be used together in a desired combination and ratio. 虽然碱水溶液中的碱化合物的浓度在这里不受限制,但通常将碱化合物的浓度优控在5wt % -1 Owt %,以控制反应期间中的碱水溶液的pH为10-12。 Although the concentration of the alkali compound in the aqueous alkaline solution is not limited herein, but typically the concentration of the alkaline compound is preferably controlled in 5wt% -1 Owt%, a pH in the aqueous alkaline solution during the reaction is controlled 10-12. 另外当光气鼓泡时,双酚化合物与碱化合物的摩尔比通常设定为1:1.9以上、且1:3.2以下(进一步优选为1:2.0以上、 且1:2.5以下),从而控制水相的pH为10-12(优选为10-11)。 When the addition was bubbled phosgene, the molar ratio of a bisphenol compound with a base compound is usually set to 1: 1.9 or more, and 1: 3.2 or less (more preferably 1: 2.0 or more, and 1: 2.5 or less), so as to control water phase has a pH of 10-12 (preferably 10-11).

[0027]所述聚合催化剂的实例包括:脂肪族叔胺,例如三甲胺、三乙胺、三丁胺、三丙胺和三己胺等;脂环族叔胺,例如N,N'_二甲基环己胺和N,N'_二乙基环己胺等;芳香族叔胺,例如N,N'_二甲基苯胺和N,N'_二乙基苯胺等;季铵盐,例如三甲基苄基氯化铵、四甲基氯化铵和三乙基苄基氯化铵等;吡啶;鸟嘌呤;和胍盐等。 [0027] Examples of the polymerization catalyst include: aliphatic tertiary amines, such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and the like; alicyclic tertiary amines such as N, N'_ dimethyl cyclohexyl amine and N, N'_ diethyl cyclohexylamine; aromatic tertiary amines such as N, N'_-dimethylaniline and N, N'_ diethylaniline and the like; quaternary ammonium salts, e.g. trimethyl benzyl ammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride and the like; pyridine; guanine; and guanidine salts. 在实际操作中,可以使用一种聚合催化剂,或者可以以期望的组合和比例一起使用其两种以上。 In practice, a polymerization catalyst may be used, or two or more types thereof may be used together in a desired combination and ratio.

[0028] 所述分子量调节剂的实例包括:具有一价酚式羟基的芳香族酚;脂肪族醇,例如甲醇和丁醇等;硫醇;和邻苯二甲酰亚胺类;等等,并且上述材料中,优选用芳香族酚,且所述芳香族酚的具体实例包括:烷基取代的酚,例如间甲基苯酚、对甲基苯酚、间丙基苯酚、对丙基苯酚、对叔丁基苯酚和对-长链烷基取代的苯酚等;含乙烯基的酚,例如异丙烯基苯酚;含环氧基的酚;和含羧基的酚,例如邻羟基苯甲酸和2-甲基-6-羟基苯基乙酸等。 [0028] Examples of the molecular weight modifier include: phenol having an aromatic monovalent phenolic hydroxyl group; aliphatic alcohols, such as methanol and butanol and the like; mercaptan; phthalimide and the like; and the like, and the above materials, specific examples of preferably used aromatic phenol, and the aromatic phenols include: alkyl-substituted phenols, such as m-cresol, p-methyl phenol, m-propyl phenol, p-propyl phenol, and p-t-butylphenol - long-chain alkyl-substituted phenols and the like; vinyl-containing phenols such as isopropenylphenol; epoxy group-containing phenol; and a carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl acid-6-hydroxyphenyl and the like. 在实际操作中,可以使用一种分子量调节剂,或者可以以期望的组合和比例一起使用其两种以上。 In practice, molecular weight modifier may be used, or two or more types thereof may be used together in a desired combination and ratio. 另外,所述分子量调节剂的用量通常相对于每100摩尔二羟基化合物为0.5摩尔以上、且50摩尔以下,进一步优选为1摩尔以上、且30摩尔以下;设定分子量调节剂的用量至该范围内可以改进聚碳酸酯树脂组合物的热稳定性和耐水解性。 Further, the molecular weight adjusting agent usually used in an amount per 100 mole of the dihydroxy compound is 0.5 mol or more, and 50 mol or less, more preferably 1 mol or more, and 30 mol; molecular weight modifier in an amount set to this range the polycarbonate resin composition can be improved in thermal stability and hydrolysis resistance.

[0029] 反应基质、反应介质、催化剂和添加剂等可以在反应期间以任意期望的顺序混合在一起,只要可以获得期望的聚碳酸酯树脂即可,并且可以按需要建立适合的顺序。 [0029] The reaction substrate, reaction medium, catalyst and additives may be mixed in any desired sequence together during the reaction, as long as the polycarbonate resin to obtain a desired, suitable order and may be established as needed. 例如, 当光气用作碳酸酯前体时,分子量调节剂可以在二羟基化合物与光气的反应(光气化)时和在聚合反应开始时之间的任意期望的时机添加。 For example, when the front phosgene is used as carbonate precursor, molecular weight modifier can be the reaction of the dihydroxy compound with phosgene (phosgenation) and added to the polymerization at any desired time between the start of the reaction. 反应温度通常设定为0~40°C,反应时间通常在几分钟(如lOmin)至几小时(如6h)的范围内。 The reaction temperature is generally set at 0 ~ 40 ° C, the reaction time is usually in the range of several minutes (lOmin) to several hours (e.g., 6h) of.

[0030]接下来,对通过熔融酯交换法来制备聚碳酸酯树脂的制造方法进行说明:在熔融酯交换法中,例如为酯交换反应在碳酸二酯和二羟基化合物之间进行。 [0030] Next, a manufacturing method for preparing polycarbonate resin by the melt transesterification method will be described: In the melt transesterification method, the reaction is carried out, for example, between a carbonic acid diester and the dihydroxy compound transesterification. 其中,碳酸二酯的实例包括:碳酸二烷基酯化合物,例如碳酸二甲酯、碳酸二乙酯和碳酸二叔丁酯;碳酸二苯酯; 和取代的碳酸二苯酯,例如碳酸二甲苯酯等。 Wherein examples of carbonic diesters include: dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and di-tert-butyl carbonate; diphenyl carbonate; and substituted diphenyl carbonates such as ditolyl esters and the like. 在上述材料中,碳酸二苯酯和取代的碳酸二苯酯是优选的,特别优选用碳酸二苯酯。 In the above-described materials, diphenyl carbonate and substituted diphenyl carbonate are preferred, with diphenyl carbonate is particularly preferred. 另外在实际操作中,可以使用一种碳酸二酯,或者可以以期望的组合和比例一起使用其两种以上。 Also in practice, the carbonic acid diester may be used, or two or more types thereof may be used together in a desired combination and ratio.

[0031 ]为获得目标聚碳酸酯树脂,可以使用期望比例的二羟基化合物与碳酸二酯,但是相对于每1摩尔二羟基化合物,使用1摩尔当量以上、且1.30摩尔当量以下的碳酸二酯是优选的,并且碳酸二酯的用量可进一步优选为1.01摩尔当量以上且1.30摩尔当量以下。 [0031] The polycarbonate resin to obtain the target, the desired ratio may be used a dihydroxy compound with a carbonic diester, but per 1 mole of the dihydroxy compound, using 1 molar equivalent or more, and 1.30 molar equivalents of carbonic acid diester is preferably, the amount of the carbonic acid diester and further preferably 1.01 molar equivalent and 1.30 molar equivalents. 末端羟基的量可以通过设定两种化合物的比例在上述范围内而调节至优选的范围。 The amount of terminal hydroxyl groups can be adjusted to a preferred range by setting the ratio of the two compounds in the above range.

[0032] 聚碳酸酯树脂中末端羟基的量倾向于极大影响热稳定性、耐水解性和色调等。 [0032] The polycarbonate resin in an amount of terminal hydroxyl groups tend to significantly affect the thermal stability, hydrolysis resistance and color tone. 因此,末端羟基的量可以通过任意公知的期望方法并根据需要来调节。 Thus, the amount of terminal hydroxyl groups and may be adjusted by any known method desired needs. 在酯交换反应中,调节末端羟基的量的聚碳酸酯树脂通常可以通过在反应期间调节碳酸二酯和芳香族二羟基化合物之间的混合比、及压力减小的程度等来获得。 In the transesterification reaction, adjusting the amount of the terminal hydroxyl groups of the polycarbonate resin generally be prepared by adjusting the degree of reduced pressure and the mixing ratio between the carbonic diester and the aromatic dihydroxy compound obtained during the reaction. 另外,所得聚碳酸酯树脂的分子量通常也可以通过该过程来调节。 Further, the molecular weight of the obtained polycarbonate resin usually may be adjusted by the process. 端羟基的量还可以通过在反应期间单独地添加链终止剂的方法作为更有效地调节方法,所述链终止剂的实例包括:单价酚、单价羧酸和碳酸二酯等,可以使用一种链终止剂,或者可以以期望的组合和比例一起使用其两种以上。 The amount of terminal hydroxyl group may also be a method by adding a chain terminating agent is more effective as a method of individually adjusting during the reaction, examples of chain terminators include: monovalent phenols, monovalent carboxylic acids and carbonic acid esters and the like, may be used chain terminators, or two or more types thereof may be used together in a desired combination and ratio.

[0033] 当通过熔融酯交换法生产聚碳酸酯树脂时,通常使用酯交换催化剂,可以使用任意期望的酯交换催化剂,当然碱金属化合物和/或碱土金属化合物的使用是优选的。 [0033] When producing a polycarbonate by the melt ester-exchange resin method, a transesterification catalyst is generally used, it may be any desired transesterification catalysts, of course, and an alkali metal compound and / or alkaline earth metal compound are preferable. 此外, 作为辅助化合物,可以使用碱性化合物,如碱性硼化合物、碱性磷化合物、碱性铵化合物和碱性胺化合物等。 Further, as an auxiliary compound, a basic compound may be used, such as a basic boron compound, basic phosphorus compound, basic ammonium compound and a basic amine compound. 可以使用一种酯交换催化剂,或者可以以期望的组合和比例一起使用其两种以上。 Transesterification catalyst may be used, or two or more types thereof may be used together in a desired combination and ratio. 熔融酯交换法中的反应温度通常为l〇〇°C~320°C,反应通常在2mmHg以下的减压下进行;详细过程应该为其中熔融缩聚反应在上述条件下进行、同时除去副产物如芳香族羟基化合物等的过程。 The reaction temperature in the melt transesterification process is generally l〇〇 ° C ~ 320 ° C, the reaction is usually carried out under reduced pressure 2mmHg or less; detailed process in which melt polycondensation reaction should be carried out under the above conditions, while removing by-products such as process aromatic hydroxy compound or the like.

[0034] 熔融缩聚反应可以通过分批法或连续法来进行。 [0034] The melt polycondensation reaction may be carried out by a batch process or a continuous process. 当进行分批法时,反应基质、反应介质、催化剂和添加剂等可以任意期望的顺序混合在一起,只要可以获得目标芳香族聚碳酸酯树脂即可,并且可以按需要建立适合的顺序。 When a batch process, can be mixed together in any desired order reaction substrate, reaction medium, catalyst, and additives, as long as certain aromatic polycarbonate resin can be obtained, and may establish a suitable order as desired. 然而,考虑到例如聚碳酸酯和聚碳酸酯树脂组合物的稳定性,通过连续过程进行熔融缩聚是优选的。 However, in view of stability such as polycarbonate and polycarbonate resin composition, the melt polycondensation is preferably carried out by a continuous process. 催化剂失活剂可以在熔融酯交换法中根据需要来使用,任意期望的中和酯交换催化剂的化合物可以用作催化剂失活剂, 实例包括含硫有机化合物及其衍生物等;可以使用一种催化剂失活剂,或者可以以期望的组合和比例一起使用其两种以上。 The catalyst deactivator may be used in the melt transesterification method according to the needs, and in any desired compound transesterification catalyst can be used as the catalyst deactivator, a sulfur-containing organic compounds and derivatives thereof Examples include and the like; may be used catalyst deactivator, or two or more types thereof may be used together in a desired combination and ratio. 催化剂失活剂的用量通常相对于酯交换催化剂中包含的碱金属或碱土金属为0.5重量当量以上、且10重量当量以下,进一步优选为1重量当量以上、 且5重量当量以下;另外,其浓度通常相对于芳香族聚碳酸酯树脂为lppm以上、且lOOppm以下,进一步优选为lppm以上、且20ppm以下。 The catalyst deactivator is used in an amount usually the alkali metal or alkaline earth metal transesterification catalyst contained 0.5 weight equivalents or more, and 10 weight equivalents or less, more preferably 1 weight equivalent or more and 5 weight equivalents; Further, the concentration typically the aromatic polycarbonate resin lppm or more, and lOOppm or less, more preferably lppm or more and 20ppm or less.

[0035] 在本发明中,所述聚碳酸酯选自经上述特别优选制备方法制得的芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯中的至少一种;优选的,所述聚碳酸酯选用粘均分子量为13000~40000的芳香族聚碳酸酯,进一步优选的,所述聚碳酸酯选用粘均分子量为17000~24000的芳香族聚碳酸酯,当芳香族聚碳酸酯的粘均分子量为17000~24000时,具有良好的机械强度和优异的成型性。 [0035] In the present invention, the polycarbonate is selected by the above-described particularly preferred method of preparing an aromatic polycarbonate prepared, aliphatic polycarbonates, aromatic - aliphatic polycarbonate, branched polycarbonate at least one; preferably, the viscosity average molecular weight polycarbonate selected aromatic polycarbonate is 13,000 to 40,000, more preferably, the viscosity average molecular weight polycarbonate selection of 17,000 to 24,000 an aromatic poly carbonate, when the aromatic polycarbonate as 24,000 viscosity average molecular weight 17,000 to having good mechanical strength and excellent moldability.

[0036] (lb)磷酸共聚碳酸酯:在制备聚碳酸酯组合物时,若选用重均分子量较小的磷酸共聚碳酸酯,会降低聚碳酸酯组合物的耐热性;而若选用重均分子量较大的磷酸共聚碳酸酯,则会使聚碳酸酯组合物出现诸如降解的相容性和外观不良等问题。 [0036] (lb) phosphate copolycarbonate: When the polycarbonate composition was prepared, if the choice of a smaller weight average molecular weight copolycarbonates phosphate, reduce the heat resistance of the polycarbonate composition; and if the choice of the weight average large molecular weight copolycarbonates phosphate, the polycarbonate composition will occur compatibility issues such as poor appearance and degraded. 本发明通过若干次试验反复验证,优选用重均分子量为50000~70000的磷酸酯-碳酸酯共聚物,能够有效提高高耐热阻燃聚碳酸酯组合物的耐热性、相容性和外观。 The present invention is verified by several repeated tests, preferably with a weight-average molecular weight of 50,000 to 70,000 ester - carbonate copolymers, can improve the heat resistance of the flame retardant polycarbonate compositions of high heat resistance, compatibility, and appearance .

[0037] 本发明所用磷酸酯-碳酸酯共聚物由以下化学式(1)表示的磷酸盐单元与化学式(2)表示的双酸A单元组成; [0037] The present invention is used as a phosphate - carbonate copolymer composed of phosphate units represented by the following formula (1) diacid A unit of formula (2);

[0038] [0038]

Figure CN106084718AD00071

[0039]化学式(1)中,R为含1~10个碳原子的烷基,支链上可包括甲基、乙基、丙基、丁基、 戊基、己基、庚丁基、辛基、壬基和癸基等。 [0039] Chemical Formula (1), R having 1 to 10 carbon atoms may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl on branched butyl, octyl , nonyl, decyl, and the like. 作为优选的烷基,碳原子数为1~8个,更优选碳原子数为1~6个,再进一步优选为具有1~4个碳原子,特别是一个甲基或乙基或丙基,其中甲基和乙基是优选,最优选是甲基。 Preferred examples of the alkyl group carbon atoms of 1 to 8, carbon atoms, more preferably 1 to 6, further preferably having 1 to 4 carbon atoms, especially a methyl or ethyl or propyl group, wherein methyl and ethyl are preferred, most preferably methyl.

[0040] 磷酸酯-碳酸酯共聚物中的磷酸盐单元与碳酸酯单元摩尔比优选为10:90~90: 10,更优选为20:80~80:20,特别优选为30:70~70:30。 [0040] phosphate - carbonate copolymer with carbonate units to phosphate units molar ratio is preferably 10: 90 ~ 90: 10, more preferably 20: 80 ~ 80: 20, particularly preferably 30: 70 to 70 : 30.

[0041] (lc)阻燃剂:在本发明中,所述阻燃剂选自含氮阻燃剂、含磷阻燃剂、有机磺酸金属盐阻燃剂中的至少一种或几种(选自无卤阻燃剂);或者,所述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、溴化芳香族交联聚合物中的至少一种(选自卤系阻燃剂,优选为溴化聚苯乙烯)。 [0041] (lc) Flame Retardant: In the present invention, the flame retardant is selected from nitrogen containing flame retardants, phosphorus flame retardant, at least one or more organic sulfonic acid metal salt flame retarder (halogen-free flame retardant selected); or the flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene - maleic anhydride copolymer It was brominated epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, full-bromo tricyclic pentadecane, aromatic brominated crosslinked polymer at least one (selected from a halogen-based flame retardant, preferably a brominated polystyrene).

[0042] 在实际操作中,所述阻燃剂优选用为有机磺酸金属盐阻燃剂,有机磺酸金属盐阻燃剂的引入可促进聚碳酸酯树脂在燃烧期间碳化层的形成,因而可很好的提高聚碳酸酯的阻燃性,可以以优良的水平维持聚碳酸酯拥有的性质,如电气性质、耐热性、耐冲击性。 [0042] In practice, the flame retardant used is preferably an organic sulfonic acid metal salt flame retardant, an organic sulfonic acid metal salt flame retardant is incorporated may promote the formation of polycarbonate resin during combustion of the char layer, thus is favorably improved flame retardant polycarbonate can be maintained to have excellent properties of the polycarbonate level, such as electrical properties, heat resistance and impact resistance. [0043]对有机磺酸金属盐中的金属没有特别限制,但优选金属如钠、锂、钾或铯,或碱土金属如铍、镁、钙、锶、或钡。 [0043] There are no particular limitations on the metals in metal salts of organic sulfonic acids, but are preferably metals such as sodium, lithium, potassium or cesium, or an alkaline earth metal such as beryllium, magnesium, calcium, strontium, or barium. 但从阻燃性和耐水解性方面考虑,优选钾。 However, flame retardancy and hydrolysis resistance viewpoint, preferably potassium.

[0044]有机磺酸金属盐包括:含氟脂肪族磺酸的金属盐、含氟芳族磺酰亚胺的金属盐、芳族磺酸的金属盐和芳族磺酰胺的金属盐。 [0044] The organic sulfonic acid metal salt include: metal salts and metal salts of aromatic sulfonamides fluorinated aliphatic sulfonic acid, metal salts of fluorine-containing aromatic sulfonimide, aromatic sulfonic acids. 优选为含氟脂肪族磺酸的金属盐和芳族磺酸的金属盐(如二苯基砜有机磺酸金属盐、全苯基丁烷磺酸钾),特别优选含氟脂肪族磺酸的金属盐。 Preferably a fluorine-containing aliphatic sulfonic acid metal salt and metal salts of aromatic sulfonic acids (e.g., diphenyl sulfone metal organic sulfonate, potassium diphenyl butane sulfonate whole), particularly preferably a fluorinated aliphatic sulfonic acid metal salts. 该含氟脂肪族磺酸的金属盐包括:分子中包含至少一个CF键的含氟脂肪族磺酸的碱金属盐,如全氟丁烷磺酸钾、全氟丁烷磺酸锂、全氟丁烷换算铯、三氟甲烷磺酸锂、三氟甲烷磺酸钠、三氟甲烷磺酸钾、五氟乙烷磺酸钾、七氟丙烷磺酸钾、以及十氟-4-(五氟乙基)环己烷磺酸钾等,特别优选为全氟丁烷磺酸钾。 The fluorine-containing aliphatic sulfonic acid metal salt include: alkali metal salt of a fluorine-containing molecule contains at least one aliphatic sulfonic acid CF bond, such as potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, perfluoro butane conversion, cesium, lithium trifluoromethane sulfonate, trifluoromethane sulfonate, potassium trifluoromethane sulfonate, potassium pentafluoroethane sulfonate, potassium heptafluoropropane sulfonate, and ten-fluoro-4- (pentafluoroethyl ) cyclohexanecarboxylic acid potassium, and particularly preferred is potassium perfluorobutane sulfonate.

[0045] (Id)在上述聚碳酸酯树脂与磷酸共聚碳酸酯、阻燃剂混合时,还可以根据需要适当添加其它助剂,所述其它助剂选自热稳定剂、抗氧剂、抗滴落剂、光稳定剂、增塑剂、填料、 着色剂中的至少一种。 [0045] (Id) copolycarbonate in the polycarbonate resin with phosphoric acid, when mixed flame retardant, other additives may also be suitably added as necessary, the other additives selected from heat stabilizers, antioxidants, drip agents, light stabilizers, plasticizers, fillers, at least one coloring agent. 其中, among them,

[0046] 合适的热稳定剂包括: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。 [0046] Suitable heat stabilizers include: organic phosphites such as triphenyl phosphite, tris _ (2,6-dimethylphenyl) phosphite, tris - nonyl phenyl ester, di methylbenzene phosphonate, trimethyl phosphate and the like.

[0047]合适的抗氧剂包括: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、多元醇酯类等。 [0047] Suitable antioxidants include: organic phosphites, alkylated monohydric phenol or polyhydric phenol, a polyhydric phenol and a diene alkylation product, p-cresol or dicyclopentadiene butylated the reaction product, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene - bisphenols, benzyl compounds, polyhydric alcohol esters and the like.

[0048]合适的抗滴落剂优选为氟化聚烯烃,该氟化聚烯烃通常为包含含氟乙烯结构的聚合物或共聚物,且可具体示例为二氟乙烯树脂、四氟乙烯树脂、及四氟乙烯/六氟丙烯共聚物树脂,其中优选四氟乙烯树脂。 [0048] Suitable anti-dripping agent is preferably a fluorinated polyolefin, fluorinated polyolefin generally comprises a fluorine-containing ethylenic polymer or copolymer structures, and may be specifically exemplified by vinylidene fluoride resin, tetrafluoroethylene resin, and tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene resin being preferred.

[0049] 合适的光稳定剂包括苯并三唑类、二苯甲酮类中的至少一种。 [0049] Suitable light stabilizers include benzotriazoles, at least one of the benzophenone.

[0050] 合适的增塑剂为邻苯二甲酸酯。 [0050] Suitable plasticizers are phthalate esters.

[0051 ]合适的填料包括钛白粉、滑石粉、云母、硫酸钡等。 [0051] Suitable fillers include titanium dioxide, talc, mica, barium sulfate and the like.

[0052]合适的着色剂包括各种颜料、染料。 [0052] Suitable colorants include various pigments, dyes.

[0053] (2)制备本发明所述的高耐热阻燃聚碳酸酯组合物 [0053] (2) a high heat of the flame retardant polycarbonate compositions of the present invention was prepared

[0054]实施例1~7、以及对比例1~2均根据表1中所述的原料所占的重量份,并按照以下制备步骤来制备聚碳酸酯组合物:首先,称取配方量的聚碳酸酯、磷酸共聚碳酸酯、阻燃剂和其它助剂,并皆投入到混合机中进行共混,混合均匀后再投入至双螺杆挤出机中进行熔融混合,并挤出造粒,得到聚碳酸酯组合物;其中,所述双螺杆挤出机的螺杆直径为40:1,各段螺筒温度设置为250~260°C,螺杆转速为400~500rpm。 [0054] Examples 1 to 7 and Comparative Examples 1 to 2 in Table 1 are parts of the proportion by weight of starting material, and to prepare a polycarbonate composition prepared according to the following steps: First, a weighed amount of formula polycarbonate, copolycarbonates phosphate, flame retardant and other additives, are put into a mixer and blended, uniformly mixed and then melt-mixed into a twin-screw extruder, pelletized and extruded, obtained polycarbonate composition; wherein said twin-screw extruder having a screw diameter of 40: 1, barrel temperature of each segment is set to 250 ~ 260 ° C, a screw speed of 400 ~ 500rpm.

[0055] 表1:单位:重量份 [0055] Table 1: Unit: weight parts

[0056] [0056]

Figure CN106084718AD00091

[0057] 注:聚碳酸酯PC S-2000F:粘均分子量为25000(日本三菱);磷酸共聚碳酸酯0)6000:重均分子量为65000$1«);磷酸共聚碳酸酯0)3000:重均分子量为53000$1«) ;阻燃剂:Bayowet C4(朗盛化学);抗氧剂4〇1〇76:0-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯(CAS N0·:〔2082-79-3〕);抗滴落剂:Tefl:〇n*30 N PTFE(DuPont)。 [0057] Note: The polycarbonate PC S-2000F: viscosity-average molecular weight of 25,000 (Mitsubishi); phosphate copolycarbonate 0) 6000: weight average molecular weight of 65,000 $ 1 «); phosphate copolycarbonate 0) 3000: weight average a molecular weight of 53,000 $ «); flame retardant: Bayowet C4 (Lanxess); antioxidant 4〇1〇76: 0- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ten eight carbon alcohol esters (CAS N0 ·: [2082-79-3]); anti-dripping agent: Tefl: 〇n * 30 N PTFE (DuPont).

[0058] (3)产品物性测试 [0058] (3) Test Product properties

[0059] 按照行业标准,分别对上述实施例1~7、以及对比例1~2所制得的九种聚碳酸酯组合物进行多项基本物性测试。 [0059] accordance with industry standards, each of the above Examples 1 to 7 and Comparative Examples 1 to 2 obtained nine polycarbonate composition was substantially more testing. 其中,多项基本物性测试的测试标准或方法为: Wherein the number of tests or standard method for testing basic physical properties:

[0060] ① UL94阻燃性的测定方法: [0060] ① UL94 flame retardancy measurement method:

[0061 ]按照"塑料材料的可燃性测试,UL94"的规程进行可燃性测试。 [0061] Flammability tests were performed according to the "Tests for Flammability of Plastic Materials, UL94" procedures. 基于燃烧速率、熄灭时间、抵抗滴落的能力、以及落滴(drip)是否正燃烧,来得出阻燃等级。 Based on the combustion rate, time to extinguish, ability to resist dripping, drop and drop (drip) whether it is burning to obtain flame retardant grade. 用于测试的样品:尺寸为125mm长度X 13mm宽度X不大于13mm厚度的棒,本发明在进行测试时棒的厚度选为1.5mm。 Samples for testing: a size of 125mm length X 13mm width X is greater than the thickness of the rod 13mm, preferably 1.5mm thickness bars during testing of the present invention. 根据该UL94规程,并基于针对五个样品获得的测试结果,可以将材料阻燃等级分类为(UL94-HB): VO、VI、V2、5VA和/或5VB;但在本发明中,仅将材料的阻燃等级分类为:VO、VI 和V2,且各阻燃等级的分类标准为: According to the UL94 procedure, based on the test results obtained for five samples, the material may be classified as flammability rating (UL94-HB): VO, VI, V2,5VA and / or 5VB; in the present invention, only the flame rating classes of materials: VO, VI and V2, and each is a flame retardant grade classification criteria:

[0062] V0:在放置使得其长轴相对于火焰是180度的试样中,除去点燃火焰以后,燃烧和/ 或熏烧的时期不超过10秒,并且垂直放置的试样没有产生引燃脱脂棉的燃烧颗粒的滴落。 [0062] V0: in place so that its long axis with respect to the flame is 180 degrees in the sample, after removing the igniting flame, flaming and / or smoldering time less than 10 seconds and the vertically placed samples no ignition drips of burning particles absorbent cotton. 第五个棒的消焰时间是五个棒的消焰时间,每个点燃两次,其中,第一点燃的消焰时间(tl) 和第二点燃的消焰时间(t2)的总和(即为最大消焰时间(tl+t2))小于或等于50秒。 Fifth bar flame out time is five bar flame out time, wherein the first ignition flame out time (TL) and a second sum of each lit twice for flame ignition time (t2) (i.e. a maximum flame out time (tl + t2)) is less than or equal to 50 seconds.

[0063] VI:在放置使得其长轴相对于火焰是180度的试样中,除去点燃火焰以后,燃烧和/ 或熏烧的时期不超过30秒,并且垂直放置的试样没有产生引燃脱脂棉的燃烧颗粒的滴落。 [0063] VI: in place so that its long axis with respect to the flame is 180 degrees in the sample, after removing the igniting flame, flaming and / or smoldering time less than 30 seconds and the vertically placed samples no ignition drips of burning particles absorbent cotton. 第五个棒的消焰时间是五个棒的消焰时间,每个点燃两次,其中,第一点燃的消焰时间(tl) 和第二点燃的消焰时间(t2)的总和(即为最大消焰时间(tl+t2))小于或等于250秒。 Fifth bar flame out time is five bar flame out time, wherein the first ignition flame out time (TL) and a second sum of each lit twice for flame ignition time (t2) (i.e. a maximum flame out time (tl + t2)) is less than or equal to 250 seconds.

[0064] V2:在放置使得其长轴相对于火焰是180度的试样中,除去点燃火焰以后,燃烧和/ 或熏烧的平均时期不超过30秒,但是垂直放置的试样产生引燃棉的燃烧颗粒的滴落。 [0064] V2: positioned such that its long axis in relation to the flame is 180 degrees in the sample, after removing the igniting flame, flaming and / or smoldering average period less than 30 seconds, but the vertically placed samples produce ignition burning particles drip cotton. 第五个棒的消焰时间是五个棒的消焰时间,每个点燃两次,其中,第一点燃的消焰时间(tl)和第二点燃的消焰时间(t2)的总和(即为最大消焰时间(tl+t2))小于或等于250秒。 Fifth bar flame out time is five bar flame out time, wherein the first ignition flame out time (TL) and a second sum of each lit twice for flame ignition time (t2) (i.e. a maximum flame out time (tl + t2)) is less than or equal to 250 seconds.

[0065] ②阻燃稳定性(Flame stabi 1 i ty)的测定方法:取20根尺寸为"125mm长度X 13mm 宽度X不大于13mm厚度"的棒(本发明在进行测试时棒的厚度选为1.5mm),按照UL94规程对其测试,得出20根棒中符合V0等级的棒的数目,则,阻燃稳定性= n/20(其中0彡η彡20),很明显η越大,材料的阻燃稳定性越好。 [0065] ② Determination of flame stability (Flame stabi 1 i ty): Take 20 dimension "13mm 125mm length X 13mm width X is greater than the thickness" rod (bar thickness during testing of the present invention preferably 1.5mm), according to the UL94 testing procedures thereof, the number of bars in line with rods 20 V0 rating derived, then, flame stability = n / 20 (where 0 San San η 20), it is clear that the larger η, better stability of the flame retardant material.

[0066]③熔体流动速率(MFR)的测定方法:让塑料粒在一定时间(10分钟)内、一定温度及压力下(各种材料标准不同),融化成塑料流体,然后测量通过一直径为2.1mm圆管所流出的克数。 [0066] ③ The melt flow rate (MFR) measurement method: Let plastic pellets in a predetermined time (10 minutes), at a certain temperature and pressure (standard different materials), the plastic melts into a fluid and then measuring a diameter by is the number of grams of the outflow pipe 2.1mm. 流出的克数值越大,表示该塑胶材料的加工流动性越佳,反之则越差;本文中采用测试标准是ASTM D1238,单位:g/10min。 The larger the value g of flowing, represents the better processing flowability of the plastic material, otherwise the worse; employed herein are standard test ASTM D1238, unit: g / 10min. 采用测试条件为:在300°C、1.2kg载荷下的熔体流动速率(MFR)。 Test conditions were employed: a melt flow rate (MFR) at 300 ° C, 1.2kg load.

[0067]④热挠曲温度(HDT)的测定方法:根据测试标准ASTM D648,在1.82MPa负载下,用3.2mm和/或6.4mm厚度的棒平放测定HDT,以°C记录结果。 [0067] ④ heat deflection temperature (HDT) The measurement method: According to the test standard ASTM D648, at 1.82MPa load HDT measured with 3.2mm flat and / or rod 6.4mm thickness, recording the results in ° C.

[0068] ⑤悬臂梁冲击强度的测定方法:在23°C温度条件下,使用3.2_厚的模制缺口悬臂梁冲击棒测定缺口悬臂梁冲击强度。 [0068] ⑤ Determination of Izod impact strength: at a temperature of 23 ° C for used 3.2_ thick molded bars measuring notched Izod impact notched Izod impact strength. 根据ASTM D256测定缺口悬臂梁冲击强度,以焦耳/米记录结果。 Measured according to ASTM D256 Notched Izod impact strength, joules / meter record results. 在室温(23 °C)下进行测试。 It was tested at room temperature (23 ° C).

[0069] 本发明实施例1~7、以及对比例1~2所制得的九种聚碳酸酯组合物通过进行上述物性测试,取平均值,测试结果如表2所示: [0069] The present invention of Examples 1 to 7 and Comparative Examples 1 to 2 prepared nine kinds of polycarbonate compositions by the above-described physical property tests were averaged test results are shown in Table 2:

[0070] 表2:本发明实施例1~7、以及对比例1~2所制得聚碳酸酯组合物的基本物性测试结果 [0070] Table 2: Examples 1 to 7 of the present invention, and the basic physical properties Comparative test results of the obtained polycarbonate composition is 1 - 2

[0071] [0071]

Figure CN106084718AD00101

[0072] 从表2中可见,对比例2所制得的聚碳酸酯组合物的阻燃等级稍差,阻燃稳定性不很理想;对比例1所制得的聚碳酸酯组合物不仅阻燃等级差,且阻燃稳定性也很不理想;而本发明实施例所制得的聚碳酸酯组合物不仅具有优异的韧性和耐热性,还具有优异的薄壁阻燃等级及阻燃稳定性,特别适用于使用环境要求比较高的场合。 [0072] seen from Table 2, Comparative flammability rating prepared polycarbonate composition 2 was slightly inferior, flame stability is not ideal; Comparative Example 1 prepared polycarbonate composition not only barrier fuel level difference, and the flame stability is also very good; prepared in Example polycarbonate composition and embodiment of the present invention has not only excellent toughness and heat resistance, also excellent in thin-wall stability and flame retardant grades especially suitable for use where environmental requirements are relatively high.

[0073] 而本发明所制得的聚碳酸酯组合物之所以能够在韧性、耐热性、阻燃等级及阻燃稳定性方面具有优势,主要得益于对原料配方进行优化改进,具体表现为:本发明于原料配方中加入了磷酸酯共聚碳酸酯,该磷酸酯共聚碳酸酯与有机磺酸盐阻燃剂复配使用后,可以极大地提高有机磺酸盐阻燃性能的发挥,从而使聚碳酸酯组合物具有极佳的薄壁阻燃等级和阻燃稳定性;此外,由于磷酸共聚碳酸酯为高分子聚合物,其与聚碳酸酯的相容性极好,不会影响聚碳酸酯组合物的韧性和冲击强度,且对聚碳酸酯的耐热性影响很小;而且磷酸共聚碳酸酯在体系中的流动性相对较好,有利于有机磺酸金属盐的均匀分散。 [0073] And the present invention prepared polycarbonate composition was able to have an advantage in terms of toughness, heat resistance, flame retardant rating and stability, mainly due to the raw material formulation to optimize the improvement of specific performance as follows: the present invention was added to the phosphate raw material formulation copolycarbonate, copolycarbonate using the phosphate flame retardant compound and the organic sulfonic acid, can greatly improve the flame retardant properties of organic sulfonates play, whereby polycarbonate composition has excellent thin-wall flame retardant levels and stability; in addition, since phosphoric acid co-polymer of polycarbonate, its excellent compatibility with the polycarbonate, the polycarbonate will not affect toughness and impact strength of the composition, and the heat resistance of the polycarbonate is small impact; and copolycarbonates phosphate relatively good fluidity in the system, and to facilitate uniform dispersion of the organic sulfonic acid metal salt. 因此,本发明通过在原料配方中加入了磷酸酯共聚碳酸酯,从而能够实现在不影响聚碳酸酯韧性和耐热性的情况下,还极大的提高了聚碳酸酯组合物的阻燃等级和阻燃稳定性。 Accordingly, the present invention is by the addition of the phosphoric acid ester co-polycarbonate material in the formulation, can be achieved without affecting the toughness and heat resistance of the polycarbonate, but also greatly improved in flame retardancy grade polycarbonate compositions and flame stability.

[0074] 本发明所制得的高耐热阻燃聚碳酸酯组合物产品可广泛应用于例如手机、MP3播放器、计算机、笔记本电脑、照相机、录像机、平板电脑、手持受话器、厨房电器或者电气壳体的一部分、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,等等;具有广阔的市场前景和市场效益。 [0074] The present invention is made of a high heat flame retardant polycarbonate composition can be widely used such as mobile phones, MP3 players, computers, laptop computers, cameras, video recorders, a tablet computer, a handheld receiver, or an electrical kitchen appliances portion of the housing, automotive parts, housing or cover the field of construction, and electrical appliance housing and borders, and the like; and has broad market prospect market efficiency.

[0075] 以上对本发明做了详尽的描述,其目的在于让熟悉本领域的技术人员能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围内。 [0075] more than to do a detailed description of the present invention, the purpose is to allow a person skilled in the art to understand the content of the present invention and implemented, and not in order to limit the scope of the present invention, where the spirit of the invention essence made equivalent variations or modifications shall fall within the scope of the present invention.

Claims (10)

  1. 1. 一种高耐热阻燃聚碳酸酯组合物,其特征在于:按重量份计,具有如下原料配方:聚碳酸酯70~99份、磷酸共聚碳酸酯0.01~25份、阻燃剂0.01~5份、其它助剂0~10份;且各组分的重量份之和为100份。 A flame retardant polycarbonate composition of high heat resistance, comprising: parts by weight, the raw material having the following formulation: 70 to 99 parts of polycarbonate, copolycarbonate phosphate 0.01 to 25 parts, a flame retardant 0.01 to 5 parts, other additives 0 to 10 parts; parts by weight and the sum of the components is 100 parts.
  2. 2. 根据权利要求1所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述聚碳酸酯选自通过界面聚合法、熔融酯交换法、吡啶法、环状碳酸酯化合物的开环聚合法、预聚物的固相酯交换法制备的聚碳酸酯中的至少一种。 The high heat of the flame retardant polycarbonate composition of claim 1, wherein: the polycarbonate is selected by interfacial polymerization, melt transesterification method, a pyridine method, a cyclic carbonate compound ring-opening polymerization, the prepolymer solid-phase ester exchange at least one polycarbonate prepared by the.
  3. 3. 根据权利要求1或2所述的高耐热阻燃聚碳酸酯组合物,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、支化聚碳酸酯中的至少一种。 The high heat or flame retardant polycarbonate composition according to claim 1, wherein: the polycarbonate is selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic - aliphatic polycarbonate, at least one branched polycarbonate.
  4. 4. 根据权利要求3所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述聚碳酸酯选用粘均分子量为13000~40000的芳香族聚碳酸酯。 4. The high heat of the flame retardant polycarbonate composition of claim 3, wherein: the selection of viscosity average molecular weight polycarbonate of the aromatic polycarbonate is 13,000 to 40,000.
  5. 5. 根据权利要求4所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述聚碳酸酯选用粘均分子量为17000~24000的芳香族聚碳酸酯。 The high heat of the flame retardant polycarbonate composition according to claim 4, wherein: the selection of viscosity average molecular weight polycarbonate of the aromatic polycarbonate is 17,000 to 24,000.
  6. 6. 根据权利要求1所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述磷酸共聚碳酸酯选用重均分子量为50000~70000的磷酸酯-碳酸酯共聚物。 The high heat of the flame retardant polycarbonate composition of claim 1, wherein: said selection phosphate copolycarbonates having a weight average molecular weight of 50,000 to 70,000 ester - carbonate copolymer.
  7. 7. 根据权利要求1所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述阻燃剂选自含氮阻燃剂、含磷阻燃剂、有机磺酸金属盐阻燃剂中的至少一种; 或者,所述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、溴化芳香族交联聚合物中的至少一种。 The high heat of the flame retardant polycarbonate composition as claimed in claim 1, characterized in that: the flame retardant is selected from nitrogen containing flame retardants, phosphorus containing flame retardants, organic sulfonic acid metal salt flame retardant at least one agent; or the flame retardant is selected from brominated polystyrene, brominated polyphenylene ether, brominated bisphenol a type epoxy resin, brominated styrene - maleic anhydride copolymer, bromine epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, full-bromo tricyclic pentadecane, aromatic brominated crosslinked polymer of at least one of species.
  8. 8. 根据权利要求7所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述阻燃剂选用为有机磺酸金属盐阻燃剂,且所述有机磺酸金属盐阻燃剂为二苯基砜有机磺酸金属盐、全氟丁烷磺酸钾、全苯基丁烷磺酸钾中的至少一种。 8. The high heat of the flame retardant polycarbonate composition of claim 7, wherein: the choice of the flame retardant is an organic sulfonic acid metal salt flame retardant, and the organic sulfonic acid metal salt flame retardant diphenyl sulfone agent is a metal organic sulfonate, potassium perfluorobutane sulfonate, potassium at least one of full-diphenyl butane sulfonic acid.
  9. 9. 根据权利要求1所述的高耐热阻燃聚碳酸酯组合物,其特征在于:所述其它助剂选自热稳定剂、抗氧剂、抗滴落剂、光稳定剂、增塑剂、填料、着色剂中的至少一种。 9. The high heat of the flame retardant polycarbonate composition of claim 1, wherein: said other additives selected from heat stabilizers, antioxidants, anti-drip agents, light stabilizers, plasticizing agents, fillers, at least one coloring agent.
  10. 10. 根据权利要求1-9中任一项所述的高耐热阻燃聚碳酸酯组合物的制备方法,其特征在于:包括以下制备步骤:首先,称取配方量的聚碳酸酯、磷酸共聚碳酸酯、阻燃剂和其它助剂,并皆投入到混合机中进行共混,混合均匀后再投入至双螺杆挤出机中进行熔融混合,并挤出造粒,得到所述高耐热阻燃聚碳酸酯组合物;其中,所述双螺杆挤出机的螺杆直径为40:1,各段螺筒温度设置为250~260°C,螺杆转速为400~500rpm。 The method of preparing high heat resistant flame retardant polycarbonate composition as claimed in any one of claims 1-9, characterized in that: the preparation step comprises: first weighed amount of the polycarbonate formulation, phosphoric acid copolycarbonate flame retardant and other additives, are put into a mixer and melt mixed for blending, mixing uniformly and then put into a twin-screw extruder, extruded and pelletized, to obtain a high resistance to hot flame retardant polycarbonate composition; wherein said twin-screw extruder having a screw diameter of 40: 1, barrel temperature of each section is set to 250 ~ 260 ° C, a screw speed of 400 ~ 500rpm.
CN 201610423112 2016-06-14 2016-06-14 High heat-resistant flame-retardant polycarbonate composition and preparation method thereof CN106084718A (en)

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CN102532816A (en) * 2011-12-31 2012-07-04 宁波长阳科技有限公司 Macromolecular char formation flame-retardant polyester material, polyester thin film and preparation methods thereof
CN103467959A (en) * 2013-09-03 2013-12-25 上海锦湖日丽塑料有限公司 High-heat-resistance easily-formed halogen-free flame-retardant polycarbonate (PC) composition and preparation method thereof
CN103619959A (en) * 2011-04-14 2014-03-05 Frx聚合物股份有限公司 Polyphosphonate and copolyphosphonate additive mixtures
CN103827169A (en) * 2011-09-21 2014-05-28 第一毛织株式会社 Polycarbonate and a production method therefor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103619959A (en) * 2011-04-14 2014-03-05 Frx聚合物股份有限公司 Polyphosphonate and copolyphosphonate additive mixtures
CN103827169A (en) * 2011-09-21 2014-05-28 第一毛织株式会社 Polycarbonate and a production method therefor
CN102532816A (en) * 2011-12-31 2012-07-04 宁波长阳科技有限公司 Macromolecular char formation flame-retardant polyester material, polyester thin film and preparation methods thereof
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