CN115058059A - 一种pvc用钙锌热稳定剂及制备方法和应用 - Google Patents
一种pvc用钙锌热稳定剂及制备方法和应用 Download PDFInfo
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- 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
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Abstract
本发明属于塑料添加剂领域,具体涉及一种PVC用钙锌热稳定剂及制备方法和应用。本发明以金属锌化合物和Atz为原料开发了一种具有空间三维结构的金属有机骨架Zn‑Atz,将Zn‑Atz、硬脂酸钙及亚磷酸酯等复配,得到一种含金属有机骨架Zn‑Atz的PVC用钙锌热稳定剂。本发明制备的钙锌热稳定剂具有无毒、无重金属、环保等特点,赋予其更好的初期和长期热稳定性及透明性。该制备方法简单、原料来源丰富且价格低廉。
Description
技术领域
本发明属于塑料添加剂领域,具体涉及一种PVC用钙锌热稳定剂及制备方法和应用。
背景技术
聚氯乙烯(PVC)因其优异的性能而被广泛使用。由于PVC链中的结构缺陷,当熔融处理或使用温度高于100℃时,会因其降解而发生变色和机械性能劣化。目前,添加热稳定剂是延缓PVC降解的有效途径。一些传统的热稳定剂,如碱性铅盐,可与热降解过程中逸出的氯化氢反应,从而抑制氯化氢的进一步催化作用;如金属皂和二烷基锡的酯或硫醇,可与PVC主链中的不稳定氯置换生成更稳定的络合物。尽管铅盐和有机锡稳定剂具有高效的热稳定性,但因毒性限制其使用。金属皂热稳定剂,如硬脂酸钙、硬脂酸锌,往往需要复配才能发挥协同热稳定作用。此外,硬脂酸锌的热稳定转化产物氯化锌是脱氯化氢过程的强催化剂,容易导致制品的突然黑化。纯有机热稳定剂,包括含氮有机化合物、酰胺类有机热稳定剂、席夫碱类有机热稳定剂和含氨基热稳定剂,因其不含重金属的性质和广阔的应用前景而受到广泛关注。然而,成本和热稳定效果有待进一步提高。
3-氨基-1,2,4-三唑(ATZ)含氮量高,这使其比其他含氮有机物吸收更多氯化氢。同时,Atz的熔点为158.8℃,低于PVC样品的加工温度。因此,在PVC加工过程中,Atz以液态形式存在,有利于其在PVC中更好地分散,提高热稳定效率。因此,Atz作为辅助热稳定剂可以显著提高PVC的热稳定性。例如,Chen等人以Atz为原料制备了二维层状配合物[Zn(ttr)(OAc),并提出了一种新的“两步热稳定机制”:(1)[Zn(ttr)(OAc)]在初始阶段吸收大量HCl形成Atz盐酸盐,它在稳定PVC方面起着关键作用,可以显著提高PVC的热稳定性。(2)当温度超过280℃时,Atz盐酸盐开始分解并释放大量HCl,导致PVC产品快速降解。因此,热稳定剂的热稳定性对PVC样品的热稳定效果至关重要。研究发现,当含氮有机分子与金属配合形成稳定的空间三维结构时,它们的热稳定性会提高。例如,汪等人使用沸石咪唑骨架(ZIF-8)作为热稳定剂,显著提高PVC产品的热稳定性。因此,如果具有良好初始热稳定效果的锌与Atz协调以形成稳定的空间结构,则有望显著提高所获得材料的热稳定性,进而显著提高其稳定PVC产品的初始颜色和长期热稳定性。
本发明以碳酸锌氢氧化物水合物和Atz为原料开发了一种具有空间三维结构的金属有机骨架Zn-Atz,并对其热稳定性和对PVC的热稳定作用进行了研究。
发明内容
为解决现有市场上PVC热稳定剂产品所存在的问题,本发明提供一种PVC用钙锌热稳定剂及制备方法和应用,将Zn-Atz与硬脂酸钙、辅助热稳定剂复配,得到了一种初期和长期热稳定性都十分优异的钙锌复合热稳定剂。
本发明采用的技术方案如下:
一种PVC用钙锌热稳定剂,其特征在于:所述的热稳定剂由Zn-Atz、硬脂酸钙、亚磷酸酯按质量比0.1-0.6:0-0.67:0-0.8复配所得。
上述一种PVC用钙锌热稳定剂,其特征在于Zn-Atz的制备步骤为:取金属锌化合物、草酸和Atz混合,金属锌化合物、草酸和Atz的质量为1:(0.5~2):(1~5),升温至160~200℃下反应24~72h,获得Zn-Atz。
进一步优选的,金属锌化合物、草酸和Atz的质量比为1:1:4,反应温度为180℃,反应时间为48h。
所述金属锌化合物为水合碳酸锌、氧化锌、乙酸锌、硫酸锌和氯化锌中的一种,优选水合碳酸锌。
所述的亚磷酸酯为亚磷酸三苯酯、亚磷酸(三壬基苯基)酯、亚磷酸一苯二异辛酯和磷酸双酚A烷基酯中的一种,优选亚磷酸三苯酯。
上述一种PVC用钙锌热稳定剂在PVC制品中的应用。
有益效果:①Zn-Atz边缘的非配位氮原子能迅速吸收氯化氢和氯自由基,并表现出良好的初始热稳定性。②当Zn-Atz与CaSt2和亚磷酸三苯酯一起使用时,CaSt2和亚磷酸三苯酯可以快速吸收氯化氢和氯自由基,为氯化氢和不稳定的氯原子在Zn-Atz孔结构中的扩散提供更长的反应时间,从而显著提高长期热稳定性效果。
附图说明
图1中(A)为Atz(a)、水合碳酸锌(b)和Atz(c)的FT-IR谱图;(B)为Zn-Atz的模拟、Zn-Atz、水合碳酸锌的X射线衍射谱图;(C)为Zn-Atz的SEM图像;(D)为Zn-Atz的TGA曲线;
具体实施方式
文中未涉及部分均与现有技术相同或可采用现有技术加以实现。下述便是本发明的优选实施例,但本发明也不局限于以下仅有的实施例,在实施例上稍做改进也将视为本发明的保护范围。
实施例1
(1)取质量比为1:1:4的水合碳酸锌、草酸和Atz,升温至180℃下反应48h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为2:2:1),作为PVC热稳定剂
本实施例制备的Zn-Atz材料的FT-IR光谱结果见图1(A)所示。观察到Atz在3419cm-1、3327cm-1和1638cm-1区域显示三个特征吸收带,这归因于Atz中三唑环的氨基拉伸振动和C=N振动。碳酸氢氧化锌水合物在1385cm-1处强吸收带被指定为CO3 2-的特征峰。在最终产品中,1385cm-1处的特征峰消失,表明碳酸锌氢氧化物完全反应。同时,三唑环中的C=N吸收带在在1638cm-1处迁移到1666cm-1,表明Atz的化学环境发生变化。FT-IR结果表明Zn-Atz被成功制备。同时,通过XRD图谱进一步验证了制备的产物(图1B)。结果发现,合成的Zn-Atz在10.5°、15.9°、17.2°和20.3°处呈现四个主峰,与Zn-Atz的模拟粉末XRD图谱匹配良好,表明Zn-Atz的制备成功。图1(C)SEM图像显示Zn-Atz呈现规则的多面体形态,这与之前的报道一致。利用热重分析法研究了Zn-Atz的热稳定性,见图1(D),发现,Zn-Atz主要表现为两个阶段的质量损失。100℃以下的第一阶段轻微质量损失归于Zn-Atz上吸附的客体分子的损失。320-500℃的质量急剧损失与Zn-Atz中配体Atz的分解有关。热重分析结果表明,Zn-Atz的分解温度远高于PVC的加工温度。因此,当忽略其他因素时,Zn-Atz在加工过程中是稳定的。
实施例2
(1)取质量比为1:2:5的乙酸锌、草酸和Atz,升温至200℃下反应72h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为2:2:1),作为PVC
热稳定剂。
实施例3
(1)取质量比为1:0.5:1的氧化锌、草酸和Atz,升温至160℃下反应24h,获得Zn-Atz。
(2)取0.75g的Zn-Atz和CaSt2复配(质量比为1:2),作为PVC热稳定剂。
实施例4
(1)取质量比为1:0.5:5硫酸锌、草酸和Atz,升温至160℃下反应72h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为2:2:1),作为PVC热稳定剂。
实施例5
(1)取质量比为1:1:4的水合碳酸锌、草酸和Atz,升温至180℃下反应48h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为1:1:1),作为PVC热稳定剂。
实施例6
(1)取质量比为1:2:5的乙酸锌、草酸和Atz,升温至200℃下反应72h,获得Zn-Atz。
(2)取0.75g的Zn-Atz和CaSt2复配(质量比为1.5:1),作为PVC热稳定剂。
实施例7
(1)取质量比为1:0.5:5的硫酸锌、草酸和Atz,升温至160℃下反应72h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为0.5:0.5:1),作为PVC热稳定剂。
实施例8
(1)取质量比为1:2:1的氯化锌、草酸和Atz,升温至200℃下反应24h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为0.25:0.25:2),作为PVC热稳定剂。
实施例9
(1)取质量比为1:2:1的氯化锌、草酸和Atz,升温至200℃下反应24h,获得Zn-Atz。
(2)取0.75g的Zn-Atz、CaSt2和TP复配(质量比为2:2:1),作为PVC热稳定剂。
比较例1:
将目前市场上常用的品牌钙锌热稳定剂与自制的钙锌热稳定剂在同一配方同一用量的情况下,比较其PVC制品的性能。
实验组1:
表1实验组1组成
原料 | 用量(g) |
PVC | 25 |
DOTP | 12.5 |
实施例1制备的钙锌热稳定剂 | 0.75 |
对比组1:
表1对比组1组成
原料 | 用量(g) |
PVC | 25 |
DOTP | 12.5 |
硬脂酸钙 | 0.6 |
硬脂酸锌 | 0.15 |
对比组2:
表5对比组4组成
原料 | 用量(g) |
PVC | 25 |
DOTP | 12.5 |
实施例3制备的钙锌热稳定剂 | 0.75 |
对比组3:
表4对比组3组成
原料 | 用量(g) |
PVC | 25 |
DOTP | 12.5 |
实施例5制备的钙锌热稳定剂 | 0.75 |
静态热稳定性实验:将实验组1、对比组1至对比组3配方的物料混合均匀,分别在双滚开炼机上160-165℃下塑炼3min,压成薄膜片。依据GB/T2917.1-2002刚果红实验法和ASTM D2115-04热老化烘箱法于180℃下考察制品的静态热稳定性优劣。
将上述配方组成的物料混合均匀,在双辊开炼机上162℃下塑炼5min,得到厚度均一的PVC薄片。其静态热老化稳定性依据ISO 182-1-1990刚果红实验法和ISO 305-1990(E)热老化烘箱法进行测试,实验结果如表6所示。综合以上结果可知:与和江苏嘉仁禾科技有限公司的市售钙锌热稳定剂(LTS-Zn/Ca)相比,自制钙锌复合热稳定剂具有更优异的长期热稳定性。
表6实验组与对比组热稳定剂的静态热稳定性对比
Claims (7)
1.一种PVC用钙锌热稳定剂,其特征在于:所述的热稳定剂由Zn-Atz、硬脂酸钙、亚磷酸酯按质量比0.1-0.6:0-0.67:0-0.8复配所得;所述Zn-Atz的制备步骤为:取金属锌化合物、草酸和3-氨基-1,2,4-三唑(ATZ)混合,金属锌化合物、草酸和Atz的质量为1:(0.5~2):(1~5),升温至160~200℃下反应24~72h,获得Zn-Atz。
2.如权利要求1所述的一种PVC用钙锌热稳定剂,其特征在于:金属锌化合物、草酸和Atz的质量比为1:1:4,反应温度为180℃,反应时间为48h。
3.如权利要求2所述的一种PVC用钙锌热稳定剂,其特征在于:所述金属锌化合物为水合碳酸锌、氧化锌、乙酸锌、硫酸锌和氯化锌中的一种.
4.如权利要求3所述的一种PVC用钙锌热稳定剂,其特征在于:所述金属锌化合物为水合碳酸锌。
5.如权利要求1所述的一种PVC用钙锌热稳定剂,其特征在于:所述的亚磷酸酯为亚磷酸三苯酯、亚磷酸(三壬基苯基)酯、亚磷酸一苯二异辛酯和磷酸双酚A烷基酯中的一种。
6.如权利要求1所述的一种PVC用钙锌热稳定剂,其特征在于:所述的亚磷酸酯为亚磷酸三苯酯。
7.如权利要求1所述的一种PVC用钙锌热稳定剂的用途,其特征在于:用于制备PVC制品。
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