CN106188553A - Copolyester electronic insulating pad and manufacture method thereof - Google Patents

Copolyester electronic insulating pad and manufacture method thereof Download PDF

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Publication number
CN106188553A
CN106188553A CN201610653611.5A CN201610653611A CN106188553A CN 106188553 A CN106188553 A CN 106188553A CN 201610653611 A CN201610653611 A CN 201610653611A CN 106188553 A CN106188553 A CN 106188553A
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copolyester
insulating spacer
esterification
step
electronic
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CN201610653611.5A
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李彦
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苏州柯创电子材料有限公司
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Publication of CN106188553A publication Critical patent/CN106188553A/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/85Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86Germanium, antimony, or compounds thereof
    • C08G63/863Germanium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/85Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86Germanium, antimony, or compounds thereof
    • C08G63/866Antimony or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/914Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421Polyesters
    • H01B3/422Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds

Abstract

The invention discloses a copolyester electronic insulating pad, made from the following materials, in percent by weight: 50-70% of terephthalic acid, 20-40% of ethylene glycol, 1-3% of 1,4-cyclohexanedimethanol, 0.2-2% of polyoxypropylene triol, 0.2-2% of pentaerythritol, 0.2-2% of 1,3,5-cyclohexanetriol, 0.1-1% of antimony acetate, 0.1-1% of germanium dioxide, 0.1-2% of trimethyl phosphate, 0.5-5% of maleic anhydride, 0.5-5% of styrene, 3-8% of polybutylene terephthalate, adding up to 1-100% by weight. By adding the maleic anhydride and styrene that improve toughening property, impact tolerance of the insulating pad is improved.

Description

共聚酯电子绝缘垫块及其制造方法 Electrical insulating spacer and a method for producing copolyesters

技术领域 FIELD

[0001] 本发明属于电子绝缘材料领域,特别涉及一种共聚酯电子绝缘垫块及其制造方法。 [0001] The present invention belongs to the field of electronic insulating materials, and particularly relates to an electronic insulating spacer and a manufacturing method copolyesters.

背景技术 Background technique

[0002] 绝缘垫块广泛应用于电器中,起到绝缘支撑的作用,特别是由PET绝缘材料构成的绝缘垫块,是一种性能比较全面的的绝缘材料。 [0002] In widely used in electrical insulation mat, functions as an insulating support, in particular made of PET insulation, spacer, a more comprehensive performance of the insulating material. 聚对苯二甲酸乙二醇酯简称PET,为高分子聚合物,由对苯二甲酸乙二醇酯发生脱水缩合反应而来。 Acronym polyethylene terephthalate PET as a polymer, a polyethylene terephthalate from dehydration condensation reaction. 对苯二甲酸乙二醇酯是由对苯二甲酸和乙二醇发生酯化反应所得。 Terephthalate is obtained from terephthalic acid and ethylene glycol esterification reaction. PET是乳白色或浅黄色、高度结晶的聚合物,表面平滑有光泽。 PET is milky white or pale yellow, highly crystalline polymers, the surface smooth and shiny. 在较宽的温度范围内具有优良的物理机械性能,长期使用温度可达120°C,电绝缘性优良,甚至在高温高频下,其电性能仍较好,但耐电晕性较差,抗蠕变性,耐疲劳性,耐摩擦性、尺寸稳定性都很好。 It has excellent physical and mechanical properties over a wide temperature range, long-term use temperature of up to 120 ° C, excellent in electrical insulating properties, even at high temperature, its electrical properties are still good, but poor corona resistance, creep resistance, fatigue resistance, abrasion resistance, dimensional stability is very good. PET塑料分子结构高度对称,具有一定的结晶取向能力,故而具有较高的成膜性和成性。 Highly symmetrical molecular structure of PET plastic, having a certain crystal orientation ability, and therefore has high resistance to deposition and. PET塑料具有很好的光学性能和耐候性,非晶态的PET塑料具有良好的光学透明性。 PET plastic having excellent optical properties and weatherability, amorphous PET plastic having good optical transparency. 另外PET塑料具有优良的耐磨耗摩擦性和尺寸稳定性及电绝缘性。 Further PET plastic with excellent frictional wear resistance and dimensional stability and electrical insulation. PET做成的瓶具有强度大、透明性好、无毒、防渗透、质量轻、生产效率高等因而受到了广泛的应用,特别是在电气绝缘材料、电容器膜、柔性印刷电路板及薄膜开关等电子领域和机械领域。 PET bottles made with strength, transparency, non-toxic, anti-penetration, light weight, high production efficiency and thus subject to a wide range of applications, particularly in electrical insulation materials, capacitor films, flexible printed circuit boards and membrane switch electronics and machinery.

[0003] 由PET作为载体的绝缘垫块在增韧性能不足,导致绝缘垫块的受冲击性能下降,绝缘垫块容易开裂或破碎,直接影响绝缘垫块的绝缘和支撑功能,甚至导致电器出现故障,由此,亟需一种耐受冲击强度高的绝缘垫块。 [0003] As a carrier of PET is insufficient in toughening spacer insulating performance, resulting in decreased impact properties by an insulating spacer, the insulating spacer prone to cracking or breaking, directly affects the insulating spacer insulating and supporting functions, and even lead to electrical failure fault, whereby, a need for an impact resistant high strength insulating spacer.

发明内容 SUMMARY

[0004] 针对上述技术问题,本发明中提出了一种共聚酯电子绝缘垫块及其制造方法,本发明通过对PET进行改性,添加了提高增韧性能的马来酸酐和苯乙烯,提高了绝缘垫块的受冲击能力。 [0004] For the above technical problems, the present invention proposes an electronic method of producing an insulating spacer and copolyesters, of the present invention, by modifying PET, is added to improve the performance of toughened styrene and maleic anhydride, improved shock resistance by the insulation pad.

[0005] 为了实现根据本发明的这些目的和其它优点,提供了一种共聚酯电子绝缘垫块, 包括以下步骤: 对苯二甲酸50%~70%; [0005] To achieve these objects and other advantages of the present invention, there is provided an electrical insulation spacer copolyester, comprising the steps of: terephthalic acid, 50% to 70%;

[0006] 乙二醇20%~40%; I,4-坏己烷二甲醇I %~3 %; 聚氧化丙烯三醇0,2%~2%; 季戊四醇0.2%-2%; 1,3,5-环己烷三醇0.2%~2%; 醋酸锑0,1 %~1 %; [0006] glycol 20% ~ 40%; I, 4- dimethanol bad I% ~ 3%; polyoxypropylene triol 0,2% to 2%; 0.2% -2% of pentaerythritol; 1,3 , 5-cyclohexane-triol 0.2% to 2%; antimony acetate 0,1% to 1%;

[0007] 二氧化锗0,1%~1%; 磷酸三甲酯0,1%~2%; 马来截酐0.5%-5%; 苯乙烯0.5%~5%; 聚对苯二甲酸丁二醇酷3%~8%; [0007] germanium dioxide 0,1% to 1%; trimethyl 0,1% to 2% of phosphoric acid; maleic anhydride cross 0.5-5%; 0.5% to 5% of styrene; poly-butoxy cool diol 3% to 8%;

[0008] 以上材料的质量百分含量总和为100%。 Mass percentage of the total [0008] material is 100% or more.

[0009] 优选的,所述二氧化锗为能够通过800目筛网的白色粉末。 [0009] Preferably, the germanium dioxide through a screen of 800 mesh as a white powder.

[0010] 优选的,所述醋酸锑能够通过6〇〇目筛网。 [0010] Preferably, the antimony acetate through 6〇〇 mesh.

[0011] -种共聚酯电子绝缘垫块的制造方法,包括以下步骤: [0011] - A method for producing an electronic kind of co-polyester insulating spacer, comprising the steps of:

[0012] 步骤1)按上述原料配方的比例进行称取; [0012] Step 1) by the ratio of the raw material formulation is weighed;

[0013] 步骤2)将称取好的对苯二甲酸、乙二醇、1,4-环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇、醋酸锑、二氧化锗和磷酸三甲酯组成的混合物料混合均匀后送至第一酯化反应器中进行酯化反应,生成第一酯化物; [0013] Step 2) The weighed good terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, polyoxypropylene triol, pentaerythritol, 1,3,5_ cyclohexane triol, mixed materials antimony acetate, trimethyl phosphate and germanium dioxide uniformly mixed composition to the esterification reaction in the first esterification reactor to produce a first esterification product;

[0014] 步骤3)将所述第一酯化物和称取好的所述马来酸酐和苯乙烯同时放入第二酯化反应器中进行酯化反应,生成第二酯化物; [0014] Step 3) the first and weighed the esterified maleic anhydride and styrene while good into a second esterification reactor esterification reaction to produce a second esterification product;

[0015] 步骤4)将第二酯化物和称取好的所述聚对苯二甲酸丁二醇酯送入预缩聚反应器中进行预缩聚反应,生成第一预聚物,将所述第一预聚物经过预聚物过滤器过滤后送入终缩聚反应器中进行终缩聚反应,最终通入氮气,输出共聚酯切片; [0015] Step 4) and the second esterified product weighed good the poly (butylene terephthalate) into a pre-polycondensation reactor pre-polycondensation reaction to produce a first prepolymer, said first a prepolymer after the prepolymer is filtered through a filter into the final polycondensation reactor for the final polycondensation reaction, the final nitrogen gas, the output common polyester chips;

[0016] 步骤5)将所述共聚酯切片进行后续加工处理,得到绝缘垫块。 [0016] Step 5) the copolyester slice subsequent processing to give an insulating spacer.

[0017] 优选的,所述步骤2)中,将所述混合物料送入浆料调配槽中,在浆料调配槽搅拌器的作用下,搅拌均勾,搅拌器的转速为I 〇r/min,搅拌混合时间为3h。 [0017] Preferably, in the step 2), the mixed material into the slurry preparation tank, slurry preparation tank under the action of a stirrer, stirring was hook, a stirrer speed of 〇r I / min, stirring and mixing time was 3h.

[0018] 优选的,所述第一酯化反应温度为245~255°C,第二酯化反应温度为255~265°C, 所述预缩聚反应器的操作压力为9~llkPa,所述终缩聚反应器的工作温度为265~275°C。 [0018] Preferably, the first esterification reaction temperature is 245 ~ 255 ° C, the second esterification reaction temperature is 255 ~ 265 ° C, the pre-polycondensation reactor operating pressure is 9 ~ llkPa, the final polycondensation reactor operating temperature is 265 ~ 275 ° C. [0019]优选的,所述步骤5)中,所述的后续加工处理为:依次进行预结晶、干燥处理、加热熔融塑化和过滤后,注塑成型,经整形测试后得到最终产物绝缘垫块。 [0019] Preferably, the step 5), the subsequent processing of: sequentially preliminarily crystallized, dried, filtered and melted by heating plasticization, injection molding, by the plastic insulation test pad to give the final product .

[0020]优选的,所述二氧化锗为能够通过800目筛网的白色粉末;所述醋酸锑能够通过600目筛网。 [0020] Preferably, the germanium dioxide through a 800 mesh as a white powder; antimony acetate through a 600 mesh screen.

[0021] 优选的,预结晶和干燥温度为150 °C~170 °C,干燥时间3~4h。 [0021] Preferably, the pre-crystallization and the drying temperature is 150 ° C ~ 170 ° C, the drying time is 3 ~ 4h.

[0022]优选的,所述加热熔融塑化的加热温度为275°C~285°C。 [0022] Preferably, the hot-melt plasticized heating temperature of 275 ° C ~ 285 ° C.

[0023] 本发明至少包括以下有益效果: [0023] The present invention comprises at least the following advantages:

[0024] 1、本发明的绝缘垫块通过添加多种多元醇,提高了绝缘垫块的致密度,由此提高了绝缘垫块的绝缘电阻和机械性能; [0024] 1, the insulating spacer of the present invention by adding more polyols, improve the density of the insulating spacer, thereby improving the insulating spacer insulation resistance and mechanical properties;

[0025] 2、本发明的绝缘垫块通过添加聚对苯二甲酸丁二醇酯,提高了绝缘垫块的耐热性能,同时缩小了绝缘垫块的受热收缩率; [0025] 2, the insulating spacer of the present invention is by adding a poly (butylene terephthalate), improved heat insulating performance of the pad, as well as reduced by the heat shrinkage of the insulating spacer;

[0026] 3、本发明的绝缘垫块的制备工艺简单可行,便于产业化; [0026] 3, it is simple and feasible preparation process of the insulating spacer of the present invention, to facilitate industrialization;

[0027] 4、本发明的绝缘垫块通过添加马来酸酐和苯乙烯,提高了绝缘垫块的增韧性能, 耐受冲击强度更高。 [0027] 4, the insulating spacer of the present invention by the addition of maleic anhydride and styrene, insulating spacer improves the toughening performance, withstand higher impact strength.

[0028] 本发明的其它优点、目标和特征将部分通过下面的说明体现,部分还将通过对本发明的研究和实践而为本领域的技术人员所理解。 [0028] Additional advantages, objects and features of the invention will be reflected in part by the following description, the section will also be appreciated by the skilled person on the research and practice of the invention and in the art.

具体实施方式 Detailed ways

[0029] 下面对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。 [0029] The following further detailed description of the present invention, in order to make those skilled in the art with reference to the description text can be implemented accordingly.

[0030] 应当理解,本发明所使用的诸如"具有"、"包含"以及"包括"术语并不配出一个或多个其它元件或其组合的存在或添加。 [0030] It should be understood that, as used in the present invention, "having", "including" and "comprising" term is not equipped with one or more other elements, or a combination of the presence or addition.

[0031] 本发明以对苯二甲酸一乙二醇为基础,并引入1,4-环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇作为添加剂,旨在充分提高绝缘垫块的致密度,使得绝缘垫块的绝缘性能加强,同时提高了绝缘垫块的机械性能。 [0031] In the present invention, an ethylene terephthalate-based, and the introduction of 1,4-cyclohexanedimethanol, polyoxypropylene triol, pentaerythritol, cyclohexane triol as an additive 1,3,5_ , an insulating spacer designed to fully improve the density, so that the insulation reinforcing spacer insulating properties, while improving the mechanical properties of the insulating pad. 同时,引入醋酸锑、二氧化锗和磷酸三甲酯作为酯化和缩聚反应过程催化剂,并且引入马来甘酸和苯乙烯,作为绝缘垫块的增韧剂,旨在提高绝缘垫块的耐受冲击能力,最后配合加入适量的聚对苯二甲酸丁二醇酯, 旨在提高了绝缘垫块的耐热性能,同时缩小了绝缘垫块的受热收缩率,保障绝缘垫块的绝缘性能,提高使用该绝缘垫块的电器的可靠性。 At the same time, the introduction of antimony acetate, trimethyl phosphate and germanium dioxide as an esterification reaction and a polycondensation catalyst, and introducing styrene and maleic creatinine, the insulating spacer as a toughening agent, designed to improve the tolerance of the insulating spacer shocks, and finally added with an appropriate amount of poly (butylene terephthalate), designed to improve the heat resistance of the insulating spacer, as well as reduced by the heat shrinkage of the insulating spacer, the insulating spacer insulating properties to protect and improve the the operational reliability of electrical insulation pads.

[0032] 制备采用过程采用两次酯化、两次缩聚,与马来酸酐、苯乙烯以及聚对苯二甲酸丁二醇酯混合后依次进行预结晶、干燥处理、加热熔融塑化和过滤后,注塑成型,经整形测试后得到最终产物绝缘垫块。 After preparation [0032] The esterification process using two, two condensation with maleic anhydride, styrene, and mixed esters of polyethylene terephthalate, polybutylene sequentially after pre-crystallized, dried, heated and plasticized melting filter , injection molding, the shaped final product was obtained after testing the insulation spacer.

[0033] 常规的以对苯二甲酸和乙二醇为原料,催化酯化制备的聚酯绝缘垫块的增韧性能不高,影响绝缘垫块的受冲击能力,同时,在高温条件下,极容易收缩变形,造成绝缘垫块性能下降。 [0033] In conventional terephthalic acid and ethylene glycol as raw materials, the toughening properties of the polyester prepared insulating spacer catalytic esterification is not high impact shock resistance by an insulating spacer, while at high temperature, very easy to shrinkage, resulting in degraded insulating spacer. 为此,进行以下配方改进: To this end, the following formula improvements:

[0034] 1)引入1,4_环己烷二甲醇,其范围控制在lwt%~3wt%,在合成绝缘垫块中引入1,4_环己烷二甲醇可以降低合成过程中聚酯的熔点、升高璃化温度,将共聚物变为非结晶结构,从而使得绝缘垫块更加致密,减少水分子透过率; [0034] 1) introducing 1,4_ cyclohexanedimethanol, their control in lwt% ~ 3wt%, introduced in the synthesis of the insulating spacer can be reduced 1,4_ cyclohexanedimethanol polyester synthesis process melting point, raising the glass transition temperature, the copolymer becomes non-crystalline structure, so that the insulating pad is denser, reducing the permeability of water molecules;

[0035] 2)引入多种多元醇,其中,聚氧化丙烯三醇的加入量为0.2wt%~2wt%;季戊四醇的加入量为0.2wt%~2wt% ; 1,3,5-环己烧三醇的加入量为0.2wt%~2wt% ;多元醇的引入,降低了聚酯大分子的结晶速度,使得聚酯分子间排列更加致密,降低由于结晶速度过快而导致绝缘垫块内部生成的过多缺陷,进一步增加了绝缘垫块的致密度; [0035] 2) introducing more polyols, wherein the polyoxypropylene triol was added in an amount of 0.2wt% ~ 2wt%; pentaerythritol was added in an amount 0.2wt% ~ 2wt%; 1,3,5- cyclohexyl burn triol was added in an amount of 0.2wt% ~ 2wt%; polyhydric alcohol is introduced, reducing the crystallization rate of polyester macromolecules, such that the polyester molecules arranged between the more dense and reduce the crystallization rate is too fast because the insulating spacer internally generated too many defects, to further increase the density of the insulating spacer;

[0036] 3)引入马来酸酐和苯乙烯作为增韧剂,其控制范围都在0.5wt%~5wt%,增韧剂的引入提高了绝缘垫块耐受冲击强度,提高了使用该绝缘垫块电器的可靠性; [0036] 3) introducing maleic anhydride and styrene as a toughening agent, in which the control range of 0.5wt% ~ 5wt%, the toughening agent is introduced to improve the impact resistant strength of the insulating spacer, the increased use of insulating pad block electrical reliability;

[0037] 4)引入聚对苯二甲酸丁二醇酯,其控制范围在3wt %~8wt %,聚对苯二甲酸丁二醇酯的引入提高了绝缘垫块的耐热性能,同时缩小了绝缘垫块的受热收缩率,并且进一步提高了绝缘垫块的机械性能。 [0037] 4) introduced into the poly (butylene terephthalate), which controls the range of 3wt% ~ 8wt%, poly (butylene terephthalate) is incorporated to improve the heat resistance of the insulating spacer, as well as reduced by heat shrinkage of the insulating pad, and to further improve the mechanical properties of the insulating pad.

[0038] 为了实现上述目的,本发明采用以下技术方案:一种共聚酯电子绝缘垫块,原料配方由以下质量百分含量的材料组成: 对苯二甲酸50%~70%; 乙二醇20%~40%; 1,4-环己烷二甲醇1%~3%; [0038] To achieve the above object, the present invention employs the following technical solutions: A copolyester electrical insulation spacer, a material feed formulation composed of the following mass percentage: 50% to 70% acid; glycol 20% to 40%; 1,4-cyclohexanedimethanol, 1% to 3%;

[0039] 聚氧化丙烯三醇0.2%~2%; 季戊四醇0.2%~2%; 1,3,5-环己烷三醇0.2%~2%: 醋酸锑0J%~1%; 二氧化锗0,1%~1%; 磷酸三甲酯0,1 %~2%; [0039] polyoxypropylene triol 0.2% to 2%; 0.2% to 2% of pentaerythritol; 1,3,5-cyclohexane triol 0.2% to 2%: antimony acetate 0J% ~ 1%; 0 germanium dioxide , 1% to 1%; trimethyl 0,1% to 2% phosphoric acid;

[0040] 马来酸酐0.5%~5%; 苯乙烯0.5%~5%; 聚对苯二甲酸丁二醇酯3%~8%:¾ [0040] Maleic anhydride 0.5% to 5%; 0.5% to 5% of styrene; polybutylene terephthalate ester 3% to 8%: ¾

[0041] 以上材料的质量百分含量总和为100%。 Mass percentage of the total [0041] material is 100% or more.

[0042] 上述技术方案中,所述二氧化锗为能够通过800目筛网的白色粉末,所述醋酸锑能够通过600目筛网。 [0042] In the above technical solution, through the germanium dioxide is a white powder 800 mesh, antimony acetate through a 600 mesh screen. 二氧化锗和醋酸锑作为催化剂,粒度分布更均匀、细致,催化性能越高; 同时,添加适量的1,4_环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇,二元醇和多元醇的加入可以降低共聚酯的结晶速率,提高绝缘垫块的致密度。 Germanium dioxide and antimony acetate as catalyst, the particle size distribution is more uniform, fine, the higher the catalytic performance; the same time, an appropriate amount of 1,4_ cyclohexanedimethanol, polyoxypropylene triol, pentaerythritol, 1,3,5_ cyclohexane triol, diols and polyols can be added to reduce the rate of crystallization of the copolyester to improve the density of the insulating spacer.

[0043] -种共聚酯电子绝缘垫块的制造方法,包括以下步骤: [0043] - A method for producing an electronic kind of co-polyester insulating spacer, comprising the steps of:

[0044] 步骤1)按上述原料配方的比例进行称取; [0044] Step 1) by the ratio of the raw material formulation is weighed;

[0045] 步骤2)将称取好的对苯二甲酸、乙二醇、1,4-环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇、醋酸锑、二氧化锗和磷酸三甲酯组成的混合物料混合均匀后送至第一酯化反应器中进行酯化反应,生成第一酯化物; [0045] Step 2) The weighed good terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, polyoxypropylene triol, pentaerythritol, 1,3,5_ cyclohexane triol, mixed materials antimony acetate, trimethyl phosphate and germanium dioxide uniformly mixed composition to the esterification reaction in the first esterification reactor to produce a first esterification product;

[0046] 步骤3)将所述第一酯化物和称取好的所述马来酸酐和苯乙烯同时放入第二酯化反应器中进行酯化反应,生成第二酯化物; [0046] Step 3) the first and weighed the esterified maleic anhydride and styrene while good into a second esterification reactor esterification reaction to produce a second esterification product;

[0047] 步骤4)将第二酯化物和称取好的所述聚对苯二甲酸丁二醇酯送入预缩聚反应器中进行预缩聚反应,生成第一预聚物,将所述第一预聚物经过预聚物过滤器过滤后送入终缩聚反应器中进行终缩聚反应,最终通入氮气,输出共聚酯切片; [0047] Step 4) and the second esterified product weighed good the poly (butylene terephthalate) into a pre-polycondensation reactor pre-polycondensation reaction to produce a first prepolymer, said first a prepolymer after the prepolymer is filtered through a filter into the final polycondensation reactor for the final polycondensation reaction, the final nitrogen gas, the output common polyester chips;

[0048] 步骤5)将所述共聚酯切片进行后续加工处理,得到绝缘垫块。 [0048] Step 5) the copolyester slice subsequent processing to give an insulating spacer.

[0049] 具体的,将称取好的对苯二甲酸、乙二醇、1,4-环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇、醋酸锑、二氧化锗和磷酸三甲酯送入浆料调配槽中,在浆料调配槽搅拌器的作用下,搅拌均匀,搅拌器的转速为l〇r/min,搅拌时间为3h;配置完成的浆料通过浆料输送栗输送至第一酯化反应器中进行酯化反应,所述第一酯化反应器为立式夹套反应釜,其内设置有加热盘管且带搅拌器。 [0049] Specifically, the weighed good terephthalic acid, ethylene glycol, 1,4-cyclohexanedimethanol, polyoxypropylene triol, pentaerythritol, 1,3,5_ cyclohexane triol, antimony acetate, trimethyl phosphate and germanium dioxide into the slurry preparation tank, slurry preparation tank under the action of a stirrer, stir, stirrer speed of l〇r / min, the stirring time is 3H; configuration the slurry is completed by esterification of the slurry fed to the first conveyance Li esterification reactor, the first esterification reactor is a vertical reactor jacket, within which is provided with a heating coil and equipped with a stirrer . 反应物在第一酯化反应釜内反应生成第一酯化物,将所述第一酯化物放入第二酯化反应器,并将称取好的所述马来酸酐和苯乙烯同时放入所述第二酯化反应器中,进行接枝共聚反应,第二酯化反应器是一个有内外室结构的反应器,物料先进入室外,再通过套筒上的夹缝流入内室,内室设置有加热盘管,并靠搅拌器循环加热,将物料温度提高到265°C,乙二醇分离塔回流的乙二醇在内室,提高了反应摩尔比,进一步加速反应进行,在第二酯化反应器的酯化率达到了96.5 %,靠压差送到预缩聚反应器,该反应器的盘管加热使用液相热媒,该反应器夹套和气相管路加热使用气相热媒,与预缩聚反应器共用一套气相热媒反应器,反应器内反应温度是通过调节一次热媒的补充量来改变二次热媒加热的温度来控制的。 Generating a first reactant esterified in a first esterification reactor, the first esterified product placed in a second esterification reactor, and the said take good simultaneously into maleic anhydride and styrene the second esterification reactor, graft copolymerization, a second esterification reactor there is a chamber structure inside and outside the reactor, before entering outdoor materials, then flows into the chamber through the nip on the sleeve, the internal chamber is provided with a heating coil, a stirrer and by circulating heated to raise the batch temperature to 265 ° C, the ethylene glycol separation column reflux inner chamber, the molar ratio improved to further accelerate the reaction is carried out in the second esterification reactor esterification rate reached 96.5%, against a pre-pressure to the polycondensation reactor, the reactor was heated using a liquid phase coil heat medium, the vapor conduit and the reactor jacket was heated using heat medium gas with a common pre-polycondensation reactor gas phase reactor heat medium in the reactor the reaction temperature was changed to a secondary heat medium heated by adjusting the temperature of a supplemental amount of the heat medium is controlled. 通过调节酯化反应的温度、压力、液位以及乙二醇的回流量等,可以控制第二酯化反应的酯化率。 By adjusting the temperature of the esterification reaction, pressure, level and flow back to the ethylene glycol and the like, may be controlled esterification of the second esterification reaction.

[0050] 上述技术方案中,所述第一酯化反应温度为245~255°C,第二酯化反应温度为255 ~265°C,所述预缩聚反应器的操作压力为9~llkPa,所述终缩聚反应器的工作温度为265 ~275。 [0050] In the above aspect, the first esterification reaction temperature is 245 ~ 255 ° C, the second esterification reaction temperature is 255 ~ 265 ° C, the pre-polycondensation reactor operating pressure is 9 ~ llkPa, the final polycondensation reactor operating temperature from 265 to 275. . .

[0051] 上述技术方案中,所述步骤5)中,所述的后续加工处理为:依次进行预结晶、干燥处理、加热熔融塑化和过滤后,注塑成型,经整形测试后得到最终产物绝缘垫块。 [0051] In the above aspect, the step 5), the subsequent processing of: sequentially preliminarily crystallized, dried, filtered and melted by heating plasticization, injection molding, by the plastic insulation test to give the final product pad.

[0052]上述技术方案中,所述二氧化锗为能够通过800目筛网的白色粉末;所述醋酸锑能够通过600目筛网。 [0052] The above technical solution, through the germanium dioxide is a white powder 800 mesh; antimony acetate through a 600 mesh screen.

[0053]上述技术方案中,预结晶和干燥温度为150°C~170°C,干燥时间3~4h。 [0053] In the above technical solution, and drying the pre-crystallization temperature of 150 ° C ~ 170 ° C, the drying time is 3 ~ 4h.

[0054]上述技术方案中,所述加热熔融塑化的加热温度为275°C~285°C。 [0054] In the above technical solution, the hot-melt plasticized heating temperature 275 ° C ~ 285 ° C.

[0055] 预缩聚反应器反应生成的预聚物分别经熔体夹套三通阀出料、预聚物出料栗增压后和熔体夹套三通阀汇集后,经过预聚物过滤器,再经特殊设计的熔体夹套管送至终缩聚反应器中。 [0055] Prepolymerization reactor prepolymer by the melt reaction of a jacketed three-way valve respectively, the material, the prepolymer melt and a rear three-way valve jacket material together after pressurization Li, filtered through a prepolymer It is, by a special design to the end of jacketed pipe melt polycondensation reactor.

[0056] 预缩聚物料被连续送入终缩聚反应器,在搅拌和高真空条件下就可到达最终产品质量。 [0056] Prepolymerization material is continuously fed to the final polycondensation reactor, the final product quality can be reached with stirring and under high vacuum conditions. 控制压力、温度和停留时间到适当水平,使得作为聚合度测量的粘度可调。 Controlling the pressure, temperature and residence time to the appropriate level, the degree of polymerization such that the viscosity as measured adjustable. 通过调节热媒的温度,可以调节反应器中物料温度,控制出口物料的特性粘度。 By adjusting the temperature of the heat transfer medium, the reactor contents can be adjusted temperature, viscosity control characteristics of the material outlet. 通入氮气,输出PET共聚醋切片。 Purged with nitrogen, PET copolymerized vinegar output slice.

[0057] PET的预结晶和干燥设备一般采用带有结晶床的填充塔,同时配有干空气制备装置,包括空压机、分子筛去湿器、加热器等。 [0057] PET pre-crystallization and drying equipment generally employ a packed column with a bed of crystals, while with dry air preparation device, comprising a compressor, a molecular sieve dehumidifier, heater and the like. 预结晶和干燥温度为150°C~170°C,干燥时间约3~4h,干燥后的PET切片湿含量要求控制在30~50ppm。 Drying and pre-crystallization temperature of 150 ° C ~ 170 ° C, drying time of about 3 ~ 4h, PET chips moisture content after drying is controlled in claim 30 ~ 50ppm.

[0058]所述加热熔融塑化的加热温度为275°C~285°C,为了去除熔体中可能存在的杂质、凝胶粒子、鱼眼等异物,常在熔体管线上计量栗的前后各安装一个过滤器,过滤器加热温度控制在275 °C~285 °C。 [0058] The hot-melt plasticized heating temperature 275 ° C ~ 285 ° C, to remove impurities that may be present in the melt impurities, gel particles, fish eye, often on the melt metering Li longitudinal line the installation of a filter, the filter control the heating temperature 275 ° C ~ 285 ° C.

[0059] 本案制得的绝缘垫块本发明的绝缘垫块,通过添加多种多元醇,提高了绝缘垫块的致密度,由此提高了绝缘垫块的绝缘电阻和机械性能通过添加聚对苯二甲酸丁二醇酯, 提高了绝缘垫块的耐热性能; [0059] The spacer insulating case made of an insulating spacer according to the present invention, by adding more polyols, increased density insulating spacer, thereby improving the insulation resistance of the insulating spacer and mechanical properties by the addition of polyethylene polybutylene terephthalate, to improve the heat resistance of the insulating spacer;

[0060] 同时缩小了绝缘垫块的受热收缩率;同时,通过添加马来酸酐和苯乙烯,提高了绝缘垫块的增韧性能,耐受冲击强度更高,且本发明的绝缘垫块的制备工艺简单可行,便于产业化。 [0060] as well as reduced by the heat shrinkage of the insulating spacer; the same time, by adding maleic anhydride and styrene, insulating spacer improves the performance of toughened, high impact resistant strength, and the insulating spacer of the present invention. preparation process is simple and feasible, easy industrialization.

[0061] 以下表一所示的是不同实施例的具体原料配方: [0061] Examples of specific embodiments are different formulation of raw materials shown in Table 1 below:

[0062] 表一 [0062] Table I

[0063] [0063]

[〇 [Square

Figure CN106188553AD00091

[0065」尽管本友明的买施万案巳公升如上,但其并小仅仅I很十说明爷和买施万式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。 [0065 "go ahead and buy this case Friends of the Schwann Pat liters above, but I was only ten and a small description and Lord use to buy the listed Schwann type, it can be applied to various fields suitable for the invention, for the person skilled in the art, it can be easily realized a further modification, thus without departing from the generic concept claims and equivalents as defined by the scope of the present invention is not limited to the specific details.

Claims (10)

1. 一种共聚酯电子绝缘垫块,其特征在于,原料配方由以下质量百分含量的材料组成: 对苯二甲酸50%~70%; 乙二醇20%~40%; 1,4-环己烷二甲醇1%~3%; 聚氧化丙烯三醇0.2%~2%; 季戊四醇0.2%~2%; 1,3,5-环己烷三醇0.2%~2%; 醋酸锑0.1%~1%;: 二氧化锗0.1%~1%; 磷酸三甲酯0.1%~2%;: 马来酸酐0.5%~5%;: 苯乙烯0,5%~5½;: 聚对苯二甲酸丁二醇酯3 %~8%; 以上材料的质量百分含量总和为100%。 An electrical insulating spacer copolyester, characterized in that the raw material formulation by the mass percentage of the following composition: terephthalic acid 50% 70%; 20% to 40% ethylene glycol; 1,4 - cyclohexane dimethanol 1% to 3%; polyoxypropylene triol 0.2% to 2%; 0.2% to 2% of pentaerythritol; 1,3,5-cyclohexane triol 0.2% to 2%; antimony acetate 0.1 % to 1% germanium dioxide ;: 0.1% to 1%; trimethyl phosphate ;: 0.1% to 2% maleic anhydride, 0.5% to 5% of styrene ;: 0,5% ~ 5½ ;: polyethylene terephthalate acid butylene glycol 3% to 8%; mass percentage of the total material is 100% or more.
2. 根据权利要求1所述的共聚酯电子绝缘垫块,其特征在于,所述二氧化锗为能够通过800目筛网的白色粉末。 The copolyester of claim 1, said electronically insulating spacer, wherein said germanium dioxide through a screen of 800 mesh as a white powder.
3. 根据权利要求1所述的共聚酯电子绝缘垫块,其特征在于,所述醋酸锑能够通过600 目筛网。 3. The copolyester of claim 1, said electronically insulating spacer, wherein the antimony acetate through 600 mesh screen.
4. 一种共聚酯电子绝缘垫块的制造方法,其特征在于,包括以下步骤: 步骤1)按权利要求1所述原料配方的比例进行称取; 步骤2)将称取好的对苯二甲酸、乙二醇、1,4_环己烷二甲醇、聚氧化丙烯三醇、季戊四醇、1,3,5_环己烷三醇、醋酸锑、二氧化锗和磷酸三甲酯组成的混合物料混合均匀后送至第一酯化反应器中进行酯化反应,生成第一酯化物; 步骤3)将所述第一酯化物和称取好的所述马来酸酐和苯乙烯同时放入第二酯化反应器中进行酯化反应,生成第二酯化物; 步骤4)将第二酯化物和称取好的所述聚对苯二甲酸丁二醇酯送入预缩聚反应器中进行预缩聚反应,生成第一预聚物,将所述第一预聚物经过预聚物过滤器过滤后送入终缩聚反应器中进行终缩聚反应,最终通入氮气,输出共聚酯切片; 步骤5)将所述共聚酯切片进行后续加工处理,得到绝缘垫 A method of manufacturing an electronic insulating spacer copolyester, characterized in that it comprises the following steps: Step 1) as claimed in claim formulation ratio of the raw material is weighed; Step 2) Weigh the good p dicarboxylic acid, glycol, cyclohexanedimethanol 1,4_, polyoxypropylene triol, pentaerythritol, triols 1,3,5_ cyclohexane, antimony acetate, trimethyl phosphate and germanium dioxide composition mixed uniformly mixed feed supplied to the first esterification reactor esterification reaction to produce a first esterification product; step 3) the first esterified product and the good weighed simultaneously discharge maleic anhydride and styrene esterification into the second esterification reactor to produce a second esterification product; step 4) and the second esterified product weighed good the poly (butylene terephthalate) into a pre-polycondensation reactor pre-polycondensation reaction to produce a first prepolymer, the prepolymer after the first prepolymer filters into the final polycondensation reactor in the final polycondensation reaction is carried out, the final nitrogen gas, the output common polyester chips ; step 5) the copolyester slice subsequent processing, to obtain an insulating pad .
5. 如权利要求4所述的共聚酯电子绝缘垫块的制造方法,其特征在于,所述步骤2)中, 将所述混合物料送入浆料调配槽中,在浆料调配槽搅拌器的作用下,搅拌均匀,搅拌器的转速为10r/min,搅拌混合时间为3h。 The copolyester of claim 4, wherein the electronic insulating spacer of the manufacturing method, wherein 2) the step of mixing the material into the slurry preparation tank, stirring the slurry preparation tank under the action of the device, stir, stirrer speed is 10r / min, stirring and mixing time was 3h.
6. 如权利要求5所述的共聚酯电子绝缘垫块的制造方法,其特征在于,所述第一酯化反应温度为245~255°C,第二酯化反应温度为255~265°C,所述预缩聚反应器的操作压力为9 ~llkPa,所述终缩聚反应器的工作温度为265~275°C。 6. The copolyester of claim 5, wherein the electronic method for producing an insulating spacer, characterized in that the first esterification reaction temperature is 245 ~ 255 ° C, the second esterification reaction temperature is 255 ~ 265 ° C, the pre-polycondensation reactor operating pressure is 9 ~ llkPa, the final polycondensation reactor operating temperature is 265 ~ 275 ° C.
7. 如权利要求6所述的共聚酯电子绝缘垫块的制造方法,其特征在于,所述步骤5)中, 所述的后续加工处理为:依次进行预结晶、干燥处理、加热熔融塑化和过滤后,注塑成型,经整形测试后得到最终产物绝缘垫块。 7. The electronic copolyester according to claim 6 a method for producing an insulating spacer, characterized in that, said step 5), the subsequent processing of: sequentially pre-crystallization, drying, heating and melting the plastic after filtration and injection molding, the shaped final product was obtained after testing the insulation spacer.
8. 如权利要求7所述的共聚酯电子绝缘垫块的制造方法,其特征在于,所述二氧化锗为能够通过800目筛网的白色粉末;所述醋酸锑能够通过600目筛网。 8. The copolyester of claim 7, the electronic method for producing an insulating spacer, characterized in that the germanium dioxide through a screen of 800 mesh as a white powder; antimony acetate through a 600 mesh screen .
9. 如权利要求8所述的共聚酯电子绝缘垫块的制造方法,其特征在于,预结晶和干燥温度为150°C~170°C,干燥时间3~4h。 9. The electronic copolyester according to claim 8 method of producing an insulating spacer, characterized in that the pre-crystallization and the drying temperature is 150 ° C ~ 170 ° C, the drying time is 3 ~ 4h.
10. 如权利要求9所述的共聚酯电子绝缘垫块的制造方法,其特征在于,所述加热熔融塑化的加热温度为275°C~285°C。 10. The copolyester of claim 9, the electronic method for producing an insulating spacer, characterized in that the hot-melt plasticized heating temperature of 275 ° C ~ 285 ° C.
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