CN106696115A - 一种aes树脂的制备方法 - Google Patents

一种aes树脂的制备方法 Download PDF

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CN106696115A
CN106696115A CN201611156731.0A CN201611156731A CN106696115A CN 106696115 A CN106696115 A CN 106696115A CN 201611156731 A CN201611156731 A CN 201611156731A CN 106696115 A CN106696115 A CN 106696115A
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aes
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san
resin
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刘秋丽
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Shaanxi Gaohua Zhiben Chemical Technology Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/76Measuring, controlling or regulating
    • B29C45/78Measuring, controlling or regulating of temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/003Compositions 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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/06Compositions 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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C2045/0096Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor drying the moulding material before injection, e.g. by heating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2945/00Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
    • B29C2945/76Measuring, controlling or regulating
    • B29C2945/76494Controlled parameter
    • B29C2945/76531Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Oral & Maxillofacial Surgery (AREA)
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Abstract

一种AES树脂的制备方法,属于材料制备领域,其特征在于包括如下步骤:(1)将AES接枝共聚物剪碎在抽真空干燥箱中脱溶剂到恒重,SAN树脂在烘箱中干燥,放入高速搅拌机中混合均匀;(2)然后通过双螺旋挤出机挤出造粒;(3)用注塑机成型;(4)然后冷压5min拿出,用裁片机裁成需要大小,完成制备。通过对现有工艺的改进,利用溶液法制备AES接枝共聚物,AES接枝共聚物与SAN共混制得AES树脂。随AES接枝共聚物用量的增多,SAN熔融时间缩短,材料的加工扭矩增大。

Description

一种AES树脂的制备方法
技术领域
本发明属于材料制备领域,尤其涉及一种AES树脂的制备方法。
背景技术
AES树脂也称为EPSAN树脂,是三元乙丙橡胶接枝苯乙烯、丙烯腈的共聚物。橡胶相采用耐候性极好的三元乙丙橡胶,赋予AES树脂优良的耐老化性能,即使长时间暴露在室外紫外线照射,雨林,光和臭氧条件下无涂层也可以保持性能不变,广泛应用于户外产品。AES树脂不仅具有优良的耐老化性能,由于橡胶相EPDM玻璃化转变温度低,使AES的耐低温冲击性能优于ABS、AAS,因此,越来越多的被应用于汽车配件,广告牌等使用寿命长,安全可靠的领域。不需要采取措施来减缓其老化使其在价格上、使用时间上更有竞争力。
AES树脂产品为颗粒状,乳白色,无毒,无味。具有优良的耐冲击性能、低温使用性、着色性、耐油性、绝缘性等性能,其耐候性是ABS树脂的4-8倍,加工性能、表面光泽度与ABS树脂相似,可以代替ABS树脂在一些耐候性要求高的领域使用。
AES树脂是由两种材料共混的产物,两相界面的粘结力决定了材料性能的好坏。在共混过程中界面层的形成可以分为两个步骤:第一,两相相互接触,然后两种高分子聚合物链之间相互扩散。在两种类型的交互界面层,一个是双组份化学键链接,如接枝共聚物和嵌段共聚物;第二类是依靠范德华力结合,接枝共聚物和嵌段共聚物也存在范德华力,所以这类聚合物界面层中既有化学键又有范德华力。相互接触的两组分之间会产生界面张力,界面张力越小,其结合强度更大。
发明内容
本发明旨在解决上述问题,提供一种AES树脂的制备方法。
本发明的技术方案为:
一种AES树脂的制备方法,其特征在于包括如下步骤:(1)将AES接枝共聚物剪碎在抽真空干燥箱中脱溶剂到恒重,SAN树脂在烘箱中干燥,EBS是增塑剂,其用量占AES接枝共聚物和SAN树脂质量的5%,原料放入高速搅拌机中混合均匀;(2)然后通过双螺旋挤出机挤出造粒,颗粒在40℃烘箱中干燥12h;(3)用注塑机成型;将平板硫化机升温到175℃,将下好片的AES树脂片材放入模具中,保证充满模具,模具厚度4mm,预热10min,加压至150x105Pa,保压5min;(4)然后冷压5min拿出,用裁片机裁成需要大小,完成制备。
本发明所述的AES树脂的制备方法,所述双螺旋挤出机的温度为140-170℃。
本发明所述的AES树脂的制备方法,所述双螺旋挤出机的主机转速为80rpm。
本发明所述的AES树脂的制备方法,所述注塑机的温度为33-190℃。
本发明所述的AES树脂的制备方法,所述注塑机的注射压力为60bar。
本发明所述的AES树脂的制备方法,所述注塑机的冷却时间为5s。
本发明的技术效果在于:
本发明所述的AES树脂的制备方法,通过对现有工艺的改进,利用溶液法制备AES接枝共聚物,AES接枝共聚物与SAN共混制得AES树脂。随AES接枝共聚物用量的增多,SAN熔融时间缩短,材料的加工扭矩增大;橡胶含量低于10%时冲击强度缓慢增长,脆韧转变发生在橡胶相含量15%~20%;TDDM用量在1%时,AES树脂冲击强度达到最大;随橡胶相用量增加,AES树脂拉伸强度变小,断裂伸长率增大。
具体实施方式
实施例
一种AES树脂的制备方法,其特征在于包括如下步骤:(1)将AES接枝共聚物剪碎在抽真空干燥箱中脱溶剂到恒重,SAN树脂在烘箱中干燥,EBS是增塑剂,其用量占AES接枝共聚物和SAN树脂质量的5%,原料放入高速搅拌机中混合均匀;(2)然后通过双螺旋挤出机挤出造粒,颗粒在40℃烘箱中干燥12h;(3)用注塑机成型;将平板硫化机升温到175℃,将下好片的AES树脂片材放入模具中,保证充满模具,模具厚度4mm,预热10min,加压至150x105Pa,保压5min;(4)然后冷压5min拿出,用裁片机裁成需要大小,完成制备。
本发明所述的AES树脂的制备方法,所述双螺旋挤出机的温度为140℃。
本发明所述的AES树脂的制备方法,所述双螺旋挤出机的主机转速为80rpm。
本发明所述的AES树脂的制备方法,所述注塑机的温度为33-190℃。
本发明所述的AES树脂的制备方法,所述注塑机的注射压力为60bar。
本发明所述的AES树脂的制备方法,所述注塑机的冷却时间为5s。冲击强度是衡量AES树脂的重要指标,对三元乙丙橡胶进行接枝改性就是为了使橡胶在SAN树脂中可以均匀的分散,使两相可以达到很好地相容性。EPDM分散在塑料中起到应力集中中心的作用,受到外力的作用可以诱发大量银纹和剪切带,吸收大量能量,从而起到增韧SAN树脂的作用。橡胶相在塑料中可以很好地分散条件下,随橡胶相的增加,体系中橡胶相的粒径会增加,橡胶相的增加同时会给加工带来困难,造成熔融粘度高,注塑过程中需要增加注塑料量。
采用接枝率为25%的EPDM3960Q接枝共聚物,橡胶相含量为20%,通过与SAN树脂共混制备不同橡胶含量的AES树脂,同时采用不改姓橡胶作对照研究橡胶相含量对AES树脂冲击强度的影响。纯SAN树脂冲击强度2KJ/m2,橡胶相含量低于10%时,随着橡胶相的增加,AES树脂冲击强度缓慢增加;橡胶相含量8%时,冲击强度只有4.2KJ/m2,与纯SAN相比增加1倍;橡胶相含量在10%~20%,冲击强度增长加快,冲击强度由5.2 KJ/m2增长到15.4 KJ/m2,与纯SAN相比冲击强度提高了7.7倍。乙丙橡胶不经过改性直接与SAN树脂共混,随着橡胶相的增加,冲击强度没有明显变大,基本没有增韧效果。
EPDM橡胶粒子在增韧体系中发挥两个重要作用,一是作为应力集中中心诱发大量银纹和剪切带,二是控制银纹的发展,并使银纹终止,而不致发展成破坏性裂纹,银纹尖端的应力场可诱发剪切带的产生,而剪切带也可阻止银纹的进一步发展,银纹和剪切带的产生和发展要消耗大量的能量,因而使材料冲击强度显著提高。
随橡胶相的增加,AES树脂拉伸强度逐渐降低,断裂伸长率逐渐增大。橡胶相增多,材料的硬度会逐渐下降,受到拉应力作用产生的银纹数量就会增多,达到相同的应变所需的应力就会减小。
分子量调节剂的用量影响苯乙烯、丙烯腈共聚反应,使接枝到EPDM上的SAN分子量降低,同时游离的SAN树脂分子量减小,从而对冲击强度产生影响。AES树脂中橡胶相含量20%,AES接枝共聚物制备时橡塑比20:80。改变分子量调节剂用量,制备多组AES接枝共聚物,与一定比例SAN树脂共混造粒,制成标准样条,测定其冲击强度,并测定被提取SAN的分子量,分子量调节剂对游离SAN分子量有显著影响,因为TDDM为链转移剂,可以诱发链转移,降低产物分子量。实验中加入TDDM后,降低了EPDM的接枝率,使EPDM表层接枝SAN量减少。随分子量调节剂用量的不同,用量在1%时,冲击强度达到峰值,接枝到EPDM上的SAN分子量与TDDM用量成反比,在TDDM用量为1%时达到最佳值。
TDDM可以有效调节AES树脂分子量,它的化学性质非常活泼,易于跟大分子活性链自由基发生链转移反应,使活性链失去活性并同时自身又生成新的自由基,这种新的自由基继续引发聚合16511。MFR越大,材料的流动性越好,同类材料分子量越低。随着TDDM用量的增加,AES树脂的熔体流动速率不断增大,相对分子质量不断降低。当TDDM质量分数超过0.4%时,AES树脂MFR提高显著。随AES接枝共聚物用量的增多,SAN熔融时间缩短,材料的加工扭矩增大。

Claims (6)

1.一种AES树脂的制备方法,其特征在于包括如下步骤:(1)将AES接枝共聚物剪碎在抽真空干燥箱中脱溶剂到恒重,SAN树脂在烘箱中干燥, EBS是增塑剂,其用量占AES接枝共聚物和SAN树脂质量的5%,原料放入高速搅拌机中混合均匀;(2)然后通过双螺旋挤出机挤出造粒,颗粒在40℃烘箱中干燥12h;(3)用注塑机成型;将平板硫化机升温到175℃,将下好片的AES树脂片材放入模具中,保证充满模具,模具厚度4mm,预热10min,加压至150x105Pa,保压5min;(4)然后冷压5min拿出,用裁片机裁成需要大小,完成制备。
2.根据权利要求1所述的AES树脂的制备方法,其特征在于:所述双螺旋挤出机的温度为140-170℃。
3.根据权利要求1所述的AES树脂的制备方法,其特征在于:所述双螺旋挤出机的主机转速为80rpm。
4.根据权利要求1所述的AES树脂的制备方法,其特征在于:所述注塑机的温度为33-190℃。
5.根据权利要求1所述的AES树脂的制备方法,其特征在于:所述注塑机的注射压力为60bar。
6.根据权利要求1所述的AES树脂的制备方法,其特征在于:所述注塑机的冷却时间为5s。
CN201611156731.0A 2016-12-15 2016-12-15 一种aes树脂的制备方法 Pending CN106696115A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107599255A (zh) * 2017-08-31 2018-01-19 无锡南理工科技发展有限公司 胶样的硫化制造和检验方法
CN107722486A (zh) * 2017-09-19 2018-02-23 广东圆融新材料有限公司 一种耐候抗菌防霉aes材料及其制备方法
CN110964269A (zh) * 2019-12-02 2020-04-07 天津金发新材料有限公司 一种耐低温、永久抗静电、耐热aes组合物及其制备方法与应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107599255A (zh) * 2017-08-31 2018-01-19 无锡南理工科技发展有限公司 胶样的硫化制造和检验方法
CN107722486A (zh) * 2017-09-19 2018-02-23 广东圆融新材料有限公司 一种耐候抗菌防霉aes材料及其制备方法
CN110964269A (zh) * 2019-12-02 2020-04-07 天津金发新材料有限公司 一种耐低温、永久抗静电、耐热aes组合物及其制备方法与应用

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Application publication date: 20170524