CN110204723B - 一种耐热性聚苯硫醚的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 claims abstract description 13
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 11
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims abstract description 9
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
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- 239000011593 sulfur Substances 0.000 description 5
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
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- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
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- 229940079101 sodium sulfide Drugs 0.000 description 2
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- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
本发明提供了一种空心球状耐热性聚苯硫醚的制备方法，首先将九水硫化钠经过高温隔氧处理得到无水硫化钠，再以碳酸钾、碳酸钠与氯化锂为组合催化剂，与上述制备的无水硫化钠溶液混匀，用氢氧化钠调溶液至pH=9~10，然后在氮气保护下升温至220~225℃，恒温反应6~8 h；洗涤，过滤，干燥，得到空心球状的聚苯硫醚。经测试，空心球状聚苯硫醚的熔点在297℃，具有很好的耐热性，而且，这种聚苯硫醚具有更大的比表面积，能更多的与其他物质的相容，因此可以很容易的在空壳中引入各种基团（无机大分子/金属氧化物等），从而用于制备各种基团修饰的聚苯硫醚复合材料。
Description
技术领域
本发明涉及一种聚苯硫醚的制备方法，尤其涉及一种空心球状结构的耐热性聚苯硫醚的制备方法，属于材料制备领域。
背景技术
聚苯硫醚（Polyphenylene sulfide，缩写PPS）是分子中含有对亚苯基硫醚重复结构单元的聚合物，是一种新型功能性工程塑料，在电子、汽车、机械及化工领域均有广泛应用。pps具有机械强度高、耐高温、高阻燃、耐化学药品性能强等优点；具有硬而脆、结晶度高、难燃、热稳定性好、机械强度较高、电性能优良等优点。聚苯硫醚又是一种两疏性物质，在其苯环与硫原子的交替排列的结构中可以看出其刚性非常强，基本不溶任何溶剂，从而决定它的宏观性质——高机械强度。因此，聚苯硫醚可如同催化剂载体或者复合材料基底存在。
目前合成PPS的方法很多，如卤硫酚盐的自缩聚，对卤二苯和硫磺的熔融聚合，硫磺和苯的亲电子反应，碱金属硫化物与对二卤苯的溶液缩聚(硫化钠法)，硫磺和对二氯苯的溶液缩聚(硫磺溶液法)，二苯二硫醚在路易斯酸作用下的聚合等等。目前用于工业生产的为硫化钠法和硫磺溶液法，制备的聚苯硫醚的微观形态有片层状、球状、花状、网状等，尺寸扩展到几微米也可小到纳米级。但是，这些结构的聚苯硫醚耐热性较差，因而限制了其应用。
发明内容
本发明的目的是提供一种空心球状结构的耐热性聚苯硫醚的制备方法。
本发明空心球状结构聚苯硫醚的制备，是在持续通氮气的条件下，先将九水合硫化钠分散于N-二甲基吡咯烷酮中，于150~160℃下反应1.5~2 h，得到无水硫化钠溶液；再在无水硫化钠溶液中加入组合催化剂混匀，用氢氧化钠调溶液至pH=9~10，升温至70~80℃，加入对二氯苯搅拌均匀；然后升温至220~225℃，恒温反应6~8 h；反应结束后洗涤，过滤，干燥，得到空心球状的耐热性聚苯硫醚。
所述组合催化剂由氯化锂、碳酸钾、碳酸钠组成，且氯化锂与碳酸钾的质量比为4:1~3.5:1；氯化锂与碳酸钾的质量比为3.5:1~3.0:1。组合催化剂的与九水合硫化钠的质量比为1:4~1:5；对二氯苯与九水合硫化钠的质量比为1:1.5~1:2。
为了达到更好的分散效果，先将组合催化剂以1:40~1:45g/mL的质量体积比分散于N-二甲基吡咯烷酮中，再加入到无水硫化钠溶液。持续通入氮气的气体速率为 10~15mL/min。
图1为本发明制备的空心球状聚苯硫醚的扫描电镜图。从图1中可以看到，聚苯硫醚呈空心球状，并且分布均匀，而且具有大规模的平整结构。因此可以很容易的在空隙中引入各种基团（如金属离子、大分子无机物或有机物等），从而制得由各种基团修饰的聚苯硫醚复合材料。
表1为不同形貌的聚苯硫醚的耐热性能。由表1可知，本发明制备的空心球状的聚苯硫醚的耐热性能明显优于其他形状的聚苯硫醚。
本发明用氯化锂、碳酸钠、碳酸钾组合催化剂，对亲核取代反应有极大的促进作用；形成的空心球状聚苯硫醚具有更大的比表面积，能更多的与其他物质的相容，同时空心球状结构有效隔阻了其传热效能，进而提高了空心球状聚苯硫醚的熔点，赋予其良好的耐热性能，拓宽了聚苯硫醚的应用。
附图说明
图1为本发明制备的空心球状聚苯硫醚在0℃下干燥后的扫描电镜图。
具体实施方式
下面通过具体实例对本发明一种空心球状结构聚苯硫醚的制备、形貌等作进一步说明。
（1）无水硫化钠的制备：称取九水合硫化钠79.5 g，加入到180mL N-二甲基吡咯烷酮中，持续通入氮气隔氧保护（氮气流速保持在10 mL/min）下，在150~160℃中反应1 h，得到绿色的无水硫化钠溶液，降温后倒入反应釜中；
（2）组合催化剂的制备：称取5.933 g无水氯化锂，1.658 g无水碳酸钾，1.732 g无水碳酸钠，密封混匀，防止被氧化和潮解；
（3）空心球聚苯硫醚的制备：将组合催化剂溶于230mL N-二甲基吡咯烷酮中，加入到反应釜中混匀，在室温、搅拌（搅拌速度为40 r/min）下加入氢氧化钠将溶液调至碱性（pH=9~10），升温至70℃，搅拌下加入44.1 g对二氯苯，得到墨绿色溶液；密封反应釜后，在搅拌（搅拌速度为900 r/min）下持续通入氮气（通入氮气速率为10 mL/min ）来置换反应釜中空气；然后升温至220℃，保持此温度反应6 h，此时溶液为黑色；用去离子水、乙醇反复洗涤，60℃热过滤，0 ℃下干燥，得到10.5 g空心球状的聚苯硫醚。熔点297℃。聚苯硫醚的扫描电镜图如图1所示，聚苯硫醚呈空心球状并且分布均匀。
Claims (5)
1.一种耐热性聚苯硫醚的制备方法，持续通氮气的条件下，先将九水合硫化钠分散于N-二甲基吡咯烷酮中，于150~160℃下反应1.5~2 h，得到无水硫化钠溶液；再在无水硫化钠溶液中加入组合催化剂混匀，用氢氧化钠调溶液至pH=9~10，升温至70~80℃，加入对二氯苯搅拌均匀；然后升温至220~225℃，恒温反应6~8 h；反应结束后洗涤，过滤，干燥，得到空心球状的耐热性聚苯硫醚；所述组合催化剂由氯化锂、碳酸钾、碳酸钠组成，且氯化锂与碳酸钾的质量比为4:1~3.5:1；氯化锂与碳酸钠的质量比为3.5:1~3.0:1。
2.如权利要求1所述一种耐热性聚苯硫醚的制备方法，其特征在于：将组合催化剂以1:40~1:45g/mL的质量体积比分散于N-二甲基吡咯烷酮中，再加入到无水硫化钠溶液。
3.如权利要求1所述一种耐热性聚苯硫醚的制备方法，其特征在于：组合催化剂的与九水合硫化钠的质量比为1:4~1:5。
4.如权利要求1所述一种耐热性聚苯硫醚的制备方法，其特征在于：对二氯苯与九水合硫化钠的质量比为1:1.5~1:2。
5.如权利要求1所述一种耐热性聚苯硫醚的制备方法，其特征在于：持续通入氮气的气体速率为 10~15 mL/min。
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| CN108752586A (zh) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | 一种花束状结构聚苯硫醚的制备方法 |
| CN109517174A (zh) * | 2018-11-02 | 2019-03-26 | 西北师范大学 | 一种三维网络状结构聚苯硫醚的制备方法 |
| CN109810507B (zh) * | 2019-01-10 | 2021-06-01 | 西北师范大学 | 一种聚苯硫醚/四氧化三铁复合材料的制备方法 |
| CN109852057B (zh) * | 2019-01-18 | 2021-07-23 | 西北师范大学 | 一种聚苯硫醚/石墨烯量子点复合材料的制备方法 |
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