CN1068010C - 偏氯乙烯共聚物胶乳的制备方法 - Google Patents
偏氯乙烯共聚物胶乳的制备方法 Download PDFInfo
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- CN1068010C CN1068010C CN 97110436 CN97110436A CN1068010C CN 1068010 C CN1068010 C CN 1068010C CN 97110436 CN97110436 CN 97110436 CN 97110436 A CN97110436 A CN 97110436A CN 1068010 C CN1068010 C CN 1068010C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004816 latex Substances 0.000 title claims description 17
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940009662 edetate Drugs 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 230000002829 reductive effect Effects 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- 239000002612 dispersion medium Substances 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
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- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 238000012667 polymer degradation Methods 0.000 abstract description 2
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Abstract
本发明公开了一种偏氯乙烯共聚物胶乳的制备方法。在聚合釜内依次加入水,过硫酸盐和亚硫酸盐,十二烷基硫酸钠,乙二胺四乙酸盐,偏氯乙烯、甲基丙烯酸甲酯、丙烯酸。加料毕后冲氮气至压力为1.013×105帕斯卡(1千克/平方厘米),开启搅拌,升温至55℃进行乳液聚合,直至反应体系压力降到基本不变,升温熟化,然后降温、卸压,结束反应。本发明加入稳定剂乙二胺四乙酸盐后,它可以与易引起偏氯乙烯共聚物降解的金属离子形成螯合物,从而抑制HCl的脱落,使偏氯乙烯共聚物胶乳的颜色稳定性得到提高。
Description
本发明涉及一种共聚物的制备方法,尤其是偏氯乙烯共聚物胶乳的制备方法。
偏氯乙烯共聚物(PVDC)是当今世界上流行的三大高阻隔性聚合物材料之一,由于其优良的阻氧、阻水、阻CO2性,低的热封温度,以及耐油、耐化学等性能,目前已广泛地应用于食品、饮料、药物及其它众多商品的包装。偏氯乙烯共聚物有三种类型,一是模塑和吹塑树脂,二是可溶于有机溶剂的树脂,三是胶乳,由于胶乳不含易燃和有毒性的溶剂,且粘度低、粘性小,因此有广泛的应用,常直接涂布于PVC、BOPP、PE、PET、尼龙和纸张等膜类基材。
偏氯乙烯共聚物胶乳是采用乳液聚合法制备的,乳液聚合是聚合工业中一种重要的聚合方式,乳液聚合体系一般由单体、分散介质(比如水)、乳化剂、引发剂及其它添加剂组成。根据物料的投入和引出方式,乳液聚合又分为间歇聚合、半连续聚合和连续聚合。
日本已有多篇专利提供了偏氯乙烯共聚物的制备方法,例如昭57-57708、昭59-93706、昭57-139136、昭60-17248等,但是,由于偏氯乙烯胶乳存在脱氧化氢(HCl)反应,胶乳极易变色。颜色稳定性不好的胶乳在短时间存放过程中即变为黄色,甚至桔红色,而现有技术都没有很好地解决这一问题。
本发明的目的在于提供一种偏氯乙烯共聚物胶乳的制备方法,从而得到聚合物分子稳定性较好,胶乳颜色稳定,其它性能优良的偏氯乙烯共聚物胶乳。
本发明的目的是这样实现的:一种偏氯乙烯共聚物胶乳的制备方法,采用乳液聚合法制备,反应体系包括单体、分散介质水、乳化剂、引发剂,反应体系中还加入水量的50~400ppm的乙二胺四乙酸盐。
反应体系中还加入水量的150~250ppm的乙二胺四乙酸盐。
所说的乙二胺四乙酸盐为下列盐之一:
(1)乙二胺四乙酸钠
(2)乙二胺四乙酸钾
采用这样的技术方案,在聚合配方中加入稳定剂乙二胺四乙酸盐后,它可与易引起聚合物降解的金属离子生成螯合物,以抑制HCl的脱落,从而使偏氯乙烯共聚物胶乳的颜色稳定性得到提高。
下面结合实施例进一步说明本发明。
实施例1
依次将反应介质水80克、氧化剂过硫酸铵0.36克、还原剂亚硫酸氢钠0.18克、乳化剂十二烷基硫酸钠2.5克、稳定剂乙二胺四乙酸钠0.016克、偏氯乙烯90克、共聚单体甲基丙烯酸甲酯8.5克和丙烯酸1.5克加入反应釜中,然后充氮气至反应体系压力为1.013×105帕斯卡(1千克/平方厘米),开启搅拌并升温至55℃,开始反应。待反应体系压力降至基本不变时,升温至熟,然后降温、卸压,除去剩余单体,开釜出料,结束反应。
实施例2
依次将反应介质水80克、氧化剂过硫酸铵0.36克、还原剂亚硫酸氢钠0.18克、乳化剂十二烷基硫酸钠2.5克、稳定剂乙二胺四乙酸钾0.02克、偏氯乙烯90克、共聚单体甲基丙烯酸甲酯8.5克和丙烯酸1.5克加入反应釜中,然后充氮气至反应体系压力为1.013×105帕斯卡(1千克/平方厘米),开启搅拌并升温至55℃,开始反应。待反应体系压力降至基本不变时,升温熟化,然后降温、卸压,除去剩余单体,开釜出料,结束反应。
Claims (3)
1. 一种偏氯乙烯共聚物胶乳的制备方法,其特征在于:在聚合釜内依次加入分散介质水80重量份,引发剂过硫酸铵0.36重量份,还原剂亚硫酸氢钠0.18重量份,乳化剂十二烷基硫酸钠2.5重量份;再加入水量的50~400ppm的稳定剂乙二胺四乙酸盐,以及单体偏氯乙烯90重量份、共聚单体甲基丙烯酸甲酯8.5重量份、丙烯酸1.5重量份;加料完毕后冲氮气至反应体系压力为1.013×105帕斯卡,开启搅拌升温至55℃,开始反应,待反应体系压力降到基本不变时,升温熟化,然后降温、卸压,除去剩余单体,开釜出料,结束反应。
2. 如权利要求1所述的偏氯乙烯共聚物胶乳的制备方法,其特征在于:反应体系中加入了水量的150~250ppm的乙二胺四乙酸盐。
3. 如权利要求1或2所述的偏氯乙烯共聚物胶乳的制备方法,其特征在于:所说的乙二胺四乙酸盐为乙二胺四乙酸钠或乙二胺四乙酸钾。
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CN1178225A CN1178225A (zh) | 1998-04-08 |
CN1068010C true CN1068010C (zh) | 2001-07-04 |
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