CN1033913C - Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent - Google Patents
Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent Download PDFInfo
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- CN1033913C CN1033913C CN 93120487 CN93120487A CN1033913C CN 1033913 C CN1033913 C CN 1033913C CN 93120487 CN93120487 CN 93120487 CN 93120487 A CN93120487 A CN 93120487A CN 1033913 C CN1033913 C CN 1033913C
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Abstract
The present invention discloses epoxy unsaturated higher fatty acid rare earth which belongs to a non-toxic stabilizing agent. The present invention is prepared by the steps that 1, unsaturated higher fatty acid, hydrogen peroxide and glacial acetic acid or formic acid are used as raw materials, and concentrated sulfuric acid or strongly acidic cation-exchange is used as catalyst for epoxidation reaction; 2, products of the epoxidation reaction carry out saponification reaction with sodium hydroxide; 3, products of the saponification reaction carry out metathetical reaction with rare earth chloride to generate the epoxy unsaturated higher fatty acid rare earth. The plastic non-toxic stabilizing agent combines the stabilisation mechanisms of epoxy vegetable oil and stearic acid rare earth, and has the advantages of ageing delay, degradation delay and duplex stabilization effect. The stabilization effect of the present invention is superior to that of lead stearate, barium and the stearic acid rare earth.
Description
The present invention relates to a kind of plastics non-toxic stabilizer.
As everyone knows, the polyvinyl chloride plastic material stabilizer uses metallic soap of stearic acid (such as calcium stearate, barium, lead, cadmium etc.) usually, but in this metalloid soap, many is deleterious, can not be applied to the production of nontoxic goods.Along with current stabilizer for plastics to restriction cadmium system, transform the needs that plumbous system, nontoxic dustless direction develop, developed plastics non-toxic plasticizer stablizer---epoxidized vegetable oil and the plastics non-toxic stabilizer---rare-earth stearate of holding concurrently in the market in succession.
The stable mechanism of epoxidized vegetable oil (comprising epoxy soybean oil, epoxy cotton seed oil, epoxy rice bran wet goods) is that igelite is degraded because of factors such as light, heat in processing and use, discharge hydrogenchloride, this hydrogenchloride is the aging promotor of igelite, remove as untimely, then can quicken it and wear out.And the epoxide group in the epoxidized vegetable oil has chemically reactive, can be with hcl reaction absorbing hydrogen chloride, thereby avoid the accelerated deterioration of igelite, play the effect of stablizer.Rare-earth stearate can delay the degraded of igelite, plays function of stabilizer equally.
The objective of the invention is to propose a kind of epoxide group and rare earth metal of in molecule, containing simultaneously, the stabilization of epoxidized vegetable oil and the stabilization of rare-earth stearate can be combined, igelite is played delaying retrogradation in processing and use, the dual stabilization that delays to degrade, its stabilising effect is better than plastics non-toxic stabilizer---the epoxy unsaturated high-grade fatty acid rare earth of lead stearate, barium and rare-earth stearate.
The epoxy unsaturated high-grade fatty acid rare earth of invention is prepared from successively as follows.
The first step is a raw material with insatiable hunger higher fatty acid, hydrogen peroxide, Glacial acetic acid or formic acid, is that catalyzer carries out epoxidation reaction generation intermediate product epoxy unsaturated high-grade fatty acid with the vitriol oil or strongly acidic cation-exchange.Unsaturated high-grade fatty acid can be used Zoomeric acid, oleic acid, and linolic acid, linolenic acid or erucic acid, wherein best with oleic acid and linolic acid effect especially.Hydrogen peroxide adopts commercially available 27% or 35% concentration all can, its consumption is 1.0～1.8 times of the two key molar masss of unsaturated high-grade fatty acid, be preferably 1.1～1.4 times, Glacial acetic acid or formic acid consumption are 0.2～0.8 times of unsaturated high-grade fatty acid molar mass, are preferably 0.25～0.45 times.When making catalyzer with the vitriol oil, its consumption is generally 0.1～5% of unsaturated high-grade fatty acid weight, is preferably 0.5～3%, if when making catalyzer with strongly acidic cation-exchange, its consumption is generally 5～20% of unsaturated high-grade fatty acid weight, is preferably 7～15%.Under agitation condition hydrogen peroxide is added drop-wise in the reactor that fills unsaturated high-grade fatty acid, Glacial acetic acid or formic acid, the catalyzer vitriol oil or strongly acidic cation-exchange, its temperature of reaction is 40～70 ℃, and the reaction times is 2～5 hours.
In second step, carry out saponification reaction by intermediate product epoxy unsaturated high-grade fatty acid and sodium hydroxide and generate intermediate product epoxy unsaturated high-grade fatty acid sodium salt.The consumption of sodium hydroxide is 1.0～1.2 times of epoxy unsaturated high-grade fatty acid molar mass.The aqueous solution that sodium hydroxide generally is made into 3～10% weight concentrations uses.The saponification reaction temperature is 30～60 ℃, 20～50 minutes reaction times.
The 3rd step, carry out replacement(metathesis)reaction by intermediate product epoxy unsaturated high-grade fatty acid sodium salt and rare earth chloride, make the product epoxy unsaturated high-grade fatty acid rare earth.Wherein the consumption of rare earth chloride is 0.3～0.5 times of epoxy unsaturated high-grade fatty acid sodium salt molar mass, and the aqueous solution that rare earth chloride generally is made into 5～15% weight concentrations uses.The replacement(metathesis)reaction temperature is 30～60 ℃, 20～50 minutes reaction times.
Embodiment one:
In the 250ml there-necked flask, add oleic acid 100 grams (about 0.355 mole), 85% formic acid, 10 grams (about 0.185 mole), the vitriol oil 0.8 gram, heat temperature raising under agitation condition.When temperature is raised to 50 ℃, stop heating, beginning Dropwise 35 % hydrogen peroxide 417ml (about 0.57 mole), the control rate of addition makes temperature of reaction be no more than 65 ℃, after hydrogen peroxide dropwises, keeps about 60 ℃ of temperature, continues reaction 4 hours.The sampling analysis oxirane value is 3.7gO/100g, and iodine number is 5.5gI/100g.
Epoxyoleic acid washes with water to neutrality, move in another there-necked flask, after adding the suitable quantity of water dilution, be heated to 50 ℃ while stirring, drip 10% weight sodium hydroxide solution 160ml (about 0.40 mole), drip off follow-up continuation of insurance temperature and react half an hour, then under same temperature, drip 15% weight re chloride 330ml (about 0.14 mole), drip off follow-up continuation of insurance temperature reaction 40 minutes.
Reaction finishes the back and removes water with centrifugal separation or filtration by means of suction method, and precipitation is washed with distilled water to neutrality, promptly gets the epoxyoleic acid rare-earth products after the drying.
Embodiment two:
Remove with Glacial acetic acid 30 grams (about 0.5 mole) and replace formic acid, replace the vitriol oil to do outside the catalyzer with 732 type sulfonic acid ion exchange resins (converting Hydrogen in advance to), 10 grams, other prescription and operational condition are with embodiment one, sampling analysis after the epoxidation reaction, oxirane value is 3.9gO/100g, and iodine number is 5.0gI/100g.
Embodiment three:
In the 250ml there-necked flask, add linolic acid 100 gram (about 0.712 mole of two key mole numbers), Glacial acetic acid 40g (about 0.67 mole), the vitriol oil 1 gram, heat temperature raising under agitation condition.When temperature is raised to 55 ℃, stop heating, beginning Dropwise 35 % hydrogen peroxide 80ml (about 0.98 mole), the control rate of addition makes temperature of reaction be no more than 65 ℃, after hydrogen peroxide dropwises, keeps 65 ℃ of temperature, continues stirring reaction 4 hours.Sampling analysis, oxirane value is 6.5gO/100g as a result, iodine number is 7.8gI/100g.Later saponification reaction, replacement(metathesis)reaction prescription and operational condition are with embodiment one.
Heat stability test result is shown in table one, table two.
Table one polyvinyl chloride cable material heat stabilization test prescription comparative example one comparative example two embodiment one embodiment two embodiment three PVC-3 types 100 100 100 100 100 plasticizer 49 49 49 49 49 antimonial lead+-----rare-earth stearate-1.7 divides hard barium 1.7 by epoxyoleic acid rare earth--1.7 1.7-epoxy linoleic acid rare earth----40 40 40 40 40200 ℃ of thermally-stabilised 80 85 90 95 98 times of 1.7 other auxiliary agents
Table two polyvinyl chloride solids material heat stabilization test prescription comparative example one comparative example two embodiment one embodiment two embodiment three PVC-5 types 100 100 100 100 100 antimonial lead+---hard barium 1.8 divides by rare-earth stearate-1.8--epoxyoleic acid rare earth--1.8 1.8-epoxy linoleic acid rare earth----42 42 42 42 42200 ℃ of thermally-stabilised 55 60 70 75 78 times of 1.8 other auxiliary agents
Annotate: comparative example one: with antimonial lead+hard barium is stablizer.
Comparative example two: with the rare-earth stearate is stablizer.
Test-results shows that the thermostability of epoxy unsaturated high-grade fatty acid rare earth of the present invention is better than rare-earth stearate, more is better than stearic plumbous barium, is the plastics non-toxic stabilizer more even more ideal than rare-earth stearate.
Claims (2)
1. a plastics non-toxic stabilizer---the preparation method of epoxy unsaturated high-grade fatty acid rare earth, its preparation process is:
The first step, with unsaturated high-grade fatty acid, hydrogen peroxide, Glacial acetic acid or formic acid are raw material, are that catalyzer carries out epoxidation reaction generation epoxy unsaturated high-grade fatty acid with the vitriol oil or strongly acidic cation-exchange; In second step, carry out saponification reaction by epoxy unsaturated high-grade fatty acid and sodium hydroxide and generate the epoxy unsaturated high-grade fatty acid sodium salt; It is characterized in that the 3rd step in addition, epoxy unsaturated high-grade fatty acid sodium salt and rare earth chloride are carried out replacement(metathesis)reaction, generate epoxy unsaturated high-grade fatty acid rare earth, wherein the consumption of rare earth chloride is 0.3～0.5 times of unsaturated high-grade fatty acid sodium salt molar mass, reacts 20～50 minutes under 30～60 ℃ of temperature.
2. by the preparation method of the described epoxy unsaturated high-grade fatty acid rare earth of claim 1, it is characterized in that in the replacement(metathesis)reaction that rare earth chloride is with the aqueous solution of 5～15% weight concentrations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120487 CN1033913C (en) | 1993-12-09 | 1993-12-09 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120487 CN1033913C (en) | 1993-12-09 | 1993-12-09 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1089968A CN1089968A (en) | 1994-07-27 |
| CN1033913C true CN1033913C (en) | 1997-01-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93120487 Expired - Fee Related CN1033913C (en) | 1993-12-09 | 1993-12-09 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
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| CN (1) | CN1033913C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313453C (en) * | 2004-10-08 | 2007-05-02 | 广东联塑科技实业有限公司 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
| CN100535091C (en) * | 2006-06-27 | 2009-09-02 | 上海大学 | Preparation method of alcohol ester type environment lubricating oil |
| CN100469833C (en) * | 2007-02-15 | 2009-03-18 | 宜兴市三联化工厂 | Method of preparing polyvinylchloride composite processing auxiliary agent |
| CN103145651B (en) * | 2013-01-25 | 2015-07-08 | 江苏高科石化股份有限公司 | Preparation method of epoxy aliphatic ester biological lubricant base oil |
| CN104311420B (en) * | 2014-09-16 | 2016-01-20 | 浙江恒丰新材料有限公司 | Bio oil one kettle way prepares method and the application of polyvalent alcohol |
| CN104326911B (en) * | 2014-09-16 | 2016-06-15 | 浙江恒丰新材料有限公司 | A kind of waste grease prepares method and the application of polyhydric alcohol |
| CN109370653A (en) * | 2018-10-29 | 2019-02-22 | 董林妤 | A kind of preparation method and its equipment of biomass gasified synthesis gas |
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1993
- 1993-12-09 CN CN 93120487 patent/CN1033913C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1089968A (en) | 1994-07-27 |
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