CN113183582A - 一种各向同性的玻纤网增强pet合金板的制备方法 - Google Patents

一种各向同性的玻纤网增强pet合金板的制备方法 Download PDF

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CN113183582A
CN113183582A CN202110532396.4A CN202110532396A CN113183582A CN 113183582 A CN113183582 A CN 113183582A CN 202110532396 A CN202110532396 A CN 202110532396A CN 113183582 A CN113183582 A CN 113183582A
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pet
glass fiber
added
mass
screw extruder
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吴驰飞
计龙辉
李桂春
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Shanghai Xiansu New Material Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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    • B29C43/20Making multilayered or multicoloured articles
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    • 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
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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    • B32LAYERED PRODUCTS
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    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • B32LAYERED PRODUCTS
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    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2307/00Properties of the layers or laminate
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Abstract

本发明提供了一种各向同性玻纤网增强PET合金的制备方法,通过玻纤网与PET板复合,提高PET板的机械强度,增强所述合金的拉伸强度,弯曲强度和弯曲模量,通过对PET板的结构化处理使得改性的PET板更容易与玻纤网复合,从而提高表层的耐热性和耐候性。

Description

一种各向同性的玻纤网增强PET合金板的制备方法
技术领域
本发明涉及一种各向同性的玻纤网增强PET合金板的制备方法。
背景技术
PET是开发最早、产量最大、应用范围最广泛的聚酯产品。它的综合性能优异,可以在较宽的范围内保持优良的物理性能,广泛应用于衣着、家庭装饰、包装以及工程等领域,因此产生大量废料。而PET被认为是最容易回收的塑料,回收PET材料在价格上,环保意义上具有很大的优势。目前将回收PET用于制备建筑模板,塑料板等方面已有人开始研究,但是由于回收PET材料性能,工艺等因素,导致板材的抗拉伸强度,抗弯强度以及耐老化性能不尽如人意,还需要进一步的改进提高。
发明内容
本发明提供了一种各向同性玻纤网增强PET合金的制备方法,通过玻纤网与PET板复合,提高PET板的机械强度,增强所述合金的拉伸强度,弯曲强度和弯曲模量,通过对PET板的结构化处理使得改性的PET板更容易与玻纤网复合,从而提高表层的耐热性和耐候性。
具体的方案如下:
一种各向同性玻纤网增强PET合金板的制备方法,包括:
1) 将回收PET/PE按照一定的比例与扩链剂,相容剂和抗氧剂混合,得到混合物;
2) 将步骤1得到的混合物经过双螺杆挤出机挤出得到PET/PE条;
3) 将部分所述步骤2得到的产物再次加入到双螺杆挤出机中,加入硅烷偶联剂,挤出得到改性PET/PE条;
4) 将步骤2的产物和步骤3的产物,压板成型得到板材,所述板材由三层组成,中间层由步骤2产物压制而成,两侧面层由步骤3的产物压制而成;
5) 提供各向同性玻纤网叠置于步骤4得到的板材的两侧,热压,得到所述各向同性玻纤网增强PET合金板。
进一步的,所述PET/PE中,PET与PE的质量比为100:40-80。
进一步的,步骤2、3中的挤出温度为250-260℃。
进一步的,所述步骤4中的压板的温度为245℃,压力为25kN。
进一步的,所述步骤1中,扩链剂为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物,加入质量为PET/PE的5%;所述相容剂为HDPE-g-GMA,加入质量为PET/PE的14%;抗氧剂由质量比2:1的DPN和DLTP组成,加入质量为PET/PE的4%。
进一步的,所述步骤2中,所述步骤1得到的产物由所述双螺杆挤出机的主料进口加入,第一助剂由所述双螺杆挤出机的辅料进口加入,所述第一助剂的加入质量为所述步骤1得到的产物的8-12%,所述第一助剂由异丙烯基三乙氧基硅烷44%,过氧化二异丙苯40%,二月桂酸二丁基锡10%和三乙烯二胺6%组成。
进一步的,所述步骤3中,所述步骤2得到的产物由所述双螺杆挤出机的主料进口加入,第二助剂和硅烷偶联剂由所述双螺杆挤出机的辅料进口加入,所述第二助剂的加入质量为所述步骤2得到的产物的3-6%,所述第二助剂由苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物52%,过氧化二异丙苯36%,和氧化镧12%组成;所述硅烷偶联剂的加入质量为步骤2得到的产物的4-5%。
本发明具有如下有益效果:
1、通过混杂料中各组分配比的调控,以及相容剂等的选用方面的改进,实现了茂金属线型低密度聚乙烯在PET机体中的均匀分散,除了扩链反应之外还形成物理交联点,增加材料的强刚度;
2、第一助剂促进材料中物理交联点的形成,提高材料的韧性和强刚度;
3、硅烷偶联剂能够提高玻璃纤维的表面活性,提高玻纤网的与板材的复合度;
4、第二助剂中的氧化镧作为成核剂,提高结晶温度,促进材料的注塑性能,第二助剂中的其他成分有利于提高表层材料的结构刚性以及耐老化性能;
5、采用的压板和热压玻纤网成型方式,玻纤的取向明显,受力的时候,基体将力传导到沿拉伸方向的玻纤上,拉伸和弯曲性能提高。
本发明通过上述方法,制得的合金性能高,利用范围广泛,并且工艺简单,成本低廉,易于大规模生产。
具体实施方式
本发明下面将通过具体的实施例进行更详细的描述,但本发明的保护范围并不受限与实施例。
实施例 1
将回收PET/PE与占其质量的5%苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、14%HDPE-g-GMA,4%的抗氧剂混合60min,所述抗氧剂由质量比2:1的DPN和DLTP组成,所述PET和PE的质量比为100:40;得到的混合物由双螺杆挤出机的主料进口加入,第一助剂由所述双螺杆挤出机的辅料进口加入,所述第一助剂的加入质量为所述混合物的8%,所述第一助剂由异丙烯基三乙氧基硅烷44%,过氧化二异丙苯40%,二月桂酸二丁基锡10%和三乙烯二胺6%组成;所述挤出机的加热段温度分别为220℃,220℃,240℃,240℃,240℃,机头挤出温度为250℃,螺杆转速100r/min,挤出得到PET/PE条;将部分得到的PET/PE条再次加入双螺杆挤出机,其由所述双螺杆挤出机的主料进口加入,第二助剂由所述双螺杆挤出机的辅料进口加入,所述第二助剂的加入质量为所述PET/PE条的3%,所述第二助剂由苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物52%,过氧化二异丙苯36%,和氧化镧12%组成;所述硅烷偶联剂的加入质量为步骤2得到的产物的4%,挤出得到改性PET/PE条;将所述PET/PE条和所述改性PET/PE条压板成型得到板材,压板成型的温度为245℃,压力为25kN,所述板材由三层组成,所述板材由三层组成,中间层由所述PET/PE压制而成,两侧面层由所述改性PET/PE压制而成;提供各向同性玻纤网置于所述板材两侧面,通过高温压辊热压,压缩比为20%,压辊温度为200℃,得到厚度为5mm的合金板,将压好的板裁成100×10mm的样条。
实施例 2
将回收PET/PE与占其质量的5%苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、14%HDPE-g-GMA,4%的抗氧剂混合60min,所述抗氧剂由质量比2:1的DPN和DLTP组成,所述PET和PE的质量比为100: 80;得到的混合物由双螺杆挤出机的主料进口加入,第一助剂由所述双螺杆挤出机的辅料进口加入,所述第一助剂的加入质量为所述混合物的12%,所述第一助剂由异丙烯基三乙氧基硅烷44%,过氧化二异丙苯40%,二月桂酸二丁基锡10%和三乙烯二胺6%组成;所述挤出机的加热段温度分别为220℃,220℃,240℃,240℃,240℃,机头挤出温度为260℃,螺杆转速100r/min,挤出得到PET/PE条;将部分得到的PET/PE条再次加入双螺杆挤出机,其由所述双螺杆挤出机的主料进口加入,第二助剂由所述双螺杆挤出机的辅料进口加入,所述第二助剂的加入质量为所述PET/PE条的6%,所述第二助剂由苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物52%,过氧化二异丙苯36%,和氧化镧12%组成;所述硅烷偶联剂的加入质量为步骤2得到的产物的5%,挤出得到改性PET/PE条;将所述PET/PE条和所述改性PET/PE条压板成型得到板材,压板成型的温度为245℃,压力为25kN,所述板材由三层组成,所述板材由三层组成,中间层由所述PET/PE压制而成,两侧面层由所述改性PET/PE压制而成;提供各向同性玻纤网置于所述板材两侧面,通过高温压辊热压,压缩比为20%,压辊温度为200℃,得到厚度为5mm的合金板,将压好的板裁成100×10mm的样条。
实施例 3
将回收PET/PE与占其质量的5%苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物、14%HDPE-g-GMA,4%的抗氧剂混合60min,所述抗氧剂由质量比2:1的DPN和DLTP组成,所述PET和PE的质量比为100:60;得到的混合物由双螺杆挤出机的主料进口加入,第一助剂由所述双螺杆挤出机的辅料进口加入,所述第一助剂的加入质量为所述混合物的10%,所述第一助剂由异丙烯基三乙氧基硅烷44%,过氧化二异丙苯40%,二月桂酸二丁基锡10%和三乙烯二胺6%组成;所述挤出机的加热段温度分别为220℃,220℃,240℃,240℃,240℃,机头挤出温度为250℃,螺杆转速100r/min,挤出得到PET/PE条;将部分得到的PET/PE条再次加入双螺杆挤出机,其由所述双螺杆挤出机的主料进口加入,第二助剂由所述双螺杆挤出机的辅料进口加入,所述第二助剂的加入质量为所述PET/PE条的4%,所述第二助剂由苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物52%,过氧化二异丙苯36%,和氧化镧12%组成;所述硅烷偶联剂的加入质量为步骤2得到的产物的4.5%,挤出得到改性PET/PE条;将所述PET/PE条和所述改性PET/PE条压板成型得到板材,压板成型的温度为245℃,压力为25kN,所述板材由三层组成,所述板材由三层组成,中间层由所述PET/PE压制而成,两侧面层由所述改性PET/PE压制而成;提供各向同性玻纤网置于所述板材两侧面,通过高温压辊热压,压缩比为20%,压辊温度为200℃,得到厚度为5mm的合金板,将压好的板裁成100×10mm的样条。
测试与结果
力学性能测试:材料的拉伸性能测试按照GB/T1040.2-2006标准在室温下进行,拉伸速率为10mm/min;弯曲性能按照GB/T9341-2008标准进行测试,速率为2mm/min。每组试样测试5次以上,结果取平均值。
表1
Figure 833935DEST_PATH_IMAGE002
由表1中可见,本发明提供的产品的力学性能有明显的提升,拉伸强度和弯曲强度都成倍提高。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但是应当认识到上述的描述不应被认为是对本发明的限制。

Claims (7)

1.一种各向同性玻纤网增强PET合金板的制备方法,包括:
1)将回收PET/PE按照一定的比例与扩链剂,相容剂和抗氧剂混合,得到混合物;
2)将步骤1得到的混合物经过双螺杆挤出机挤出得到PET/PE条;
3)将部分所述步骤2得到的产物再次加入到双螺杆挤出机中,加入硅烷偶联剂,挤出得到改性PET/PE条;
4)将步骤2的产物和步骤3的产物,压板成型得到板材,所述板材由三层组成,中间层由步骤2产物压制而成,两侧面层由步骤3的产物压制而成;
5)提供各向同性玻纤网叠置于步骤4得到的板材的两侧,热压,得到所述各向同性玻纤网增强PET合金板。
2.如权利要求1所述的方法,所述PET/PE中,PET与PE的质量比为100:40-80。
3.如权利要求1所述的方法,步骤2、3中的挤出温度为250-260℃。
4.如权利要求1所述的方法,所述步骤4中的压板的温度为245℃,压力为25kN。
5.如权利要求1所述的方法,所述步骤1中,扩链剂为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物,加入质量为PET/PE的5%;所述相容剂为HDPE-g-GMA,加入质量为PET/PE的14%;抗氧剂由质量比2:1的DPN和DLTP组成,加入质量为PET/PE的4%。
6.如权利要求1所述的方法,所述步骤2中,所述步骤1得到的产物由所述双螺杆挤出机的主料进口加入,第一助剂由所述双螺杆挤出机的辅料进口加入,所述第一助剂的加入质量为所述步骤1得到的产物的8-12%,所述第一助剂由异丙烯基三乙氧基硅烷44%,过氧化二异丙苯40%,二月桂酸二丁基锡10%和三乙烯二胺6%组成。
7.如权利要求6所述的方法,所述步骤3中,所述步骤2得到的产物由所述双螺杆挤出机的主料进口加入,第二助剂和硅烷偶联剂由所述双螺杆挤出机的辅料进口加入,所述第二助剂的加入质量为所述步骤2得到的产物的3-6%,所述第二助剂由苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯共聚物52%,过氧化二异丙苯36%,和氧化镧12%组成;所述硅烷偶联剂的加入质量为步骤2得到的产物的4-5%。
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