CN112111805B - 一种增强型pet扁丝的制备方法 - Google Patents

一种增强型pet扁丝的制备方法 Download PDF

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CN112111805B
CN112111805B CN201910967618.8A CN201910967618A CN112111805B CN 112111805 B CN112111805 B CN 112111805B CN 201910967618 A CN201910967618 A CN 201910967618A CN 112111805 B CN112111805 B CN 112111805B
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polyester
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戴钧明
王玉合
王树霞
刘峰
王坤
司虎
吕占峰
吴旭华
李红芳
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China Petroleum and Chemical Corp
Sinopec Yizheng Chemical Fibre Co Ltd
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Abstract

本发明公开了一种增强型PET扁丝的制备方法,由于在PET聚合过程添加液体纳米助剂,使改性PET聚酯内部产生分散均匀的微小晶点,同时使大分子链的柔性提高。此共聚酯可大幅度提高PET扁丝的物理强度,制得的PET扁丝拉伸强度≥450Mpa,可应用于对强度、耐候性、温度等使用条件要求高的编织物的生产,尤其适用于生产高性能的编织袋和集装袋领域及高强、耐高温地毯领域。

Description

一种增强型PET扁丝的制备方法
技术领域:
本发明属于高分子材料加工领域领域,特别涉及一种增强型PET扁丝的制备方法。
背景技术:
目前国内外生产、销售、使用的塑料编织袋,都是以聚丙烯树酯(PP)为原料制造扁丝,然后编织成编织袋包装物品。由于聚丙烯编织袋容易与包装物分离、质量轻、成本低,已广泛用于化工、矿产粉体、建材及粮食等大综产品的包装。但是,由于PP耐候性差、易氧化,导致其氧化降解,在存放过程中编织袋的机械强度,尤其抗冲击强度大幅降低,影响包装效果。PET的力学性能、耐高低温性能、耐候性能等均比PP要好,但是,PET存在玻璃化温度较高,分子刚性较大,拉伸强力大,结晶速度慢等问题,以至于生产PET扁丝时断丝情况严重,无法正常连续生产,且存在拉出的扁丝强度不够等问题。即关于利用PET生产扁丝低的技术中面临着原料配方和加工工艺的改进问题。
经申请人检索发现,为了改善PET的韧性,现有技术一般在熔融挤出时共混加入一定量聚烯烃类增韧剂,同时添加一定量相容剂,但聚烯烃增韧剂加入后会导致产品强度下降;为了提高产品强度,现有技术一般在熔融挤出时共混加入一定量的碳酸钙、滑石粉、钛白粉、蒙脱土、二氧化硅等无机类填充剂,如中国专利201410059274.8,21610661881.0,201210456737.5,201310262145.4等。可以看出,现有技术仅仅通过添加增韧剂、无机填充剂等方式来解决PET扁丝生产中存在的韧性差和强度低的问题,但通过添加助剂的方式存在加入量受限、混合不均匀等问题,对强度的提升存在局限性。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容:
本发明的目的在于提供一种增强型PET扁丝的制备方法,从而克服上述现有 技术中的缺陷。
为实现上述目的,本发明提供了一种增强型PET扁丝的制备方法,其特征在于,在改性PET的制备过程中的酯化反应完成后、缩聚反应之前,添加相对于聚酯PET质量百分比0.8-1.8‰的微米级硫酸钡粒,同时相对于聚酯PET质量百分比1-2‰的液体纳米助剂,液体纳米助剂结构通式 : [CH2=CH(CH2)n]mSiX(4-m),其中0≤n≤6,1≤m≤3,X为甲氧基、乙氧基、甲氧基乙氧基、环氧基中的一种。
由于在PET聚合过程添加液体纳米助剂[CH2=CH(CH2n]mSiX(4-m),使共聚酯内部产生分散均匀的微小晶点,同时使大分子链的柔性提高。本助剂的结构式中的直链烯烃基团具有柔韧性及应力转移的功能,可产生自润滑作用,导致粘度大幅度下降,改善加工工艺,增加制品的延伸率和撕裂强度,提高冲击性能,解决了PET材料因脆性较大无法应用于扁丝领域的问题,使其韧性提高可满足扁丝加工的要求。聚合过程加入硫酸钡相比螺杆中共混添加的方式均匀性提高,同时助剂中的甲氧基、乙氧基、甲氧基乙氧基、环氧基等基团在体系中水解形成硅醇基团,然后与硫酸钡之间通过共价键进行结合,形成晶核,并进一步通过助剂中共价双键与大分子链间的共价结合,加快了结晶速率,形成众多微小的晶点,有利于强度的提升,改善了因单纯直链烯烃的加入导致扁丝强度下降的问题。
本发明进一步限定的技术方案为:
进一步的,硫酸钡粒径0.5微米-1.5微米。
进一步的,助剂添加完成后搅拌5min后再开始抽真空进入缩聚过程。
进一步的,制备方法按照如下步骤进行:
S1,精对苯二甲酸PTA、乙二醇EG在催化剂的催化下经酯化反应、添加相对于聚酯PET质量百分比0.8-1.8‰的微米级硫酸钡粒,同时相对于聚酯PET质量百分比1-2‰的液体纳米助剂,缩聚反应达到一定时间后出料,经切粒、干燥,制得PET共聚酯切片;
S2,PET共聚酯切片干燥后经螺杆挤出机熔融挤出得到熔体,螺杆温度250-290℃,熔体经50-60℃急冷辊冷却得到铸片;
S3,铸片分切后得到PET胚丝,胚丝经80-90℃预热,进行单向一级或二级拉伸,拉伸温度95-105℃,拉伸比4.5-7,然后在160-180℃下热定型,定型后收卷得到PET扁丝样品。
进一步的,步骤S1中,酯化温度255℃~265℃,压力0.2-0.3MPa;缩聚温度280℃~283℃,压力≤60Pa。
进一步的,步骤S1中,所用催化剂为STiC-01钛系催化剂,添加量≤10μg/g,酯化前酯化后添加均可。
进一步的,步骤S2中,所得PET共聚酯切片的特性粘度0.640-0.750dL/g。
进一步的,步骤S4中,得到PET扁丝样品具体为:PET扁丝宽度≤2.5mm,厚度≤50μm,单丝拉伸强度≥450Mpa,断裂伸长率≥15%。
与现有技术相比,本发明具有如下有益效果:
此改性PET可大幅度提高PET扁丝的物理强度,且挤出过程无需再添加增韧剂等助剂,制得的PET扁丝拉伸强度≥450Mpa,断裂伸长率≥15%,可应用于对强度、耐候性、温度等使用条件要求高的编织物的生产,尤其适用于生产高性能的编织袋和集装袋领域及耐高温地毯领域,同时本发明使用环境友好型钛系催化剂,制得的制品安全环保。
具体实施方式:
下面对本发明的具体实施方式进行详细描述,但应当理解本发明的保护 范围并不受具体实施方式的限制。
除非另有其它明确表示,否则在整个说明书和权利要求书中,术语“包 括”或其变换如“包含”或“包括有”等等将被理解为包括所陈述的元件或 组成部分,而并未排除其它元件或其它组成部分。
实施例1:本发明所述一种增强型PET扁丝的制备方法, 首先进行改性PET的制备,然后进行PET扁丝的制备,主要包括以下步骤:
改性PET的制备:将60Kg精对苯二甲酸、32Kg乙二醇 投入150L聚合反应釜,并加入5μg/g(质量百分比,相对于聚酯PET,下同)的STiC-01钛系催化剂,升温进行酯化反应,酯化温度255℃~265℃,压力0.2-0.3MPa,酯化结束后分别加入2‰的液体纳米助剂[CH2=CH(CH2)6]3SiOCH2CH3、1.8‰的微米硫酸钡,搅拌5min后继续升温进行缩聚反应,缩聚温度280℃~283℃,压力≤60Pa;达到一定时间后出料,经切粒、干燥,制得改性PET聚酯切片,特性粘度0.750dL/g。
PET扁丝的制备:将上述制备的改性PET聚酯经155℃真空烘箱干燥后经螺杆挤出机熔融挤出得到熔体,螺杆温度250-288℃,熔体经急冷辊(急冷辊温度55-60℃)冷却得到铸片,铸片经切刀分切后制得PET胚丝,胚丝经导辊牵引进入纵向拉伸机,经90℃预热后,进行单向二级拉伸,拉伸温度105℃,总拉伸倍率为7倍,然后在180℃下热定型,最后收卷得到PET扁丝成品,厚度40-50μm,宽度2.0-2.5mm,所得PET扁丝单丝拉伸强度900-1000Mpa,断裂伸长率15-20%。
实施例2:改性PET聚酯制备及PET扁丝的制备工艺与实施例1相同,所不同的是,总拉伸倍率为6倍,热定型温度165℃,收卷得到PET扁丝成品,厚度40-50μm,宽度1.8-2.0mm,所得PET扁丝单丝拉伸强度800-900Mpa,断裂伸长率15-25%。
实施例3:改性PET聚酯制备及PET扁丝的制备工艺与实施例1相同,所不同的是,拉伸倍率为5倍,单向一级拉伸,收卷得到PET的扁丝成品,厚度40-50μm,宽度1.6-1.8mm,所得PET扁丝单丝拉伸强度600-700Mpa,断裂伸长率25-35%。
实施例4:改性PET聚酯制备及PET扁丝的制备工艺与实施例1相同,所不同的是酯化结束后加入1.5‰的液体纳米助剂[CH2=CH(CH2)3]2Si(OCH3)2、1.2‰的微米硫酸钡,共聚酯特性粘度0.700dL/g,胚丝拉伸前预热温度85℃,拉伸温度100℃,总拉伸倍率为6倍,然后在170℃下热定型,最后收卷得到PET扁丝成品,厚度40-50μm,宽度1.4-1.6mm,所得PET扁丝单丝拉伸强度600-700Mpa,断裂伸长率20-30%。
实施例5:改性PET聚酯制备及PET扁丝的制备工艺与实施例1相同,所不同的是酯化结束后加入1‰的液体纳米助剂[CH2=CH(CH2)3]2Si(OCH2CH2OCH3)2、0.9‰的微米硫酸钡,共聚酯特性粘度0.640dL/g,PET扁丝制备路线为:熔体经55℃急冷辊冷却得到铸片,胚丝拉伸前预热温度80℃,拉伸温度95℃,一级拉伸,拉伸倍率为5倍,然后在160℃下热定型,最后收卷得到PET扁丝成品,厚度40-50μm,宽度1.2-1.4mm,所得PET扁丝单丝拉伸强度500-600Mpa,断裂伸长率20-30%。
实施例6:改性PET聚酯制备及PET扁丝的制备工艺与实施例3相同,所不同的是一级拉伸倍率为4.5倍,然后在160℃下热定型,最后收卷得到PET扁丝成品,厚度40-50μm,宽度1-1.2mm,所得PET扁丝单丝拉伸强度460-500Mpa,断裂伸长率20-30%。
实施例7:改性PET聚酯制备及PET扁丝的制备工艺与实施例1相同,所不同的是酯化结束后加入1‰的液体纳米助剂CH2=CHCH2 Si(OCH2CH2)3、0.8‰的微米硫酸钡,共聚酯特性粘度0.640dL/g,PET扁丝制备路线为:熔体经55℃急冷辊冷却得到铸片,胚丝拉伸前预热温度85℃,拉伸温度95℃,一级拉伸,拉伸倍率为5倍,然后在160℃下热定型,最后收卷得到PET扁丝成品,厚度40-50μm,宽度2.0-2.2mm,所得PET扁丝单丝拉伸强度450-500Mpa,断裂伸长率20-30%。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。 这些描述并非想将本发明限定为所公开的精确形式,并且很显然,根据上述 教导,可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在 于解释本发明的特定原理及其实际应用,从而使得本领域的技术人员能够实 现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。 本发明的范围意在由权利要求书及其等同形式所限定。

Claims (5)

1.一种增强型PET扁丝的制备方法,其特征在于,在改性PET的制备过程中的酯化反应完成后、缩聚反应之前,添加相对于聚酯PET质量百分比0.8-1.8‰的微米级硫酸钡粒,硫酸钡粒径0.5微米-1.5微米;
同时相对于聚酯PET质量百分比1-2‰的液体纳米助剂,液体纳米助剂结构通式 : [CH2=CH(CH2n]mSiX(4-m),其中0≤n≤6,1≤m≤3,X为甲氧基、乙氧基、甲氧基乙氧基中的一种;
制备方法按照如下步骤进行:
S1,精对苯二甲酸PTA、乙二醇EG在催化剂的催化下经酯化反应、添加相对于聚酯PET质量百分比0.8-1.8‰的微米级硫酸钡粒,同时相对于聚酯PET质量百分比1-2‰的液体纳米助剂,缩聚反应达到一定时间后出料,经切粒、干燥,制得PET共聚酯切片;
S2,PET共聚酯切片干燥后经螺杆挤出机熔融挤出得到熔体,螺杆温度250-290℃,熔体经50-60℃急冷辊冷却得到铸片;
S3,铸片分切后得到PET胚丝,胚丝经80-90℃预热,进行单向一级或二级拉伸,拉伸温度95-105℃,拉伸比4.5-7,然后在160-180℃下热定型,定型后收卷得到PET扁丝样品;
步骤S3中,得到PET扁丝样品具体为:PET扁丝宽度≤2.5mm,厚度≤50μm,单丝拉伸强度≥450Mpa,断裂伸长率≥15%。
2.根据权利要求1所述的增强型PET扁丝的制备方法,其特征在于,助剂添加完成后搅拌5min后再开始抽真空进入缩聚过程。
3.根据权利要求1所述的增强型PET扁丝的制备方法,其特征在于,步骤S1中,酯化温度255℃~265℃,压力0.2-0.3MPa;缩聚温度280℃~283℃,压力≤60Pa。
4.根据权利要求1所述的增强型PET扁丝的制备方法,其特征在于,步骤S1中,所用催化剂为STiC-01钛系催化剂,相对于聚酯PET,添加量为:0<STiC-01钛系催化剂≤10μg/g。
5.根据权利要求1所述的增强型PET扁丝的制备方法,其特征在于,步骤S1中,所得PET共聚酯切片的特性粘度0.640-0.750dL/g。
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