CN102227462B - 共聚物聚酯树脂和使用该共聚物聚酯树脂的模塑产品 - Google Patents
共聚物聚酯树脂和使用该共聚物聚酯树脂的模塑产品 Download PDFInfo
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- -1 cyclohexane dimethanol compound Chemical class 0.000 claims abstract description 12
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及共聚物聚酯树脂以及使用该共聚物聚酯树脂的模塑产品,更具体来说,本发明涉及一种共聚物聚酯树脂,其包含10~80摩尔%的1,4-环己烷二甲醇,0.1~30摩尔%的式HOH2C-[C6H12]m-[C6H12]-CH2OH(其中m是1~10的整数)所示的环己烷二甲醇化合物,以及余量的乙二醇,以芳族二羧酸为基准计,使得整个二醇组合物的总和可以为100摩尔%。本发明的共聚物聚酯能够提供优良的产品,所述产品能在使用热收缩标签进行模塑处理的过程中,通过弥补低温收缩性质而缩短周期时间和提高产品的成型性,那些用1,4-环己烷二甲醇共聚的现有技术的聚酯树脂可能会表现出所述的低温收缩性质。
Description
技术领域
本发明涉及包含1,4-环己烷二甲醇的共聚物聚酯树脂以及使用该树脂的模塑产品,更具体来说,本发明涉及基于热收缩聚酯的组合物,该组合物非常适合用于标签,本发明还涉及使用该组合物的膜。
背景技术
热收缩性塑料产品具有受热收缩性质,非常广泛地用于收缩包装、收缩标签等之类的膜。具体来说,基于聚氯乙烯(PVC),聚苯乙烯和聚酯的塑料膜被用来对各种容器贴标签或者进行盖封,或者直接进行包装。
但是,由PVC制造的膜在焚化的时候可能会产生氯化氢气体和产生二噁英的材料,因此受到环保方面的限制。如果此种产品用作PET容器的收缩标签,则只有在通过繁杂的分离操作,将标签与容器分离之后,才能够对容器进行回收利用。
基于聚苯乙烯的膜也可以在收缩处理过程中非常稳定地发挥作用,并且具有良好的外观,但是其耐化学性较差,需要使用具有特定组成的油墨进行印刷,这是不利的因素。另外,这种膜在室温下的储存稳定性较差,因此会自动收缩,会使得其尺寸发生不利的变形。
人们非常关注那些不存在这些问题的由聚酯树脂制备的膜作为收缩标签,用来代替上述两种材料制备的膜。另外,随着PET容器的应用的增加,人们更加迫切地需要可以很容易再生的聚酯膜,以便能够无需单独除去标签就可以对容器进行再循环。但是,常规的热收缩聚酯膜的收缩性质必需加以改进。由于收缩性质的显著改变,这些膜可能会起皱,或者发生不均匀的收缩,使得在模塑的过程中,它们的形状偏离预先的设计,可能会频繁地造成不利的问题。另外,与基于PVC的膜或者基于聚苯乙烯的膜相比,聚酯膜在低温下的收缩性较差,因此只应在高温下收缩。在此情况下,PET容器会发生不利的变形或者产生白色混浊。
发明内容
技术问题
因此,本发明用来解决相关领域遇到的问题,用来提供一种共聚物聚酯树脂,该树脂可能弥补差的低温收缩性,在使用热收缩标签进行模塑加工的过程中,可以缩短周期时间,改进产品的成型性,本发明还提供了包含所述共聚物聚酯树脂的热收缩膜。
技术方案
本发明的一个方面提供了一种共聚物聚酯树脂,其包含10~80摩尔%1,4-环己烷二甲醇,0.1~30摩尔%以下式1所示的基于环己烷二甲醇的化合物,以及余量的乙二醇,使得以芳族二羧酸为基准计,整个二醇组合物的总和为100摩尔%。
[式1]
式中m是1~10的整数。
本发明的另一个方面提供了一种通过对所述共聚物聚酯树脂进行挤出或注塑而制备的模塑产品。
有益效果
根据本发明,共聚的聚酯树脂包括特定的基于环己烷二甲醇化合物,使得共聚的聚酯树脂的收缩起始温度降低,因此可以实现与PVC类似的低温热收缩,由此防止在膜发生热收缩的时候通常会发生的PET容器的变形以及出现白色混浊。另外,可以很容易地控制收缩速度,由此减少模塑缺陷。
最佳实施方式
下面将对本发明进行详细描述。
在本发明中,在制备包含1,4-环己烷二甲醇的共聚的聚酯树脂的时候,使用式1所示的包含基于环己烷二甲醇的衍生物的二醇,使得制得的聚酯树脂具有足够的成型性,可以制得具有以下性质的膜:此种膜可以在低温下进行热收缩。另外,本发明还提供了使用所述聚酯树脂的模塑产品。
根据本发明,所述共聚物聚酯树脂是通过以下两步制备的:第一步,进行酯化,第二步,进行缩聚。
在第一步中,可以以间歇或连续的工艺进行酯化,相应的材料可以单独地加入,或者可以向二醇中加入浆液形式的对苯二甲酸。
更具体来说,芳族二羧酸以及包括乙二醇和1,4-环己烷二甲醇的二醇互相反应。特别有用的二羧酸是对苯二甲酸。
因此,以二羧酸为基准计,二醇以1.2~3.0的摩尔比加入,使得酯化反应在230~260℃以及1.0~3.0kg/cm2的条件下进行,酯化反应的反应温度可以为240~260℃,优选245~255℃,但是本发明不限于此。
另外,酯化通常需要100~300分钟,反应时间可以根据反应温度、反应压力以及二羧酸与二醇的摩尔比适当地变化,但是本发明不限于此。
在本发明中,二醇化合物用来提高排它地由对苯二甲酸以及乙二醇组成的均聚物的成型性或者其他性质,可以包括1,4-环己烷二甲醇,1,2-丙二醇,1,3-丙二醇,1,4-丁二醇,2,2-二甲基-1,3-丙二醇,1,6-己二醇,1,2-环己烷二醇,1,4-环己烷二醇,1,2-环己烷二甲醇和1,3-环己烷二甲醇。1,4-环己烷二甲醇特别适合用作二醇化合物来改进均聚物的性质。
在本发明中,1,4-环己烷二甲醇可以包括顺式异构体,反式异构体,或者两种异构体的混合物,用量可以接近最终聚合物中所需的摩尔百分数,优选为10-80摩尔%(以全部二醇组合物的总量计),以防由于结晶化造成成型性变差。可以加入乙二醇作为二醇组合物的一种组分,使得考虑到1,4-环己烷二甲醇的量,以二羧酸为基准计,全部二醇组合物的总量为100摩尔%。
酯化不需要催化剂,但是可以任选地加入催化剂以缩短反应时间。
在本发明中,包含基于环己烷二甲醇的衍生物的二醇由下式1所示。
[式1]
式中,m是1~10的整数。
以二羧酸的总量计,式1所示的二醇的用量可以为0.1~30摩尔%。如果二醇化合物的量小于0.1摩尔%,将会难以通过加入式1的二醇来改进性质。相反的,如果二醇的量超过30摩尔%,制得的膜的耐热性显著减小,不利地降低其作为热收缩膜的应用能力。
当式1所示的二醇用来代替包含对苯二甲酸的共聚物聚酯树脂的一部分二羧酸的时候,所述热收缩膜可以具有降低的收缩起始温度,因此在通过蒸汽加工过程的时候可以缩短周期时间,由此提高生产率。同时,因为在低温收缩的时候,收缩速度很慢,可以实现高效的工艺控制,有益地减小缺陷率。式1所示的二醇化合物可以包括二环己烷二甲醇,三环己烷二甲醇,四环己烷二甲醇,五环己烷二甲醇,以及它们的混合物。
在第一步中的酯化反应完成之后,进行第二步的缩聚。可以选择使用那些通常用于聚酯树脂缩聚的缩聚催化剂、稳定剂和着色剂。
可以用于本发明的缩聚催化剂是钛、锗和锑化合物,但是本发明不限于此。
钛基催化剂通常用作使用等于或大于15重量%的1,4-环己烷二甲醇(以对苯二甲酸的重量为基准计)制备的共聚物聚酯树脂的缩聚催化剂。即使当钛基催化剂的用量小于锑基催化剂的量,该反应也可以发生。另外,钛基催化剂的价格低于锗基催化剂。
可用于本发明的钛基催化剂的例子可以包括钛酸四乙酯,钛酸乙酰基三丙酯,钛酸四丙酯,钛酸四丁酯,钛酸四丁酯,钛酸多丁酯,钛酸-2-乙基己酯,钛酸辛二醇酯,乳酸酯/盐钛酸酯(lactate titanate),三乙醇胺钛酸盐(triethanolamine titanate),乙酰丙酮酸盐钛酸盐(acetylacetonatetitanate),乙酰乙酸乙酯钛酸盐(ethylacetoacetic ester titanate),硬脂酰钛酸酯(isostearyl titanate),二氧化钛,二氧化钛和二氧化硅的共沉淀物,以及基二氧化钛和二氧化锆的共沉淀物。
缩聚催化剂的量会影响最终聚合物的颜色,缩聚催化剂的量可以根据所需颜色以及稳定剂以及着色剂的种类而变化。以最终聚合物的重量为基准计,所述缩聚催化剂的用量可以包含1~100ppm钛元素,具体来说是1~50ppm钛元素,其用量包含等于或小于10ppm的硅元素。因此,如果钛元素的量小于1ppm,将无法获得所需的聚合程度。相反的,如果其用量超过100ppm,最终聚合物的颜色会变成黄色,这是人们不希望看到的。
另外,可以使用稳定剂和着色剂作为另外的添加剂。
可用于本发明的稳定剂可以包括磷酸,磷酸三甲酯,磷酸三乙酯以及二氧磷基乙酸三乙酯(triethyl phosphonoacetate),以最终聚合物的重量计,稳定剂的用量可以包括10~100ppm的磷元素。如果稳定剂的量小于10ppm,则难以确保所需的明亮色彩。相反的,如果其用量超过100ppm,则聚合程度将无法达到所需的高水平。
用来改进颜色的着色剂可以包括常规的着色剂,例如乙酸钴和丙酸钴,以最终聚合物的重量计,着色剂的用量可以为0~100ppm。
除了以上着色剂的例子以外,可以使用任何公知的有机化合物作为着色剂。
在加入这些组分之后,可以在温度为260~290℃,400~0.1毫米汞柱的减小的压力之下,在第二步中进行缩聚,但是本发明不限于此。
缩聚进行的时间要能够达到所需的特性粘度,反应温度设定在260~290℃,优选260~280℃,更优选265~275℃。
另外,缩聚反应在400~0.1毫米汞柱的减小的压力下进行,以消除作为副产物生成的二醇,由此制得包含1,4-环己烷二甲醇的共聚物聚酯树脂。
如上文所述,因为本发明的共聚物聚酯树脂具有低收缩起始温度,因此具有缓慢的收缩速度,可以进行有效的工艺控制,由此获得足够高的成型性,由此降低缺陷率。因此,通过挤出法和拉伸法对共聚物聚酯树脂进行模塑,由此可以制得具有高成型性的热收缩膜。
通过以下示例性实施例和比较例可以更好地理解本发明,以下实施例是举例说明性的,不会对本发明构成限制。
根据以下方法在实施例和比较例中进行性质测量。
◎玻璃化转变温度(Tg):使用购自TA仪器公司(TA Instrument)的差式扫描量热仪测量Tg。
◎热收缩率:将一种样品切割成尺寸为10厘米×10厘米的正方形,在无负荷的条件下,在下表1所示的温度下浸泡在温水中10秒,使其热收缩,然后在25℃的水中浸泡10秒,然后测量样品的纵向和横向的长度,然后代入以下公式。
热收缩率(%)=100×(收缩之前的长度-收缩之后的长度)/(收缩之前的长度)
◎溶体电阻率(Ωcm):将一对电极板插入在275℃熔融的碎片或膜中,对其施加120V的电压。测量此刻的电流,然后将测得的值代入以下公式,从而确定熔体电阻率Si(Ωcm)。
Si=(A/I)X(V/io)
式中A是电极的面积(cm2),I是电极之间的距离(cm),V是电压(V),io是电流(A)。
当使用该装置制备共聚物聚酯的时候,可以获得以下的结果。
发明实施方式
[实施例]
实施例1
为了制备共聚物聚酯树脂,基于6摩尔对苯二甲酸,将138克1,4-环己烷二甲醇,502克乙二醇和188克二环己烷二甲醇加入装有搅拌器和排放冷凝器的3升反应器中,并进行混合,在将其中的温度逐渐升高到255℃的同时进行反应。
由此,将产生的水排放到外界,以此进行酯化。在水的产生和排出完成之后,将制得的酯化产物转移到装有搅拌器、冷凝器和真空系统的缩聚反应器中。
在酯化产物中加入0.5克钛酸四丁酯,0.4克磷酸三乙酯和0.5克乙酸钴。在反应器的内部温度从240℃升高到275℃的同时,在50毫米汞柱的低真空气氛中除去乙二醇,所述50毫米汞柱的压力是在40分钟之内从常压降低达到的。然后,使得压力逐渐降至0.1毫米汞柱,以产生高真空气氛,在此高真空气氛下进行反应,直至达到所需的特性粘度。将反应产物从反应器移出,切割成碎屑的形式。
使用包含1,4-环己烷二甲醇的共聚物聚酯树脂,制备了热收缩膜,根据上文所述的方法测量其玻璃化转变温度、收缩起始温度、热收缩率和熔体粘度。结果见以下表1所示。
实施例2
按照与实施例1相同的方式制备了共聚物聚酯树脂,不同之处在于,加入了268克二环己烷二甲醇。然后用该树脂制备了热收缩膜,测量了该热收缩膜的玻璃化转变温度、收缩起始温度、热收缩率和熔体电阻率。结果见以下表1所示。
实施例3
按照与实施例1相同的方式制备了共聚物聚酯树脂,不同之处在于,加入了210三环己烷二甲醇。然后用该树脂制备了热收缩膜,测量了该热收缩膜的玻璃化转变温度、收缩起始温度、热收缩率和熔体电阻率。结果见以下表1所示。
比较例1
按照与实施例1相同的方式制备了共聚物聚酯树脂,不同之处在于,没有加入二环己烷二甲醇。然后用该树脂制备了热收缩膜,测量了该热收缩膜的玻璃化转变温度、收缩起始温度、热收缩率和熔体电阻率。结果见以下表1所示。
比较例2
用PVC树脂制备了热收缩膜,测量了该热收缩膜的玻璃化转变温度、收缩起始温度、热收缩率和熔体电阻率。结果见以下表1所示。
表1
Claims (7)
2.如权利要求1所述的共聚物聚酯树脂,其特征在于,所述式1所示的二醇化合物是选自以下组分的一种或多种:二环己烷二甲醇、三环己烷二甲醇以及它们的混合物。
3.如权利要求1所述的共聚物聚酯树脂,其特征在于,所述芳族二羧酸是对苯二甲酸。
4.一种模塑产品,通过对如权利要求1-3中任一项所述的共聚物聚酯树脂进行挤出或注塑而制得。
5.如权利要求4所述的模塑产品,其特征在于,所述模塑产品是热收缩膜。
6.如权利要求4所述的模塑产品,其特征在于,所述模塑产品的收缩起始温度等于或低于60℃,在60℃的最大热收缩率等于或大于2%。
7.如权利要求4所述的模塑产品,其特征在于,所述模塑产品在85℃的最大热收缩率等于或大于50%。
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