CN112111051A - 一种己内酯低聚物的合成工艺 - Google Patents
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
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- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 3
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
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- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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Abstract
本发明提供了一种己内酯低聚物的合成工艺，包括如下步骤：1）将6‑羟基己酸酯、第一催化剂先聚合反应3‑20h；2）聚合结束后加入第二催化剂和溶剂，反应3‑24h后，将产品和溶剂分离，得到聚己内酯低聚物。本发明的有益效果是：该方法过程简单，成本低，得到的己内酯低聚物分子量在1000左右，分散系数在1.1‑1.3之前，反应可控，收率高，经济效益可观。
Description
技术领域
本发明属于化工行业，具体涉及一种己内酯低聚物的合成工艺。
背景技术
己内酯低聚物一般是ε-己内酯在引发剂和催化剂作用下，在加热和真空状态下聚合得到的2-10分子低聚物，其分子量一般在1000以下，低分子量的己内酯低聚物容易解聚得到ε-己内酯。
中国专利文献CN104292206A找到了以己内酯低聚物解决制ε-己内酯的技术方案，除此之外，还可以己内酯低聚物为基础制备一些聚酯类聚氨酯，分子量<3000的低聚物有很好的弹性，也可与多种聚合材料共聚制造皮带、各种薄膜、纤维和鞋底。
关于己内酯低聚物的合成，文献中有以ε-己内酯为原料，正己醇为引发剂，卟啉铝化物催化下合成了己内酯低聚物，
发明内容
为解决上述问题，本专利以6-羟基己酸酯在一定温度和压力下，通过催化剂作用合成分子量1000左右的己内酯低聚物，大大降低了成本，提高了产率。
本发明的技术方案如下：
一种己内酯低聚物的合成工艺，包括如下步骤：
1)将6-羟基己酸酯、第一催化剂先聚合反应3-20h；
2)聚合结束后加入第二催化剂和溶剂，反应3-24h后，将产品和溶剂分离，得到聚己内酯低聚物。
步骤1)中，第一催化剂选自辛酸亚锡、钛酸四丁酯、四氯化钛、三氯化钛、三氯氧钒中的一种或几种。
步骤1)中，第一催化剂用量为6-羟基己酸酯的0.001％-5％。
步骤1)中，聚合反应温度100-200℃，压力绝压0.005-0.1MPa、时间3-20h。
步骤2)中，第二催化剂选自乙酸钴、乙二醇锑、锰、锌、钙、钴、铅的醋酸盐、无定形硅酸铝、ZSM-5型分子筛中的一种或几种。
步骤2)中，第二催化剂用量为6-羟基己酸酯的0-5％。
步骤2)中，溶剂选自THF、DMSO、氯仿、DMF、乙二醇苯醚、甘油、三硝基苯、聚乙二醇单甲醚、聚乙二醇二甲醚、硝基苯中的一种或几种。
步骤2)中，溶剂用量为6-羟基己酸酯的0-300％。
步骤2)中，反应温度在100-350℃之间。
步骤2)中，反应压力在绝压0.005-0.1MPa。
步骤2)中，反应时间在3-24h之间。
本发明的有益效果是：
该方法过程简单，成本低，得到的己内酯低聚物分子量在1000左右，分散系数在1.1-1.3之前，反应可控，收率高，经济效益可观。
具体实施方式
下面结合实例对本发明进一步描述。但本发明的保护范围不仅限于此。
实施例1
将10g6-羟基己酸酯、醋酸锌0.05g在100℃，绝压0.01MPa下反应2h，反应结束后加入醋酸锌0.05g和15mlTHF加入100ml单口烧瓶中，将烧瓶放入集热式恒温加热磁力搅拌仪中，加热至120℃，在绝压0.01MPa的条件下恒温反应6h，反应结束后降温取出，分离溶剂和产物，得己内酯低聚物9.79g，6-羟基己酸的获得率为97.9％。
实施例2-5
6-羟基己酸酯质量同实施例1，其他与实施例1不同，详见表1。
实施例6-10
6-羟基己酸酯质量为20g，其他与实施例1不同，详见表1。
实施例11-15
6-羟基己酸酯质量为30g，其他与实施例1不同，详见表1。
实施例1-15的实验数据详见表1。
表1实施例实验数据汇总
由表中可以看出，本发明方法过程简单，成本低，得到的己内酯低聚物分子量在1000左右，分散系数在1.1-1.3之前，反应可控，收率高达96％以上，经济效益可观。
Claims (9)
1.一种己内酯低聚物的合成工艺，其特征在于：包括如下步骤：
1)将6-羟基己酸酯、第一催化剂先聚合反应3-20h；
2)聚合结束后加入第二催化剂和溶剂，反应3-24h后，将产品和溶剂分离，得到聚己内酯低聚物。
2.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤1)中，第一催化剂选自辛酸亚锡、钛酸四丁酯、四氯化钛、三氯化钛、三氯氧钒中的一种或几种。
3.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤1)中，第一催化剂用量为6-羟基己酸酯的0.001％-5％。
4.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤1)中，聚合反应温度100-200℃，压力绝压0.005-0.1MPa、时间3-20h。
5.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤2)中，第二催化剂选自乙酸钴、乙二醇锑、锰、锌、钙、钴、铅的醋酸盐、无定形硅酸铝、ZSM-5型分子筛中的一种或几种。
6.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤2)中，第二催化剂用量为6-羟基己酸酯的0-5％。
7.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤2)中，溶剂选自THF、DMSO、氯仿、DMF、乙二醇苯醚、甘油、三硝基苯、聚乙二醇单甲醚、聚乙二醇二甲醚、硝基苯中的一种或几种。
8.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤2)中，溶剂用量为6-羟基己酸酯的0-300％。
9.如权利要求1所述的一种己内酯低聚物的合成工艺，其特征在于：步骤2)中，反应温度在100-350℃之间，反应压力在绝压0.005-0.1MPa，反应时间在3-24h之间。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175177A (zh) * | 2020-10-15 | 2021-01-05 | 贵州省材料技术创新基地 | 一种催化剂及其制备方法和聚乳酸的制备方法 |
| CN112892190A (zh) * | 2021-01-27 | 2021-06-04 | 成都中科绿生环境科技有限公司 | 一种化学除臭剂及其制备方法 |
| CN114044886A (zh) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | 一种聚己内酯的生产方法 |
| CN114044891A (zh) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | 一种聚己内酯的制备方法 |
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| CN106146817A (zh) * | 2015-04-21 | 2016-11-23 | 上海浦景化工新材料有限公司 | 羟基烷酸锌聚酯催化剂，其制备方法以及该催化剂的应用 |
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| CN112175177A (zh) * | 2020-10-15 | 2021-01-05 | 贵州省材料技术创新基地 | 一种催化剂及其制备方法和聚乳酸的制备方法 |
| CN112175177B (zh) * | 2020-10-15 | 2023-01-20 | 贵州省材料技术创新基地 | 一种催化剂及其制备方法和聚乳酸的制备方法 |
| CN112892190A (zh) * | 2021-01-27 | 2021-06-04 | 成都中科绿生环境科技有限公司 | 一种化学除臭剂及其制备方法 |
| CN112892190B (zh) * | 2021-01-27 | 2023-03-10 | 成都中科绿生环境科技有限公司 | 一种化学除臭剂及其制备方法 |
| CN114044886A (zh) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | 一种聚己内酯的生产方法 |
| CN114044891A (zh) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | 一种聚己内酯的制备方法 |
| CN114044891B (zh) * | 2021-12-01 | 2023-08-29 | 青岛科技大学 | 一种聚己内酯的制备方法 |
| CN114044886B (zh) * | 2021-12-01 | 2023-08-29 | 青岛科技大学 | 一种聚己内酯的生产方法 |
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