CN106700331A - 一种pvc锌基热稳定剂 - Google Patents
一种pvc锌基热稳定剂 Download PDFInfo
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 32
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 title claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 title abstract description 26
- 229920000915 polyvinyl chloride Polymers 0.000 title abstract description 25
- 229910052599 brucite Inorganic materials 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 31
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 14
- 239000000194 fatty acid Substances 0.000 claims abstract description 14
- 229930195729 fatty acid Natural products 0.000 claims abstract description 14
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 12
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000000463 material Substances 0.000 claims description 15
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- 150000004665 fatty acids Chemical class 0.000 claims description 13
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- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical class [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
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- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- ONLJZPFXSHXZTC-UHFFFAOYSA-M azanium sodium acetic acid diacetate Chemical compound C(C)(=O)[O-].C(C)(=O)O.C(C)(=O)[O-].[NH4+].[Na+] ONLJZPFXSHXZTC-UHFFFAOYSA-M 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- -1 zinc fatty acid Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 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
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Abstract
本发明公开了一种PVC锌基热稳定剂，属于化工技术领域，具体由下列物质制成：改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸、聚天门冬氨酸。本发明制得的锌基热稳定剂能有效改善PVC的热稳定性，又具有无毒环保的特点，比传统含铅/含镉稳定剂的性能更为优异，有很好的推广使用价值。
Description
技术领域
本发明属于化工技术领域，具体涉及一种PVC锌基热稳定剂。
背景技术
聚氯乙烯（PVC）是产量仅次于聚乙烯（PE）的第二大通用塑料，具有强度高且增塑、耐腐蚀、耐燃、绝缘性好、透明性高等优点，广泛应用于工业建筑、农业、日用品、包装、电力、公共事业等领域。但是，PVC存在热稳定性差，在通常的加工温度下发生严重降解的缺点。为了解决上述问题，传统方法是在PVC中添加大量的含铅、含镉的热稳定剂，但随着人们环保意识的加强，上述两种热稳定剂逐渐退出历史的舞台，开发环保高效的热稳定剂是本领域技术人员不断探索的问题之一。锌基热稳定剂是人们近年来开发的一种无毒热稳定剂，具有很好的发展潜力，但其易出现“锌烧”的问题，限制了其推广使用。
发明内容
本发明旨在提供一种PVC锌基热稳定剂。
本发明通过以下技术方案来实现：
一种PVC锌基热稳定剂，由如下重量份的物质制成：
6~9份改性水镁石粉、14~17份硬脂酸锌、26~29份脂肪酸锌、4~7份硫酸锌、3~5份氯化锌、2~4份氨基三乙酸钠、1~3份羟基乙叉二膦酸、2~4份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：25~30份水镁石、5~7份麦饭石、3~5份亚磷酸钠、2~4份六偏磷酸钠。
优选的，由如下重量份的物质制成：
8份改性水镁石粉、15份硬脂酸锌、27份脂肪酸锌、6份硫酸锌、4份氯化锌、3份氨基三乙酸钠、2份羟基乙叉二膦酸、3份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：28份水镁石、6份麦饭石、4份亚磷酸钠、3份六偏磷酸钠。
进一步的，所述改性水镁石粉的制备方法包括如下步骤：
（1）将水镁石放入质量分数为3.5%的硝酸溶液中浸泡处理1~1.5h后取出，再放入质量分数为4%的氢氧化钠溶液中浸泡处理1~1.5h后取出，用去离子水冲洗干净后备用；
（2）将步骤（1）处理后的水镁石放入温度为480~510℃的条件下煅烧处理1~2h后取出，然后将其浸渍于表面处理液中2~3h后取出备用；所述表面处理液中各组分质量百分比为：1.5~2%聚乙烯醇、0.3~0.5%单烷氧基不饱和脂肪酸钛酸酯、1~2%蓖麻油、0.4~0.6%十二烷基苯磺酸钠，余量为水；表面处理后的水镁石相容性更好，吸附、取代特性更优异，比表面积也控制在较适宜的程度，性能更佳；
（3）将步骤（2）处理后的水镁石干燥后进行粉碎，将其按颗粒大小粉碎成A、B两级，其中A级颗粒大小为300~400目，B级颗粒大小为500~600目，最后将A、B两级颗粒按重量比5：2混合均匀得分级混合物备用；合理配制的颗粒大小能有效保证其在基材中的分散效果，有增强了其与各物质成分的结合特性，更利于性能的发挥；
（4）将麦饭石粉碎后过200~300目，再同步骤（3）所得的分级混合物，以及亚磷酸钠、六偏磷酸钠共同混合，搅拌均匀即得改性水镁石粉。
进一步的，所述稳定剂的制备方法是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸、聚天门冬氨酸共同混合后，在42~45℃的条件下不断搅拌分散均匀即可。
进一步的，所述稳定剂在PVC中的添加使用质量分数为4~6%。
一种PVC锌基热稳定剂的制备方法，具体是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸和聚天门冬氨酸置于温度为38~43℃的条件下充分混拌均匀而成。
本发明具有如下有益效果：
本发明根据现有的锌基热稳定剂的缺陷，对其组成成分进行了改良，添加的改性水镁石粉作为协效稳定剂，能有效的吸收固定锌基热稳定剂中的锌离子，抑制锌烧现象的发生，同时又能吸收PVC热降解释放的HCl，消除其催化作用，对其主要水镁石成分进行了颗粒分级配比后，很好的保证了整体的填充、稳定性，更利于改性水镁石粉效果的发挥；最终在各成分的配合作用下，本发明制得的锌基热稳定剂能有效改善PVC的热稳定性，又具有无毒环保的特点，比传统含铅/含镉稳定剂的性能更为优异，有很好的推广使用价值。
具体实施方式
实施例1
一种PVC锌基热稳定剂，由如下重量份的物质制成：
6份改性水镁石粉、14份硬脂酸锌、26份脂肪酸锌、4份硫酸锌、3份氯化锌、2份氨基三乙酸钠、1份羟基乙叉二膦酸、2份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：25份水镁石、5份麦饭石、3份亚磷酸钠、2份六偏磷酸钠。
进一步的，所述改性水镁石粉的制备方法包括如下步骤：
（1）将水镁石放入质量分数为3.5%的硝酸溶液中浸泡处理1.2h后取出，再放入质量分数为4%的氢氧化钠溶液中浸泡处理1.3h后取出，用去离子水冲洗干净后备用；
（2）将步骤（1）处理后的水镁石放入温度为500℃的条件下煅烧处理1.5h后取出，然后将其浸渍于表面处理液中2.5h后取出备用；所述表面处理液中各组分质量百分比为：1.8%聚乙烯醇、0.4%单烷氧基不饱和脂肪酸钛酸酯、1.5%蓖麻油、0.5%十二烷基苯磺酸钠，余量为水；
（3）将步骤（2）处理后的水镁石干燥后进行粉碎，将其按颗粒大小粉碎成A、B两级，其中A级颗粒大小为300~400目，B级颗粒大小为500~600目，最后将A、B两级颗粒按重量比5：2混合均匀得分级混合物备用；
（4）将麦饭石粉碎后过200~300目，再同步骤（3）所得的分级混合物，以及亚磷酸钠、六偏磷酸钠共同混合，搅拌均匀即得改性水镁石粉。
进一步的，所述稳定剂的制备方法是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸、聚天门冬氨酸共同混合后，在43~44℃的条件下不断搅拌分散均匀即可。
进一步的，所述稳定剂在PVC中的添加使用质量分数为5%。
一种PVC锌基热稳定剂的制备方法，具体是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸和聚天门冬氨酸置于温度为40℃的条件下充分混拌均匀而成。
实施例2
一种PVC锌基热稳定剂，由如下重量份的物质制成：
8份改性水镁石粉、15份硬脂酸锌、27份脂肪酸锌、6份硫酸锌、4份氯化锌、3份氨基三乙酸钠、2份羟基乙叉二膦酸、3份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：28份水镁石、6份麦饭石、4份亚磷酸钠、3份六偏磷酸钠。其余方法步骤同实施例1。
实施例3
一种PVC锌基热稳定剂，由如下重量份的物质制成：
9份改性水镁石粉、17份硬脂酸锌、29份脂肪酸锌、7份硫酸锌、5份氯化锌、4份氨基三乙酸钠、3份羟基乙叉二膦酸、4份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：30份水镁石、7份麦饭石、5份亚磷酸钠、4份六偏磷酸钠。其余方法步骤同实施例1。
对比实施例1
本对比实施例1与实施例1相比，在制备改性水镁石粉的步骤（3）中，将A、B两级颗粒的重量比调整为1：1，除此外的方法步骤均相同。
对比实施例2
本对比实施例2与实施例2相比，用等质量份的普通水镁石粉取代改性水镁石粉，除此外的方法步骤均相同。
对照组
传统的铅基热稳定剂。
为了对比本发明效果，将上述六种方式对应所述的热稳定剂分别以质量分数为5%的量添加于PVC中，按相同的制备方法制成规格相同的试件，然后将其分别放入温度为220℃的烤箱中，连续加热处理60min，取出后观察表面性状以评价热稳定剂的性能，具体对比见下表1所示：
表1
| 表面性状评级 | |
| 实施例1 | 1 |
| 实施例2 | 1 |
| 实施例3 | 1 |
| 对比实施例1 | 2 |
| 对比实施例2 | 3 |
| 对照组 | 2 |
注：上表1中所述的表面性状评级中各分值表示为：1代表PVC试件表面轻微老化，伴有轻微的起泡现象；2代表PVC试件表面老化、起泡现象明显；3代表PVC试件表面老化、起泡现象严重。
由上表1可以看出，本发明制得的锌基热稳定剂使用性能较好，比传统的铅基热稳定剂更为优秀，并具有无毒环保的特点，极具推广价值。
Claims (6)
1.一种PVC锌基热稳定剂，其特征在于，由如下重量份的物质制成：
6~9份改性水镁石粉、14~17份硬脂酸锌、26~29份脂肪酸锌、4~7份硫酸锌、3~5份氯化锌、2~4份氨基三乙酸钠、1~3份羟基乙叉二膦酸、2~4份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：25~30份水镁石、5~7份麦饭石、3~5份亚磷酸钠、2~4份六偏磷酸钠。
2.根据权利要求1所述的一种PVC锌基热稳定剂，其特征在于，由如下重量份的物质制成：
8份改性水镁石粉、15份硬脂酸锌、27份脂肪酸锌、6份硫酸锌、4份氯化锌、3份氨基三乙酸钠、2份羟基乙叉二膦酸、3份聚天门冬氨酸；所述改性水镁石粉由如下重量份的物质制成：28份水镁石、6份麦饭石、4份亚磷酸钠、3份六偏磷酸钠。
3.根据权利要求1或2所述的一种PVC锌基热稳定剂，其特征在于，所述改性水镁石粉的制备方法包括如下步骤：
（1）将水镁石放入质量分数为3.5%的硝酸溶液中浸泡处理1~1.5h后取出，再放入质量分数为4%的氢氧化钠溶液中浸泡处理1~1.5h后取出，用去离子水冲洗干净后备用；
（2）将步骤（1）处理后的水镁石放入温度为480~510℃的条件下煅烧处理1~2h后取出，然后将其浸渍于表面处理液中2~3h后取出备用；所述表面处理液中各组分质量百分比为：1.5~2%聚乙烯醇、0.3~0.5%单烷氧基不饱和脂肪酸钛酸酯、1~2%蓖麻油、0.4~0.6%十二烷基苯磺酸钠，余量为水；
（3）将步骤（2）处理后的水镁石干燥后进行粉碎，将其按颗粒大小粉碎成A、B两级，其中A级颗粒大小为300~400目，B级颗粒大小为500~600目，最后将A、B两级颗粒按重量比5：2混合均匀得分级混合物备用；
（4）将麦饭石粉碎后过200~300目，再同步骤（3）所得的分级混合物，以及亚磷酸钠、六偏磷酸钠共同混合，搅拌均匀即得改性水镁石粉。
4.根据权利要求1或2所述的一种PVC锌基热稳定剂，其特征在于，所述稳定剂的制备方法是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸、聚天门冬氨酸共同混合后，在42~45℃的条件下不断搅拌分散均匀即可。
5.根据权利要求1或2所述的一种PVC锌基热稳定剂，其特征在于，所述稳定剂在PVC中的添加使用质量分数为4~6%。
6.一种如权利要求1或2所述的PVC锌基热稳定剂的制备方法，其特征在于，具体是将改性水镁石粉、硬脂酸锌、脂肪酸锌、硫酸锌、氯化锌、氨基三乙酸钠、羟基乙叉二膦酸和聚天门冬氨酸置于温度为38~43℃的条件下充分混拌均匀而成。
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