CN102186802B - 新型聚氯乙烯树脂增塑剂 - Google Patents
新型聚氯乙烯树脂增塑剂 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/08—Saturated compounds having a carboxyl group bound to a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
Abstract
本发明涉及二醇酯类增塑剂化合物,具体而言,涉及用于聚氯乙烯(PVC)树脂的增塑剂以及含有该增塑剂的塑料。更详细而言,本发明涉及由二醇与有机酸的酯化反应所制备的增塑剂。当采用本发明的酯类增塑剂制造聚氯乙烯树脂组合物时,能够获得具有优良塑化效率的产品,并且该产品的物理性能,如硬度、抗拉强度等,可得到改善。
Description
技术领域
本发明涉及酯类化合物和含有该化合物的塑料,具体而言,涉及用于聚氯乙烯(PVC)树脂的增塑剂。更确切地说,本发明涉及这样的酯类增塑剂,其是采用二醇与羧酸发生酯化反应而制备的,通过该增塑剂可以生产出具有高塑化效率和改善的物理性能(例如硬度、抗拉强度等)的聚氯乙烯树脂组合物。
背景技术
聚氯乙烯树脂为聚氯乙烯均聚物或含聚氯乙烯50%以上的共聚物,是一种常用的树脂,其可以通过挤压成型、注塑成型和压延等工艺形成各种不同的产品。这种聚氯乙烯树脂被广泛地用作各种产品的原料,所述产品例如为管材、电线、电器、玩具、膜、片材、合成皮革、焦油帆布、带材、食品包装材料、医疗用品等。可以通过合适地加入各种添加剂(例如增塑剂、稳定剂、填料、颜料等),从而赋予聚氯乙烯树脂各种物理性能。
在这些添加剂中,增塑剂是为聚氯乙烯树脂提供各种物理性能和功能(例如可加工性、韧性、电绝缘性、粘附性等)的必要添加剂。无论是把增塑剂混入塑料组合物的时候,还是在实际应用含有增塑剂的成形制品的时候,低挥发性(增塑剂的非常重要的因素)都是很重要的。另外,用于食品、饮料、医疗用品和药品领域的增塑剂,必须对人体的健康无害。这种无害的增塑剂的典型例子为邻苯二甲酸酯增塑剂。然而,因为对于邻苯二甲酸酯的再活化所引起的毒性存在争议,根据控制有毒材料的法律规定,据预测,邻苯二甲酸酯增塑剂的应用在未来将显著减少。因此,需要开发一种包含酯的增塑剂,其基本结构中不包含邻苯二甲酸酯,但具有与邻苯二甲酸酯增塑剂相当的塑化效率。
发明内容
技术问题
为了解决上述问题,本发明人对可以用作聚氯乙烯树脂增塑剂的酯类化合物进行了仔细地研究。结果,他们发现了一种具有特定结构的新型酯类化合物,其能够用作增塑剂,特别是用作聚氯乙烯树脂的增塑剂时效果非常好。基于这些发现完成了本发明。因此,本发明的一个目的是提供一种采用二醇制备的新型酯类增塑剂,其具有与传统的邻苯二甲酸酯增塑剂同等或更优的物理性能。
本发明的另一个目的是提供一种包含所述新型酯类增塑剂的增塑剂组合物。
本发明还有一个目的是提供一种包含所述增塑剂组合物的聚氯乙烯树脂组合物。
技术方案
为了实现上述目的,本发明第一个方面提供了一种如下式1所示的酯类增塑剂:
<式1>
其中,R为(CH2)n,n为0至2的整数,R1为取代或未取代的具有4至16个碳原子的烷基,R2为取代或未取代的具有5至10个碳原子的环烷基(naphthenic group)或芳基。
本发明第二个方面提供了一种酯类增塑剂组合物,其包含50~100重量%的所述酯类增塑剂。
本发明第三个方面提供了一种聚氯乙烯树脂组合物,其包含相对于聚氯乙烯树脂为10~100phr(份/100份树脂)的所述酯类增塑剂组合物。
有益效果
当应用本发明的采用了二醇的酯类增塑剂生产聚氯乙烯树脂时,有如下优点:能够获得具有良好塑化效率的产品,并且该产品的物理性能(例如抗拉强度等)得到了改善。
最佳实施方式
下文中,将对根据本发明的酯类增塑剂、以及包含所述酯类增塑剂的聚氯乙烯树脂组合物进行详细地说明。
本发明的通过二醇(特别是环己烷二醇)与至少一种羧酸的反应制得的酯类增塑剂如下式1所示:
<式1>
其中,R为(CH2)n,n为0至2的整数,R1为取代或未取代的具有4至16个碳原子的烷基,R2为取代或未取代的具有5至10个碳原子的环烷基或芳基。
更优选地,R1可为取代或未取代的具有6至10个碳原子的烷基,R2可为取代或未取代的具有5至8个碳原子的环烷基或芳基。
R1和R2可各自独立地包括具有4至20个碳原子的直链或支链烷基、具有4至20个碳原子的烯基、具有4至20个碳原子的环烷基、或具有6至10个碳原子的芳基作为取代基。
通过1,4-环己烷二甲醇与芳香族羧酸和脂肪酸的酯化反应制备所述酯类增塑剂。芳香族羧酸和脂肪酸与1,4-环己烷二甲醇的摩尔比为1∶1.8~0.4∶1.8~0.4;优选为1∶1.0~0.5∶0.7~1.6。所述摩尔比是由1,4-环己烷二甲醇中存在的羟基确定的。所述酯化反应中优选使用酸催化剂,例如硫酸氢钠。另外,对甲苯磺酸、硫酸或类似物可作为酯化反应中的催化剂。所述催化剂的用量可以为反应混合物的0.5~5重量%。
同时,酯化反应中可用的溶剂的例子包括己烷、环己烷、甲苯和二甲苯。所述酯化反应优选在100℃~160℃下进行。酯化反应后,通过添加碱性试剂(例如碳酸钠水溶液或碳酸钙水溶液)来中和未反应的有机酸和酸催化剂。将相分离后所得的粗酯用水洗涤,脱水过滤后得到目标化合物。
本发明的增塑剂组合物包含50~100重量%如式1所示的酯类增塑剂。基于酯类增塑剂组合物的总量计算,该增塑剂组合物还可以包含少于50重量%的、如式2所示的化合物和/或式3所示的化合物:
【式2】
【式3】
其中,R为(CH2)n,n为0至2的整数,R3和R4各自独立地为取代或未取代的具有4至16个碳原子的烷基,R5和R6各自独立地为取代或未取代的具有6至10个碳原子的环状烷烃(cyclicparaffin)基团或芳基。
而且,R3至R6可各自独立地包括具有4至20个碳原子的直链或支链烷基、具有4至20个碳原子的烯基、具有4至20个碳原子的环烷基、或具有6至10个碳原子的芳基作为取代基。
本发明的酯类增塑剂适合用于聚氯乙烯树脂中。所述聚氯乙烯树脂不限于聚氯乙烯。聚氯乙烯树脂的例子可以包括:含氯树脂,例如氯化聚氯乙烯、聚偏二氯乙烯、氯化聚乙烯、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-丙烯共聚物、氯乙烯-苯乙烯共聚物、氯乙烯-异丁烯共聚物、氯乙烯-偏二氯乙烯共聚物、氯乙烯与各种醚形成的共聚物、以及它们的共混物;以及含氯树脂和不含氯的树脂(例如丙烯腈-苯乙烯共聚物、丙烯腈-苯乙烯-丁二烯三元共聚物、乙烯-乙酸乙烯酯共聚物、聚酯等)形成的共混物、嵌段共聚物和接枝共聚物。
本发明的聚氯乙烯树脂组合物包含相对于聚氯乙烯树脂为10~100phr的所述酯类增塑剂组合物。可以根据聚氯乙烯树脂组合物的用途适当地调整酯类增塑剂组合物的含量。当所述酯类增塑剂组合物的含量小于10phr时,难以实现增塑剂所能表现出的韧性或可加工性。另外,当其含量超过100phr时,难以确保必要的机械性能,而且聚氯乙烯树脂组合物可能会析出。
同时,聚氯乙烯树脂组合物还可以包含相对于聚氯乙烯树脂为0~30phr的添加剂,该添加剂不包括填料和颜料。
在此,所述添加剂是可以选择性地加入到聚氯乙烯树脂组合物中的一般添加剂,其例子可以包括绝缘改良剂、各种金属盐、多元醇、环氧化合物、酚类抗氧剂或含硫抗氧剂、紫外线吸收剂、受阻胺类光稳定剂、无机稳定剂、防雾剂(anti-fogging agent)、抗雾剂(anti-mistingagent)、辅助稳定剂、有机锡化合物等。
与上述的一般添加剂不同,填料和颜料的含量相对于聚氯乙烯树脂可以为至多约200phr。当填料和颜料的含量大于200phr时,所述聚氯乙烯树脂组合物的密度、硬度或韧性会受到不利影响。填料的例子可以包括碳酸钙、硅石、粘土、玻璃珠、云母、绢云母、玻璃片、石棉、硅灰石、钛酸钾、高双折射光纤(PMF)、石膏纤维、硬硅钙石、金属氧化物半导体(MOS)、磷酸盐纤维、玻璃纤维、碳纤维、芳纶纤维,等等。
包含本发明的酯类增塑剂的聚氯乙烯树脂组合物可用于:建材,例如墙壁装饰材料、地板材料、窗框、壁纸等;配线覆盖材料;汽车内部和外部材料;农用材料,例如用于乙烯基塑料大棚、通道等的材料;食品包装材料;成膜剂,例如密封剂、塑溶胶、涂料、油墨等;以及其它物品,例如合成革、涂层织物、软管、管材、片材、婴儿玩具、手套等。然而,本发明不限于此。
使用酯类增塑剂组合物制备聚氯乙烯树脂组合物的方法为相关领域所公知,在此不做特别的限定。
本发明的实施方式
下文中,将结合实施例对本发明进行更详细的说明。然而,这些实施例仅用于说明本发明,本发明的范围不限于此。在这些实施例中,采用以下方法评价样品的物理性能。
硬度
基于ASTM D2240,将硬度测试仪(A型)的测量针完全压在样品某一点上达5秒钟,于是测得样品的硬度。在每个样品的三个点上进行硬度测试,然后得到其平均值。用硬度作为表示塑化效率的指标。
抗拉强度、伸长率、100%伸长率时的弹性模量
基于ASTM D412方法,采用UTM测量样品的抗拉强度和弹性模量。在200mm/min的横梁速度下对哑铃形样品进行拉伸后,在样品的切割点处测量其抗拉强度和弹性模量。100%伸长率时的弹性模量对应于100%伸长率时的抗拉强度,并且其与塑化效率密切相关。
量大扭矩
采用Brabender测试仪测量将聚氯乙烯与增塑剂混合时的最大扭矩。
[实施例1]
采用1,4-环己烷二甲醇、苯甲酸和2-乙基己酸制备酯类增塑剂
首先,将1.0mol的1,4-环己烷二甲醇、0.6mol苯甲酸、1.2mol2-乙基己酸、200g甲苯(作为溶剂)和3.0g硫酸氢钠(作为催化剂)置入配有搅拌器和冷凝器的2L圆底烧瓶中,然后加热至100℃,反应12个小时。
反应后,在200℃下用真空泵减压至5mmHg,用10重量%的碳酸钠水溶液中和未反应的有机酸,水洗、脱水,然后用吸附剂过滤,得到增塑剂组合物。发现所述增塑剂组合物包含符合式1的苯甲酸4-(2-乙基-己酰氧甲基)-环己基甲酯(约50重量%)作为主要成分。
制备聚氯乙烯树脂组合物
制备试样以评估所获得的酯类增塑剂的性能。即:以重量份计,将50phr所获得的增塑剂组合物(其包含式1所示的化合物作为主要成分)和1phr稳定剂(LFX-1100)与聚氯乙烯树脂(LS-100,LG化学有限公司生产)混合,然后将混合物预加热至185℃并持续1分钟,加压1.5分钟,冷却2分钟后获得厚度为2mm的薄片。将该薄片制成各种哑铃形试样。
采用这些试样进行上述测试,结果见下表1。
[实施例2]
除了用癸酸代替2-乙基己酸之外,按照与实施例1相同的方法制备酯类增塑剂和聚氯乙烯树脂组合物。测试结果见下表1。
[实施例3]
除了用环己烷甲酸(naphthenic acid)代替苯甲酸之外,按照与实施例1相同的方法制备酯类增塑剂和聚氯乙烯树脂组合物。测试结果见下表1。
[比较例1]
除了采用邻苯二甲酸二-2-乙基己酯作为增塑剂之外,按照与实施例1相同的方法制备试样。采用该试样进行与实施例1相同的测试,结果见下表1。
[比较例2]
除了采用邻苯二甲酸二异壬酯代替邻苯二甲酸二-2-乙基己酯作为增塑剂之外,按照与实施例1相同的方法制备试样。采用该试样进行与实施例1相同的测试,结果见下表1。
[比较例3]
除了采用偏苯三酸三辛酯作为增塑剂之外,按照与实施例1相同的方法制备试样。采用该试样进行与实施例1相同的测试,结果见下表1。
【表1】
从表1的结果可以推断出:实施例1、2和3中的增塑剂的塑化效率比比较例1、2和3中的增塑剂的塑化效率高;并且,实施例1、2和3中的增塑剂的物理性能(例如抗拉强度、伸长率等)与比较例1、2和3中的增塑剂的物理性能相当或更优。因此,由于本发明的新型增塑剂的塑化效率高,预计其能够形成各种形状,从而可以有各种不同的应用。
如上所述,虽然为了说明的目的公开了本发明优选的实施方案,但本领域技术人员应该了解,在不脱离如随附的权利要求书中所公开的本发明的范围和精神的情况下,对本发明进行各种修改、补充和替代都是可以的。因此,本发明不限于以上实施例。
Claims (4)
1.一种酯类增塑剂组合物,其包含50~100重量%的如下式1所示的酯类增塑剂:
<式1>
其中,R为(CH2)n,n为0至2的整数,R1为未取代的具有6至10个碳原子的烷基,R2为未取代的具有5至10个碳原子的环烷基或芳基。
2.权利要求1所述的酯类增塑剂组合物,基于所述酯类增塑剂组合物的总量计算,该酯类增塑剂组合物还包含少于50重量%的、如式2和式3所示的化合物中的至少一种:
<式2>
<式3>
其中,R为(CH2)n,n为0至2的整数,R3和R4相同,为未取代的具有6至10个碳原子的烷基;R5和R6相同,为未取代的具有5至10个碳原子的环烷基或芳基。
3.一种聚氯乙烯树脂组合物,其包含相对于聚氯乙烯树脂为10~100phr的权利要求2所述的酯类增塑剂组合物。
4.权利要求3所述的聚氯乙烯树脂组合物,其还包含相对于聚氯乙烯树脂为至多30phr的添加剂,该添加剂不包括填料和颜料。
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