CN114163602A - 一种聚苯醚-聚醚嵌段共聚物 - Google Patents
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 23
- 229920000570 polyether Polymers 0.000 title claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 14
- 229920006389 polyphenyl polymer Polymers 0.000 title claims abstract description 9
- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 229920000090 poly(aryl ether) Polymers 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920006380 polyphenylene oxide Polymers 0.000 description 6
- 238000004448 titration Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
本发明涉及一种聚苯醚‑聚醚嵌段共聚物，该嵌段共聚物有如下特征，包含聚芳醚链段A段和聚醚链段B段，形成ABA结构的共聚物。该嵌段共聚物是由单羟基封端聚苯醚在双官异氰酸酯存在下与聚醚反应得到。该嵌段共聚物具有很好的耐热性、力学性能。
Description
技术领域
本发明涉及一种聚苯醚-聚醚嵌段共聚物。
背景技术
聚芳醚，是一种通用工程塑料。具有具有优良的综合性能，最大的特点是在长期负荷下，具有优良的尺寸稳定性和突出的电绝缘性，使用温度范围广。具有自熄性。具有优良的耐水、耐蒸汽性能，制品具较高的拉伸强度和抗冲强度，抗蠕变性也好。此外，有较好的耐磨性和电性能。
但是聚苯醚与其它树脂相容性差，尤其烯烃类树脂，导致性能不佳。采用化学嵌段的方法可大大改善两种不相容聚合物的相容性和分散稳定性，得到性能均衡的新型化合物。CN101654516B公开了一种聚碳酸酯-聚苯醚嵌段共聚物，CN104704061公开了一种聚苯醚-聚硅氧烷嵌段共聚物组合物。聚醚具有很好的耐溶剂、耐低温性能，但与聚苯醚相容性极差，为改善上述问题，本发明提供了一种聚苯醚-聚醚嵌段共聚物。
发明内容
本发明提供了一种聚苯醚-聚醚嵌段共聚物，具有优良的耐热性和力学性能。
为实现上述目的，本发明提供了一种聚苯醚-聚醚嵌段共聚物，由单羟基封端聚苯醚A段、双羟基封端聚醚B段和双官异氰酸酯为原料制备得到，结构为ABA型，如式-1所示
其中，A为
B为
其中，n=5-10，m=5-2000，R1，R2为C1-C10的烷基，R为C5-C20的脂肪族或芳香族结构。
单羟基封端聚苯醚，是指特性粘度0.05-0.07dL/g，羟基含量500-600μmol/g的聚苯醚。
双羟基封端聚醚，是指双羟基聚乙二醇、双羟基聚丙二醇等但不限于上述化合物，粘度1500-2000mPa·s，羟基值25-30mgKOH/g。
双官异氰酸酯，是指具有两个异氰酸酯结构的小分子芳香族或脂肪族化合物，优选脂肪族化合物，如六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯、二苯基甲烷二异氰酸酯等，但不限于上述化合物。
制备方法如下：将单羟基聚苯醚溶于甲苯配制成5%左右的溶液，加热到110℃回流1h进行脱水，然后在氮气保护的情况下将物料温度降至40℃恒温，搅拌，同时将一定量的干燥的聚醚和双官异氰酸酯分别缓慢滴加到聚苯醚的甲苯溶液中，滴定时间1h。滴定结束后，继续反应1h，然后降至室温，用3倍的甲醇沉淀，过滤，干燥后得到共聚物。
本发明提供的嵌段共聚物具有优异的耐温性能和力学性能，与聚烯烃具有良好的相容性。
具体实施方式：
本发明提供的嵌段共聚物具有ABA的结构特征，制备方法如下：将单羟基聚苯醚溶于甲苯配制成5%左右的溶液，加热到110℃回流1h进行脱水，然后在氮气保护的情况下将物料温度降至40℃恒温，搅拌，同时将一定量的干燥的聚醚和双官异氰酸酯分别缓慢滴加到聚苯醚的甲苯溶液中，滴定时间1h。滴定结束后，继续反应1h，然后降至室温，用3倍的甲醇沉淀，过滤，干燥后得到共聚物。
实施例1
将100g单羟基聚苯醚（中沐化工，特性粘度0.06dL/g，羟基含量550μmol/g）溶于2200g甲苯配制成溶液，加热到110℃回流1h进行脱水，然后在氮气保护的情况下将物料温度降至40℃恒温，搅拌，同时将60g干燥的双羟基封端聚乙二醇（粘度1800mPa·s，羟基值28mgKOH/g）和3g异氟尔酮二异氰酸酯分别缓慢滴加到聚苯醚的甲苯溶液中，滴定时间1h。滴定结束后，继续反应1h，然后降至室温，用3倍的甲醇沉淀，过滤，干燥后得到共聚物。
应理解，本实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明的内容后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样在本申请所附权利要求书所限定的范围。
Claims (2)
1.一种聚苯醚-聚醚嵌段共聚物，其特征在于，由单羟基封端聚苯醚A段、双羟基封端聚醚B段和双官异氰酸酯为原料制备得到，结构为ABA型，如式-1所示
其中，A为
B为
其中，n=5-10，m=5-2000，R1，R2为C1-C10的烷基，R为C5-C20的脂肪族或芳香族结构。
2.根据权利要求1所述的单羟基封端聚苯醚，其特征在于，特性粘度0.05-0.07dL/g，羟基含量500-600μmol/g。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654516B (zh) * | 2009-07-13 | 2011-12-28 | 中国蓝星（集团）股份有限公司 | 一种聚碳酸酯--聚苯醚嵌段共聚物、其制备方法及其应用 |
| US20140221552A1 (en) * | 2013-02-01 | 2014-08-07 | Sabic Innovative Plastics Ip B.V. | Triblock copolymer, method for its formation, and compatibilized compositions comprising it |
| CN104704061A (zh) * | 2012-11-08 | 2015-06-10 | 沙特基础全球技术有限公司 | 增强的聚苯醚-聚硅氧烷嵌段共聚物组合物及包含其的制品 |
| CN108059722A (zh) * | 2017-12-22 | 2018-05-22 | 杭州师范大学 | 一种聚芳醚-聚硅氧烷共聚物及其制备方法 |
| CN113461895A (zh) * | 2021-06-17 | 2021-10-01 | 淮阴工学院 | 有机硅烷改性的超支化聚苯醚的制备方法 |
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- 2021-12-26 CN CN202111606239.XA patent/CN114163602A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654516B (zh) * | 2009-07-13 | 2011-12-28 | 中国蓝星（集团）股份有限公司 | 一种聚碳酸酯--聚苯醚嵌段共聚物、其制备方法及其应用 |
| CN104704061A (zh) * | 2012-11-08 | 2015-06-10 | 沙特基础全球技术有限公司 | 增强的聚苯醚-聚硅氧烷嵌段共聚物组合物及包含其的制品 |
| US20140221552A1 (en) * | 2013-02-01 | 2014-08-07 | Sabic Innovative Plastics Ip B.V. | Triblock copolymer, method for its formation, and compatibilized compositions comprising it |
| CN108059722A (zh) * | 2017-12-22 | 2018-05-22 | 杭州师范大学 | 一种聚芳醚-聚硅氧烷共聚物及其制备方法 |
| CN113461895A (zh) * | 2021-06-17 | 2021-10-01 | 淮阴工学院 | 有机硅烷改性的超支化聚苯醚的制备方法 |
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Application publication date: 20220311 |