CN101456945A - Method for producing low molecular weight polyester plasticiser - Google Patents
Method for producing low molecular weight polyester plasticiser Download PDFInfo
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- CN101456945A CN101456945A CNA2008102428668A CN200810242866A CN101456945A CN 101456945 A CN101456945 A CN 101456945A CN A2008102428668 A CNA2008102428668 A CN A2008102428668A CN 200810242866 A CN200810242866 A CN 200810242866A CN 101456945 A CN101456945 A CN 101456945A
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Abstract
The invention discloses a production method for a low-molecular-weight polyester plasticizer, which comprises the following steps: polylol, polybasic acid and monohydric alcohol is put into a reactor; a non-acid esterification reaction catalyst is added; after the reaction acid value is below 0.5, the esterification reaction finishes and semi-finished product is obtained; the obtained semi-finished product is mixed with the monohydric alcohol and monacid mixed ester to undergo ester exchange reaction with the existence of metal acetate catalysts; after the reaction acid value is below 0.1, the ester exchange reaction finishes; the excessive monohydric alcohol and monacid mixed ester, and the monohydric alcohol are steamed out of the reactor; the product is obtained by decoloring and filtering the resultant. The product produced by the invention has 25 percent of higher flash point than DOP, an order of magnitude higher electric volume resistivity as well as better performance than DOP, which belongs to non-phthalic environmental protection nontoxic plasticizer and is an environmental protection plasticizer product with excellent cost performance. Moreover, the production technology is simple and easy to operate.
Description
Technical field:
The present invention relates to a kind of production method of low molecular weight polyester plasticiser.
Background technology:
Softening agent is a kind of auxiliary agent of consumption maximum in plastics, the rubber item, China's softening agent and world developed country, and particularly with the U.S., Japan, state's gaps such as European Union are big; The softening agent product of China is based on coventional type, and class is on the low side, generally lacks medium-to-high grade kind, at non-toxic, environmental friendly, high temperature resistant, the extracting of oil resistant water, low volatilization, anti-migration, have antifouling, mildew-resistant, in the multi-functional medium-to-high grade softening agent field such as fire-retardant, the utmost point need be innovated kind.Main six kinds of phthalic esters in the existing softening agent product are banned use of by European Union in children's goods in July, 2005, and the safety of softening agent product becomes the matter of utmost importance that product uses.On the other hand, PVC goods that China's environment-protecting asepsis softening agent of annual import more than 60,000 tons is used for exporting, and home-made citric acid ester type environment-friendly plasticizer is because the relation of chemical structure, the intermiscibility of itself and polyvinyl chloride resin is bad, product oozes out more serious, influences it and promotes the use of.Therefore China is necessary to seek new environment-friendly plasticizer kind.
Summary of the invention:
The object of the present invention is to provide a kind of asepsis environment-protecting, excellent property has the production method of the low molecular weight polyester plasticiser of high flash point, high volume specific resistance.
Technical solution of the present invention is:
A kind of production method of low molecular weight polyester plasticiser is characterized in that: comprise the following steps:
(1) with polyvalent alcohol, polyprotonic acid, monohydroxy-alcohol in reactor, and drop into nonacid catalyst for esterification reaction, when question response acid number to 0.5 was following, esterification finished, work in-process;
(2) work in-process that step (1) is obtained and monohydroxy-alcohol and monacid mixed ester carry out transesterification reaction under the situation that the metal acetate saline catalyst exists, the question response acid number is 0.1 when following, transesterification reaction finishes, unnecessary monohydroxy-alcohol and monoprotic acid mixed ester, monohydroxy-alcohol are steamed reactor, the product that obtains through decolouring, after filtering product.
Polyvalent alcohol is ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, 1,4 one butyleneglycol, neopentyl glycol in the step (1), 1,10 decanediol; Monohydroxy-alcohol is an isopropylcarbinol, propyl carbinol, isooctyl alcohol, n-Octanol, nonylcarbinol or 2-Ethylhexyl Alcohol; Polyprotonic acid is Succinic Acid, hexanodioic acid, suberic acid, pentanedioic acid or sebacic acid, mixed dibasic acid (nylon acid), the third three acid.Nonacid catalyst for esterification reaction is tin protoxide, stannous oxalate, sodium aluminate, titanic acid ester, titanium oxide, zinc oxide or magnesium oxide in the step (1).In the reaction process, discharge the water of reaction generation and the alcohol of band water in the step (1), alcohol is back to reactor again.The temperature of reaction of step (1) is 180～225 ℃.In the step (2) monohydroxy-alcohol and monacid mixed ester be octyl octanoate, caproic acid monooctyl ester, capric acid monooctyl ester, 2 one thylhexoic acid monooctyl esters or own ester and the last of the ten Heavenly stems ester.To make catalyzer be in antimony acetate, zinc acetate, Cobaltous diacetate, manganese acetate, calcium acetate, magnesium acetate, the tin acetate one or more to the metal acetate salt in the step (2).The temperature of reaction of step (2) is 160～205 ℃.
The flash-point of the product that the present invention produces exceeds 25 ℃ than DOP, and volume specific resistance exceeds an order of magnitude, and performance is better than DOP, and belongs to non-adjacent phenyl ring guarantor non-toxic plasticizer, is the environment-friendly plasticizer product with good cost performance.Production technique is simple, and is easy to operate.
Following table is that the quality index of product of the present invention and DOP compares:
| Range of product | The DX-360 low molecular weight polyester plasticiser | DOP |
| Color and luster APHA≤ | 20 | 50 |
| Relative density (20 ℃) | 0.99-1.00 | 0.964-0.970 |
| Ester content % 〉= | 99.5 | 99.5 |
| Acidity %≤ | 0.015 | 0..015 |
| Weight loss on heating %≤ | 0.1 | 0.1 |
| Volume specific resistance (Ω .m) 〉= | 7.0?X?10 12 | 2.0?X?10 11 |
| Flash-point (℃) | 215 | 190 |
The invention will be further described below in conjunction with embodiment.
Embodiment:
A kind of production method of mixed polyester plasticizer comprises the following steps:
(1) with polyvalent alcohol, polyprotonic acid, monohydroxy-alcohol with mol ratio 1:0.57-0.75:0.2-0.6 (routine 1:0.6:0.3,1:0.7:0.5) in reactor, and at 150～190 ℃ of nonacid catalyst for esterification reaction of following input, stir, temperature of reaction is 180～225 ℃, in the reaction process, discharge the water of reaction generation and the alcohol of band water, alcohol is back to reactor again, reacts 3～8 hours, when question response acid number to 0.5 is following, esterification finishes, and gets work in-process; Wherein polyvalent alcohol is ethylene glycol (or polyoxyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,10 decanediol), and monohydroxy-alcohol is propyl carbinol (isopropylcarbinol, isooctyl alcohol, n-Octanol, nonylcarbinol or a 2-Ethylhexyl Alcohol); Polyprotonic acid is Succinic Acid (hexanodioic acid, suberic acid, pentanedioic acid or sebacic acid, mixed dibasic acid (nylon acid), the third three acid).Nonacid catalyst for esterification reaction is tin protoxide (or stannous oxalate, sodium aluminate, titanic acid ester, titanium oxide, zinc oxide, magnesium oxide).
(2) work in-process that step (1) is obtained and monohydroxy-alcohol and monacid mixed ester carry out transesterification reaction with mol ratio 1:1.2-1.8 (routine 1:1.3,1:1.5,1:1.8) under the situation that the metal acetate saline catalyst exists, stir, temperature of reaction is 160～205 ℃, reacted 2～3 hours, the question response acid number is 0.1 when following, transesterification reaction finishes, unnecessary monohydroxy-alcohol and monoprotic acid mixed ester, monohydroxy-alcohol are steamed reactor, the product that obtains through decolouring, after filtering product, and pack when being cooled to below 30 ℃.Wherein monohydroxy-alcohol and monacid mixed ester are octyl octanoate (or caproic acid monooctyl ester, capric acid monooctyl ester, 2-thylhexoic acid monooctyl ester, own ester and the last of the ten Heavenly stems ester), and it is antimony acetate (or in the zinc acetate, Cobaltous diacetate, manganese acetate, calcium acetate, magnesium acetate, tin acetate one or more) that the metal acetate salt is made catalyzer.The concrete grammar that above-mentioned decolouring is handled is: decolouring is carried out in the decolouring still, reduces to 130 ℃ of a certain amount of gacs of input when temperature and decolours.The raw material that decolouring drops into: gac, particle and powdery are used with, and consumption is for needing 0.2%-0.5% of decolouring product weight; The processing condition of decolouring: 120 ℃-130 ℃ of temperature, pressure: vacuum, churning time: 0.5-1 hour;
Filtering concrete grammar is: filter with being pumped to the Finda filter when decolouring still is cooled to below 100 ℃, obtain light color, clarifying product after gac and some solid impurities are eliminated.
Claims (8)
1, a kind of production method of low molecular weight polyester plasticiser is characterized in that: comprise the following steps:
(1) with polyvalent alcohol, polyprotonic acid, monohydroxy-alcohol in reactor, and drop into nonacid catalyst for esterification reaction, when question response acid number to 0.5 was following, esterification finished, work in-process;
(2) work in-process that step (1) is obtained and monohydroxy-alcohol and monacid mixed ester carry out transesterification reaction under the situation that the metal acetate saline catalyst exists, the question response acid number is 0.1 when following, transesterification reaction finishes, unnecessary monohydroxy-alcohol and monoprotic acid mixed ester, monohydroxy-alcohol are steamed reactor, the product that obtains through decolouring, after filtering product.
2, the production method of mixed polyester plasticizer according to claim 1 is characterized in that:
Polyvalent alcohol is ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, 1,4-butyleneglycol, neopentyl glycol in the step (1), 1,10 decanediol; Monohydroxy-alcohol is an isopropylcarbinol, propyl carbinol, isooctyl alcohol, n-Octanol, nonylcarbinol or 2-Ethylhexyl Alcohol; Polyprotonic acid is Succinic Acid, hexanodioic acid, suberic acid, pentanedioic acid, sebacic acid, mixed dibasic acid or the third three acid.
3, the production method of mixed polyester plasticizer according to claim 1 and 2 is characterized in that: nonacid catalyst for esterification reaction is tin protoxide, stannous oxalate, sodium aluminate, titanic acid ester, titanium oxide, zinc oxide or magnesium oxide in the step (1).
4, the production method of mixed polyester plasticizer according to claim 1 and 2 is characterized in that: in the reaction process, discharge the water of reaction generation and the alcohol of band water in the step (1), alcohol is back to reactor again.
5, the production method of low molecular weight polyester plasticiser according to claim 1 and 2 is characterized in that: the temperature of reaction of step (1) is 180～225 ℃.
6, the production method of mixed polyester plasticizer according to claim 1 and 2 is characterized in that: in the step (2) monohydroxy-alcohol and monacid mixed ester be octyl octanoate, caproic acid monooctyl ester, capric acid monooctyl ester, 2-thylhexoic acid monooctyl ester or own ester and the last of the ten Heavenly stems ester.
7, the production method of mixed polyester plasticizer according to claim 1 and 2 is characterized in that: the metal acetate saline catalyst is one or more in antimony acetate, zinc acetate, Cobaltous diacetate, manganese acetate, calcium acetate, magnesium acetate, the tin acetate in the step (2).
8, the production method of mixed polyester plasticizer according to claim 1 and 2 is characterized in that: the temperature of reaction of step (2) is 160～205 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2008102428668A CN101456945A (en) | 2008-12-24 | 2008-12-24 | Method for producing low molecular weight polyester plasticiser |
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| CNA2008102428668A CN101456945A (en) | 2008-12-24 | 2008-12-24 | Method for producing low molecular weight polyester plasticiser |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731755A (en) * | 2012-07-19 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for preparing plasticizer |
| CN103319698A (en) * | 2013-06-19 | 2013-09-25 | 佛山市顺德区天晟贸易有限公司 | Polymer polyester plasticizer as well as preparation method and application thereof |
| CN103819659A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院微生物研究所 | Long carbon chain binary acid polyester, and preparation method and application thereof |
| CN103937162A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Low-temperature resin composition and preparation method thereof |
| CN106349502A (en) * | 2016-08-26 | 2017-01-25 | 安徽泰达新材料股份有限公司 | Mixed type polybasicester plasticizer and preparation method thereof |
| CN108129316A (en) * | 2017-12-25 | 2018-06-08 | 江苏雷蒙新材料有限公司 | A kind of nylon acid two（2- ethyls）The preparation method of own ester |
| CN108752803A (en) * | 2018-06-21 | 2018-11-06 | 江南大学 | A kind of preparation method and application for the environmentally friendly polyester plasticizer of adipic acid series that molecular weight is different and controllable |
| CN112110816A (en) * | 2020-09-02 | 2020-12-22 | 山东吉青化工有限公司 | Preparation method of polyol fatty acid ester plasticizer |
-
2008
- 2008-12-24 CN CNA2008102428668A patent/CN101456945A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102731755B (en) * | 2012-07-19 | 2014-04-30 | 中国科学院长春应用化学研究所 | Method for preparing plasticizer |
| CN102731755A (en) * | 2012-07-19 | 2012-10-17 | 中国科学院长春应用化学研究所 | Method for preparing plasticizer |
| CN103819659B (en) * | 2012-11-19 | 2017-12-19 | 中国科学院微生物研究所 | A kind of long carbochain biatomic acid polyester and its preparation method and application |
| CN103819659A (en) * | 2012-11-19 | 2014-05-28 | 中国科学院微生物研究所 | Long carbon chain binary acid polyester, and preparation method and application thereof |
| CN103319698A (en) * | 2013-06-19 | 2013-09-25 | 佛山市顺德区天晟贸易有限公司 | Polymer polyester plasticizer as well as preparation method and application thereof |
| CN103937162A (en) * | 2014-04-11 | 2014-07-23 | 四川东材科技集团股份有限公司 | Low-temperature resin composition and preparation method thereof |
| CN103937162B (en) * | 2014-04-11 | 2016-08-17 | 四川东材科技集团股份有限公司 | Low-temperature resins compositions and preparation method thereof |
| CN106349502A (en) * | 2016-08-26 | 2017-01-25 | 安徽泰达新材料股份有限公司 | Mixed type polybasicester plasticizer and preparation method thereof |
| CN106349502B (en) * | 2016-08-26 | 2018-12-11 | 安徽泰达新材料股份有限公司 | Mixed type polyacid ester plasticizer and preparation method thereof |
| CN108129316A (en) * | 2017-12-25 | 2018-06-08 | 江苏雷蒙新材料有限公司 | A kind of nylon acid two（2- ethyls）The preparation method of own ester |
| CN108752803A (en) * | 2018-06-21 | 2018-11-06 | 江南大学 | A kind of preparation method and application for the environmentally friendly polyester plasticizer of adipic acid series that molecular weight is different and controllable |
| CN108752803B (en) * | 2018-06-21 | 2020-06-30 | 江南大学 | Preparation method and application of adipic acid series environment-friendly polyester plasticizer with different and controllable molecular weights |
| CN112110816A (en) * | 2020-09-02 | 2020-12-22 | 山东吉青化工有限公司 | Preparation method of polyol fatty acid ester plasticizer |
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