CN1015546B - The preparation method of double citrate plasticizer - Google Patents
The preparation method of double citrate plasticizerInfo
- Publication number
- CN1015546B CN1015546B CN 88102691 CN88102691A CN1015546B CN 1015546 B CN1015546 B CN 1015546B CN 88102691 CN88102691 CN 88102691 CN 88102691 A CN88102691 A CN 88102691A CN 1015546 B CN1015546 B CN 1015546B
- Authority
- CN
- China
- Prior art keywords
- double
- citric acid
- diethylene glycol
- ecs
- ester
- 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
Links
- 239000004014 plasticizer Substances 0.000 title claims abstract description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 52
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 40
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 citric acid ester Chemical class 0.000 claims abstract description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 4
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 2
- 230000021736 acetylation Effects 0.000 claims description 2
- 238000006640 acetylation reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 9
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 150000007513 acids Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OVZBYIWZUUXJMN-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OCCOCCO OVZBYIWZUUXJMN-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
二重柠檬酸酯增塑剂ECG的制备方法：它是以柠檬酸、二甘醇、丁醇、环氧丙烷为原料，在催化剂的作用下，经多步结合制备而成的。它全称为：二重柠檬酸(二甘醇、四丁醇)酯或二重柠檬酸(双环氧丙烷化二甘醇)酯，是属于二重柠檬酸酯类。它具有不溶于水、闪点高、沸点高、不挥发、在塑料与橡胶中的迁移性小、稳定、塑化加工性能好，不仅能起主增塑剂作用，而且还可起辅功增塑剂的作用。主要应用于聚氯乙烯树脂、制造无毒的PVC产品及医疗卫生、食品包装等用品。在聚氯乙烯的压膜中使用，各项性能指标全部达到国家部颁标准。The preparation method of double citrate plasticizer ECG: it is prepared by multi-step combination with citric acid, diethylene glycol, butanol and propylene oxide as raw materials under the action of a catalyst. Its full name is: double citric acid (diethylene glycol, tetrabutyl alcohol) ester or double citric acid (diethylene glycol) ester, which belongs to the double citric acid ester category. It is insoluble in water, high flash point, high boiling point, non-volatile, small mobility in plastics and rubber, stable, good plasticizing performance, not only can act as the main plasticizer, but also can serve as auxiliary function The role of plasticizers. It is mainly used in polyvinyl chloride resin, the manufacture of non-toxic PVC products, medical and health care, food packaging and other supplies. It is used in the pressure film of polyvinyl chloride, and all performance indicators have reached the standards issued by the national ministry.
Description
本发明制备的增塑剂ECS，全称为：二重柠檬酸（二甘醇、四丁醇）酯或二重柠檬酸（双环氧丙烷化二甘醇）酯，是属于二重柠檬酸酯类。主要应用于聚氯乙烯树脂，制造无毒的PVC产品，用于食品包装材料，医疗用品材料，建筑行业的上水管等，也是纤维素树脂合成橡胶的无毒增塑剂、软化剂。The plasticizer ECS prepared by the present invention, the full name is: double citric acid (diethylene glycol, tetrabutyl alcohol) ester or double citric acid (diethylene glycol diethylene glycol) ester, which belongs to the double citric acid ester kind. It is mainly used in polyvinyl chloride resin to manufacture non-toxic PVC products, food packaging materials, medical supplies materials, water supply pipes in the construction industry, etc. It is also a non-toxic plasticizer and softener for cellulose resin synthetic rubber.
随着高分子材料工业的发展和市场的需要，必然要发展无毒增塑剂的生产，以适应各方面的需求，柠檬酸酯增塑剂的生产，在我国还未见任何报导，国外已在六十年代开始应用。根据文献（西德专利1200528报导，国外的化合物合成路线及原料如下：Along with the development of polymer material industry and the needs of the market, it is necessary to develop the production of non-toxic plasticizers to meet the needs of all aspects. The production of citrate plasticizers has not been reported in my country, and has been abroad. Applied in the 1960s. According to literature (West Germany patent 1200528 report, foreign compound synthetic routes and raw materials are as follows:
它的原料是：柠檬酸、单元醇（丁醇等），以及己二酸、戊二酸、癸二酸等及三氯化磷。Its raw materials are: citric acid, monoalcohol (butanol, etc.), adipic acid, glutaric acid, sebacic acid, etc., and phosphorus trichloride.
合成路线大体是第一步先合成柠檬酸酯。The synthetic route is generally that the first step is to synthesize citrate.
柠檬酸与单元醇在酸催化下反应形成酯：Citric acid reacts with monoalcohols under acid catalysis to form esters:
同时使二元酸形成二酰氯Simultaneously dibasic acids form diacyl chlorides
第二步柠檬酸酯与二酰氯反应形成二重柠檬酸酯The second step is the reaction of citrate with diacid chloride to form double citrate
n一般在4-8之间n is generally between 4-8
此合成路线中需要使用价格昂贵的二元酸和三氯化磷（或三氯氧磷），二元酸-如己二酸、癸二酸等，原料在我国不易获得，在制造二酰氯过程中，使用三氯化磷等反应性能极其活泼，对生产条件的要求比较高，需要特殊的防腐设备，而且使车间的劳动条件恶化，这些条件不是一般的增塑工厂所能解决的。This synthetic route needs to use expensive dibasic acid and phosphorus trichloride (or phosphorus oxychloride), dibasic acid-such as adipic acid, sebacic acid, etc., raw materials are not easy to obtain in my country, in the process of manufacturing diacyl chloride Among them, the use of phosphorus trichloride and other reactive properties is extremely active, the requirements for production conditions are relatively high, special anti-corrosion equipment is required, and the working conditions of the workshop are deteriorated. These conditions cannot be solved by ordinary plasticizing factories.
而本发明的增塑剂ECS的生产条件大大可以简化。一般的化工设备就可进行生产，也就是一般的增塑工厂不需特殊设备与条件就可以了。However, the production conditions of the plasticizer ECS of the present invention can be greatly simplified. General chemical equipment can be used for production, that is, general plasticizing factories do not need special equipment and conditions.
本发明的二重柠檬酸酯增塑剂ECS的制备方法：The preparation method of double citrate plasticizer ECS of the present invention:
二重柠檬酸增塑剂ECS是二重柠檬酸（二甘醇、四丁醇）酯或二 重柠檬酸（双环氧丙烷化二甘醇、四丁醇）酯，它们的分子式分别为：Double citric acid plasticizer ECS is double citric acid (diethylene glycol, tetrabutanol) ester or di Double citric acid (diethylene glycol, tetrabutyl alcohol) esters, their molecular formulas are:
它们所用原料是柠檬酸、丁醇、二甘醇（一缩二乙二醇）、环氧丙烷、乙酸酐。The raw materials they use are citric acid, butanol, diethylene glycol (diethylene glycol), propylene oxide, and acetic anhydride.
（ⅰ）柠檬酸酯与丁醇以1∶2克分子比，先得酸性酯。(i) Citrate and butanol are in a molar ratio of 1:2 to obtain the acidic ester first.
在硫酸催化作用下，硫酸用量0.3-1%。Under the catalysis of sulfuric acid, the dosage of sulfuric acid is 0.3-1%.
（ⅱ）一缩二乙二醇与环氧丙烷反应形成醚醇。(ii) Diethylene glycol reacts with propylene oxide to form ether alcohols.
此反应在硫磷混合酸为催化剂，在1-8大气压下。This reaction is catalyzed by sulfur-phosphorus mixed acid under 1-8 atmospheric pressure.
（ⅲ）酸性柠檬酸酯与醚醇反应即可得ECS。(iii) ECS can be obtained by reacting acidic citric acid ester with ether alcohol.
酸性柠檬酸酯与醚醇的克分子比为2∶1。The molar ratio of acidic citric acid ester to ether alcohol is 2:1.
如果用3∶2配比，将得到更大分子量的ECS三重柠檬酸酯。If a ratio of 3:2 is used, a larger molecular weight ECS triple citrate will be obtained.
（ⅳ）乙酰化的ECS(iv) Acetylated ECS
ECS分子的两端还有两个羟基，经乙酸酐乙酰化得乙酰化的ECSThere are two hydroxyl groups at both ends of the ECS molecule, and acetylated ECS is obtained by acetylation with acetic anhydride
本发明的二重柠檬酸酯与国外文献报导的二重柠檬酸酯相比较：Double citrate of the present invention is compared with the double citrate of foreign literature report:
相同点：Same point:
（ⅰ）主要原料用柠檬酸和单元醇。(i) The main raw materials are citric acid and monoalcohol.
（ⅱ）产物都是大分子量的二重柠檬酸酯。(ii) The products are all high molecular weight dicitrates.
（ⅲ）产物结构类似，性能类似，用途也近似。(Ⅲ) The products have similar structures, similar properties, and similar uses.
所不同点：The difference:
（ⅰ）部分主要原料不同，生产成本不同。(i) Some of the main raw materials are different, and the production costs are different.
一个是用二元酸：三氯化磷（或三氯氧磷）One is to use dibasic acid: phosphorus trichloride (or phosphorus oxychloride)
一个是用二甘醇、环氧丙烷One is to use diethylene glycol, propylene oxide
（ⅱ）生产条件的不同。(ii) Differences in production conditions.
一个需用特殊的防腐设备，设备投资较大One requires special anti-corrosion equipment, and the equipment investment is relatively large
一个用一般的化工设备就可以进行生产A general chemical equipment can be used for production
制造二酰氯时，对环境易造成污染，劳动条件差。When producing diacid chloride, it is easy to cause pollution to the environment and the working conditions are poor.
二酰氯、三氯化磷在潮湿气氛中极易水解放出氯化氢气体，生产需要在干燥通风的条件下进行。Diacyl chloride and phosphorus trichloride are easily hydrolyzed to release hydrogen chloride gas in a humid atmosphere, and the production needs to be carried out under dry and ventilated conditions.
（ⅲ）经济效益的不同。(Ⅲ) Different economic benefits.
由于主要原料的不同，合成路线不同，生产的成本不同，生产条件所需设备不同，总的结果，造成经济效益的不同。Due to different main raw materials, different synthetic routes, different production costs, and different equipment required for production conditions, the overall results result in different economic benefits.
我国的情况，己二酸、癸二酸等二元酸十分缺乏，是短线产品，而二甘醇是长线产品，是生产乙二醇的付产物，供过于求、价格很便宜。环氧丙烷以丙烯为原料，丙烯由石油裂解产物，来源比较丰富。In my country, dibasic acids such as adipic acid and sebacic acid are in short supply and are short-term products, while diethylene glycol is a long-term product and a by-product of the production of ethylene glycol. The supply exceeds demand and the price is very cheap. Propylene oxide uses propylene as raw material, and propylene is a petroleum cracking product with abundant sources.
通过使用情况来看，本发明的增塑剂塑化效率高，不仅可以代替辅助增塑剂，而且还可以代替部分主增塑剂。加工性能好，适应于工业大生产。Judging from the use situation, the plasticizer of the present invention has high plasticizing efficiency, and can not only replace the auxiliary plasticizer, but also replace part of the main plasticizer. Good processing performance, suitable for large-scale industrial production.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102691 CN1015546B (en) | 1988-05-06 | 1988-05-06 | The preparation method of double citrate plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88102691 CN1015546B (en) | 1988-05-06 | 1988-05-06 | The preparation method of double citrate plasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037350A CN1037350A (en) | 1989-11-22 |
| CN1015546B true CN1015546B (en) | 1992-02-19 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88102691 Expired CN1015546B (en) | 1988-05-06 | 1988-05-06 | The preparation method of double citrate plasticizer |
Country Status (1)
| Country | Link |
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| CN (1) | CN1015546B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408646A (en) | 2001-09-25 | 2012-04-11 | 埃克森美孚化学专利公司 | Plasticised polyvinyl chloride |
| DE102009028975A1 (en) * | 2009-08-28 | 2011-03-03 | Evonik Oxeno Gmbh | Ester derivatives of 2,5-furandicarboxylic acid and their use as plasticizers |
| CN105085980A (en) * | 2014-05-09 | 2015-11-25 | 天津科技大学 | Synthesis of citric acid ether ester plasticizer |
| CN108948426A (en) * | 2018-07-05 | 2018-12-07 | 胡果青 | A kind of preparation method of plastic plasticizer |
-
1988
- 1988-05-06 CN CN 88102691 patent/CN1015546B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1037350A (en) | 1989-11-22 |
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