CN1056161C - 胺化聚(2,6－二甲基－1,4－苯醚)的合成 - Google Patents
胺化聚(2,6－二甲基－1,4－苯醚)的合成 Download PDFInfo
- Publication number
- CN1056161C CN1056161C CN96119037A CN96119037A CN1056161C CN 1056161 C CN1056161 C CN 1056161C CN 96119037 A CN96119037 A CN 96119037A CN 96119037 A CN96119037 A CN 96119037A CN 1056161 C CN1056161 C CN 1056161C
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- poly
- phenylate
- phenyl ether
- tin protochloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000005576 amination reaction Methods 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 235000011150 stannous chloride Nutrition 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 11
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 235000009518 sodium iodide Nutrition 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000010189 synthetic method Methods 0.000 claims 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 229920006351 engineering plastic Polymers 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920006380 polyphenylene oxide Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BZFKSWOGZQMOMO-UHFFFAOYSA-N 3-chloropropan-1-amine Chemical compound NCCCCl BZFKSWOGZQMOMO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyamides (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明是合成胺化聚(2，6-二甲基-1，4-苯醚)的方法。
本发明提供一种直接将氨基接到聚(2，6-二甲基-1，4-苯醚)的苯环上的合成方法，具体步骤是先将聚(2，6-二甲基-1，4-苯醚)硝化，然后将带硝基的聚(2，6-二甲基-1，4-苯醚)还原为胺化聚(2，6-二甲基-1，4-苯醚)，可获得的氨基取代度为5～65%。
本发明提供的合成方法条件简单，容易控制，经胺化后的聚(2，6-二甲基-1，4-苯醚)将成为能衍生出许多新的工程塑料合金的功能材料，在气体分离膜上也将具有良好的应用前景。
Description
本发明涉及聚(2，6-二甲基-1，4-苯醚)(PPO)的化学改性。
聚[2，6-二甲基1，4-苯醚]是本世纪六十年代发展起来的一种优良的工程塑料，为了获得一些特别的功能而对它进行化学改性的研究近十年来十分活跃。对于胺化聚(2，6-二甲基-1，4-苯醚)曾有过报导JP 05 98，149[93，98，149](C1.C08L71/12)，其方法是在氢氧化钠和氯化三辛基甲基胺的溶液中，用3-氯丙基胺将聚(2，6-二甲基-1，4-苯醚)的端羟基胺化，得到端基为氨基的聚(2，6-二甲基-1，4-苯醚)，显然这种胺化程度是很小的。本发明是在聚(2，6-二甲基-1，4-苯醚)的苯环上直接接上氨基(NH2-)，其合成路线如下：
本合成通过以下步骤实现：(1)用硝酸和硫酸的混合酸在10～40℃下硝化聚(2，6-二甲基-1，4-苯醚)。(2)将硝化的聚(2，6-二甲基-1，4-苯醚)用盐酸和氯化亚锡还原为胺化聚苯醚，其中加入冰醋酸和少量碘化钠以提高氯化亚锡的还原能力。氯化亚锡的用量是8～20g氯化亚锡/1g硝化聚(2，6-二甲基-1，4-苯醚)，冰醋酸的用量是0.6～3ml冰醋酸/1g氯化亚锡，碘化钠的用量是氯化亚锡的1/10～160重量比)，还原温度为60～80℃，氨基的摩尔取代度为5～65％。
本发明能够合成一种新型的以聚(2，6-二甲基-1，4-苯醚)为基质的功能材，它不但能保持原来聚(2，6-二甲基-1，4-苯醚)的优异的力学性能，而且由于极性基团的引入，它可以大大的提高和其它极性聚合物(如尼龙，聚碳酸酯等)的相容性。特别是氨基的氮原子上有一对孤对电子，是电子给体，表现出弱碱性，利用这些特性，可以将胺化的聚(2，6-二甲基-1，4-苯醚)和一些带有吸电子基团或酸性基团的聚合物共混，通过它们之间的离子相互作用，从而得到相容性很好的共混体系。所以，这种改性后的聚(2，6-二甲基-1，4-苯醚)将成为能衍生出许多新的工程塑料合金的功能材料。此外，胺化度达50mol％后，胺化聚(2，6-二甲基-1，4-苯醚)可完全溶解在DMSO，DMF，二氧六环，甲醇，乙醇等极性溶剂中，较宽的溶剂范围及氨基的特性将使这种改性后的聚(2，6-二甲基-1，4-苯醚)，在气体分离膜上具有良好的应用前景。本合成还具有反应条件简单，容易控制的优点。
实例1.
(1)20g聚(2，6-二甲基-1，4-苯醚)溶于400ml氯仿中，将10ml硝酸和0.3ml浓硫酸组成的混合酸缓慢滴加到该氯仿溶液，在30℃下反应20min，然后用去离子水洗该溶液到pH值为7，再用甲醇把硝化聚(2，6-二甲基-1，4-苯醚)沉淀出来，其摩尔硝化度为14％。(2)5g上述硝化聚(2，6-二甲基-1，4-苯醚)溶于100ml氯仿中，将70g二水合氯化亚锡和2g碘化钠溶于150ml的盐酸/冰醋酸(100/50/v/v)混合酸中，溶解后迅速倒入该硝化聚(2，6-二甲基-1，4-苯醚)的溶液中，在65℃、氮气保护下回流反应3小时。反应结束后倒掉酸相，用石油醚将氯仿相中的胺化聚(2，6-二甲基-1，4-苯醚)沉淀出来。
实例2.
(1)5g聚(2，6-二甲基-1，4-苯醚)溶于100ml氯仿中，将10ml硝酸和0.2ml浓硫酸组成的混合酸缓慢滴加到该氯仿溶液，在30℃下反应20min，然后用去离子水洗该溶液到pH值为7，再用甲醇把硝化聚(2，6-二甲基-1，4-苯醚)沉淀出来，其摩尔硝化度为51％。(2)5g上述硝化聚(2，6-二甲基-1，4-苯醚)溶于100ml氯仿中，将70g二水合氯化亚锡和2g碘化钠溶于150ml的盐酸/冰醋酸(100/50/v/v)混合酸中，溶解后迅速倒入该硝化聚(2，6-二甲基-1，4-苯醚)的溶液中，在65℃、氮气保护下回流反应3小时。由于胺化度超过16％后，它将不再完全溶于氯仿中，所以反应过程中要不断滴加甲醇以防止胺化的聚苯醚沉淀出来。反应结束后拆出回流装置，继续加热，将反应液中的氯仿和甲醇全部蒸发掉，则其中的胺化聚(2，6-二甲基-1，4-苯醚)从酸相沉淀出来。
Claims (3)
1、一种合成胺化聚(2，6-二甲基-1，4-苯醚)的方法，其特征在于是直接将氨基接到聚(2，6-二甲基-1，4苯醚)的苯环上，其步骤是先将聚(2，6-二甲基-1，4苯醚)用硫酸和硝酸的混合酸硝化，然后将带硝基的聚(2，6-二甲基-1，4苯醚)还原，其还原剂用氯化亚锡和盐酸，并加入还原强化剂增强还原反应，还原温度为60～80℃，反应3小时，氨基的摩尔取代度为5～65％，得到苯环上直接带氨基的胺化聚(2，6-二甲基-1，4-苯醚)。
2、根据权利要求1中所述的合成方法，其特征在于所述的还原剂氯化亚锡的用量为8～20g氯化亚锡/1g硝化聚(2，6-二甲基-1，4苯醚)。
3、根据权利要求1中所述的合成方法，其特征在于所述的还原强化剂是冰醋酸和碘化钠，冰醋酸的用量是0.6～3ml冰醋酸/1g氯化亚锡，碘化钠的用量是氯化亚锡用量的1/10～1/60重量比。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96119037A CN1056161C (zh) | 1996-03-11 | 1996-03-11 | 胺化聚(2,6－二甲基－1,4－苯醚)的合成 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96119037A CN1056161C (zh) | 1996-03-11 | 1996-03-11 | 胺化聚(2,6－二甲基－1,4－苯醚)的合成 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149593A CN1149593A (zh) | 1997-05-14 |
| CN1056161C true CN1056161C (zh) | 2000-09-06 |
Family
ID=5125498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96119037A Expired - Fee Related CN1056161C (zh) | 1996-03-11 | 1996-03-11 | 胺化聚(2,6－二甲基－1,4－苯醚)的合成 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1056161C (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115505222B (zh) * | 2022-10-26 | 2023-09-05 | 江苏绿安擎峰新材料有限公司 | 一种高导热无卤阻燃聚苯乙烯复合材料及其制备方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039499A2 (de) * | 1980-05-07 | 1981-11-11 | Leopoldo Tartarini | Scherenstossdämpfer |
| EP0350137A2 (en) * | 1988-07-07 | 1990-01-10 | Shell Internationale Researchmaatschappij B.V. | Process for preparation of modified polyphenylene ether or related polymers and the use thereof in modified high temperature rigid polymer of vinyl substituted aromatics |
| EP0403023A2 (en) * | 1989-06-13 | 1990-12-19 | Shell Internationale Researchmaatschappij B.V. | Process for modification of polyphenylene ether or related polymers with a cyclic acid anhydride and the use thereof in modified, high temperature rigid polymer of vinyl substituted aromatics |
-
1996
- 1996-03-11 CN CN96119037A patent/CN1056161C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039499A2 (de) * | 1980-05-07 | 1981-11-11 | Leopoldo Tartarini | Scherenstossdämpfer |
| EP0350137A2 (en) * | 1988-07-07 | 1990-01-10 | Shell Internationale Researchmaatschappij B.V. | Process for preparation of modified polyphenylene ether or related polymers and the use thereof in modified high temperature rigid polymer of vinyl substituted aromatics |
| EP0403023A2 (en) * | 1989-06-13 | 1990-12-19 | Shell Internationale Researchmaatschappij B.V. | Process for modification of polyphenylene ether or related polymers with a cyclic acid anhydride and the use thereof in modified, high temperature rigid polymer of vinyl substituted aromatics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1149593A (zh) | 1997-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20210202972A1 (en) | Comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity and preparation method thereof | |
| CN110437456B (zh) | 一种自愈合聚合物及其制备方法与应用 | |
| CN112759778B (zh) | 一种高强度碱性阴离子聚合物交联膜及其制备方法 | |
| CN1056161C (zh) | 胺化聚(2,6－二甲基－1,4－苯醚)的合成 | |
| CA2417679A1 (en) | Dendritic macromolecule with improved polyether polyol solubility and process for production thereof | |
| CN113372527A (zh) | 一种仿生室温自修复聚氨酯材料的制备方法 | |
| CN110041519B (zh) | 一种长支链聚芳醚腈阴离子交换膜及其制备方法 | |
| US4912246A (en) | 1,3-bis(alkylcarbonato)-nitrobenzenes | |
| CN111732717A (zh) | 含有聚芳哌啶基侧链的聚合物、制备方法及阴离子交换膜、制备方法 | |
| CN118063766A (zh) | 一种季铵化共价三嗪有机框架阴离子交换膜及其制备方法 | |
| Matsuoka et al. | Synthesis of Carbosilane Compounds Functionalized with Three or Four. BETA.-Cyclodextrin Moieties. Use of a One-Pot Reaction in Liquid Ammonia for Birch Reduction and the Subsequent SN2 Replacement. | |
| CN110317356B (zh) | 一种多官能化交联型聚亚芳基丁二酮阴离子交换膜及其制备方法 | |
| CN110117289B (zh) | 两步法制备cl-20的方法 | |
| CN115449074B (zh) | 侧链含直链烷基链和赖氨酸的聚天冬酰胺衍生物增稠剂 | |
| CN115445673B (zh) | 一种借助于氢键作用力来提升性能的共混型阴离子交换膜及制备方法 | |
| CN111517998B (zh) | 一种两性离子表面活性剂及其制备方法 | |
| CN102875813A (zh) | 一种聚硅氧烷改性聚苯胺及其制备方法 | |
| CN110317143A (zh) | 一种l-2,4-二氨基丁酸盐酸盐的制备方法 | |
| CN113321774A (zh) | 一种基于聚氨酯的形状记忆聚合物、聚合物电解质及制备 | |
| JP4088666B2 (ja) | モノマーおよびスルホン酸樹脂 | |
| CN115403720A (zh) | 酚醛树脂交联剂及其制备方法 | |
| CN116622101B (zh) | 一种羧甲基纤维素交联微球的制备工艺 | |
| CN103613506B (zh) | 一种双(脂肪醇聚氧烷烯醚)仲胺的制备方法 | |
| CN1546547A (zh) | 阳离子芳香族水性聚氨酯树脂的后扩链工艺方法 | |
| CN101323578A (zh) | 对氨基苯甲胺的合成方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Pan Yan Inventor after: Huang Yuhui Inventor after: Liao Bing Inventor after: Cong Guangmin Inventor before: Pan Yan Inventor before: Huang Yuhui Inventor before: Cong Guangmin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: PAN YAN; HUANG YUHUI; CONG GUANGMIN TO: PAN YAN; HUANG YUHUI; LIAO BING; CONG GUANGMIN |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |