CN1966497A - Epoxy fatty acid methyl ester - Google Patents
Epoxy fatty acid methyl ester Download PDFInfo
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- CN1966497A CN1966497A CN 200610068817 CN200610068817A CN1966497A CN 1966497 A CN1966497 A CN 1966497A CN 200610068817 CN200610068817 CN 200610068817 CN 200610068817 A CN200610068817 A CN 200610068817A CN 1966497 A CN1966497 A CN 1966497A
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- methyl ester
- acid methyl
- fatty acid
- plasticizer
- plastics
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Abstract
The invention discloses a non-toxic plasticizer of biomass compound epoxy fatty acid methyl ester used in plastics and rubbers processing, which can be represented by the general formula I, wherein R, R' are CnH2n +1 (n = 0~15). The nontoxic plasticizer is prepared with fatty acid methyl ester as raw material, hydrogen peroxide as oxygen body, organic acid as oxygen-carrier, acidic matter as catalyst, and complex as stabilizer through epoxidation. The plasticizer not only has the advantages of excellent toughness, good compatibility, low volatile, small migration, non-toxic, and light and heat stability, but also has superior lubricity, compatibility and dispersibility. It can be used in PVC processing with addition of as many as 5-30%, completely replacing DOP to manufacture nontoxic PVC products for food packaging, medical supplies materials, toys, water supply pipeline, and surfactant, softening agent and dispersing agent used in plastics and rubber industries.
Description
One, technical field
The present invention relates to organic chemical industry's product, particularly the biomass epoxy compounds.
Two, background technology
In organic chemical industry's industry,, need to add a certain proportion of softening agent in order to improve the processing characteristics of plastics, rubber.Generally use phthalic ester plasticizer at present, as DOP (dioctyl phthalate (DOP)), because of it contains aromatic nucleus, readily biodegradable not, and poisonous, belong to non-renewable petrochemicals again, use range is subjected to bigger restriction.Domestic existing many non-toxic plasticizer researchs and the relevant report of producing, as with soybean oil, Oleum Gossypii semen, Rice pollard oil, rapeseed oil, flax wet goods vegetables oil as raw material, obtain a kind of nontoxic, tasteless epoxidized vegetable oil through epoxidation production, as the softening agent thermo-stabilizer of holding concurrently, light and heat had the satisfactory stability effect.But there is following problem in they: 1. relatively poor with plastics such as PVC (polyvinyl chloride) consistency, must with phthalate such as the composite use of DOP, could produce better action, that is can only be as the secondary softening agent of PVC, generally in polyvinyl chloride resin, add 1-3%, to bring poisonous of phthalic ester plasticizer and be difficult for biodegradable problem, can only play and alleviate effect and can not fundamentally solve; 2. with vegetables oil as raw material, production cost is higher.Agricultural science and technology net (the http://www.ahnw.gov.cn/2006nykj/Show.asp of Anhui Province? ContentID=%7B23E4B56C-76E1-4148-9A93-255COB6B97D8%7D) a kind of method of producing chloro methoxyl group fatty acid methyl ester with fatty acid methyl ester through the chloro methoxylation is disclosed, though as non-toxic plasticizer overcome and plastics between the relatively poor problem of consistency, but it is produced process need and uses chlorine in a large number, therefore environmental pollution is serious, large-scale industrial production not as yet.
Three, summary of the invention
The purpose of this invention is to provide a kind of nontoxic, readily biodegradable, and plastics and rubber between consistency is good, production cost is low biomass compound softening agent.
For realizing above purpose, the invention provides a kind of biomass compound epoxy aliphatic acid methyl ester, it is made of following general formula:
R, R ' are C in the formula
nH
2n+1, n=0-15.
Above-mentioned biomass compound epoxy aliphatic acid methyl ester is used for plastics and Rubber processing as non-toxic plasticizer.
Epoxidized vegetable oil such as soybean oil typical case molecular formula are C
57H
104O
9, its structural formula molecular formula general formula is:
And chloro methoxyl group fatty acid methyl ester typical component molecular formula is C
20H
38O
3Cl
2, its structural formula molecular formula general formula is:
Contrasting above three kinds of structural formula molecular formula general formulas can find, although epoxidized vegetable oil and epoxy aliphatic acid methyl ester all have epoxy group(ing), but epoxy aliphatic acid methyl ester is because of having polar group methoxycarbonyl and nonpolar chain alkyl, and its structural formula molecular formula and epoxidized vegetable oil are still had any different; And compare with chloro methoxyl group fatty acid methyl ester, because of the latter does not have epoxy group(ing), so both structural formula molecular formula have significant difference.
Because of epoxy aliphatic acid methyl ester has polar group methoxycarbonyl and epoxy group(ing)
Has nonpolar chain alkyl again, therefore make softening agent when at high temperature mixed mutually with it with polyvinyl chloride (PVC) resin isopolarity macromolecular material, plasticizer molecule is alternately between polymer molecular chain, partly attract each other by polarity and to form uniform and stable system, even temperature decline post-plasticization agent molecule also can be stayed between the polymer molecular chain, thereby show and polyvinyl chloride (PVC) resin isopolarity macromolecular material between consistency good, volatility is low, the characteristic that transport property is little, be used for the adding proportion that macromolecule material product adds man-hour thereby improved greatly, adding proportion is up to 5-30%, and it is nontoxic to replace the DOP softening agent to produce fully, degradable, the macromolecular material product of environmental protection; And that its long nonpolar moieties plays the barrier polymers molecular chain is approaching mutually, thereby weakens their gravitation, makes the polymkeric substance deliquescing, reaches plasticization effect.In addition, epoxy aliphatic acid methyl ester can absorb the hydrogenchloride of emitting when PVC decomposes, and light and heat is had the satisfactory stability effect, thereby polyvinyl chloride resin is played function of stabilizer.Therefore, epoxy aliphatic acid methyl ester be that a kind of ideal is nontoxic, degradable, environment-friendly type plastic and rubber plastizing agent and stablizer.
Compare with the epoxidized vegetable oil softening agent, the epoxy aliphatic acid methyl ester softening agent not only can replace the DOP softening agent to produce PVC product nontoxic, environmental protection fully, be used for food product pack, medical article material, toy and water supply line etc., simultaneously also as celluosic resin and elastomeric non-toxic plasticizer and tenderizer, in the processing of goods, adding epoxy aliphatic acid methyl ester can obviously improve physical properties of articles and prolong digestion time, with metal(lic)stabilizer and times spent such as barium, cadmium, zinc, good synergy is arranged.In addition, because of it also has good lubricity, consistency and dispersion performance, go back useful as surfactants and dispersion agent and be applied to production industries such as epoxy coating and Resins, epoxy.
According to the purposes of epoxy aliphatic acid methyl ester, its relevant physical and chemical index is as follows:
| Index name | Measure unit | Epoxy plasticizer | Testing method |
| Outward appearance | Light yellow oily liquid | Range estimation | |
| Iodine number | I 2/100g | ≤6 | GB/T1676 |
| Acid number | mgKOH/g | ≤1 | GB/T1668 |
| Proportion | 20℃ | 0.85-0.87 | GB/T1667 |
| Condensation point | ℃ | ≤5 | GB/T1671 |
| Oxirane value | ％ | 3.5-6.0 | GB/T1677 |
Four, embodiment
Below by the synthetic specific embodiment of product the present invention is described in further detail with product application.
Product synthesizes embodiment 1: in 5000 liters enamel still, coefficient is by 0.75, fatty acid methyl ester is Uniphat A60 15-25 by weight (%) component, methyl stearate 2-5, Witconol 2301 40-50, methyl linoleate 25-35, the weight of material proportioning is pressed fatty acid methyl ester: hydrogen peroxide: organic acid: catalyzer: complex compound stablizer=1: (0.3-0.6): (0.1-0.12): (0.005-0.006): (0.001-0.003), organic acid adopts formic acid, make catalyzer with the vitriol oil, the urea used as stabilizers is to guarantee that peroxyformic acid has certain stability under reaction environment; Earlier fatty acid methyl ester, formic acid, sulfuric acid and urea are packed in the enamel still by proportioning, under stirring state, be warmed up to 48 ℃, stop heating, begin to drip concentration and be 35% hydrogen peroxide; Owing to be thermopositive reaction, adopt the water coolant temperature adjustment, be 50-70 ℃ to keep temperature in the kettle; The hydrogen peroxide dropping time was controlled at 3.5-4.5 hour, dropwised and was incubated 3-4 hour again, made the interior epoxidation reaction of still fully thorough, obtained thick non-toxic plasticizer; Obtain the epoxy aliphatic acid methyl ester finished product after separation, washing, dehydration, press filtration, its typical component is the epoxyoleic acid methyl esters, and molecular formula is C
19H
36O
3
Product synthesizes embodiment 2: organic acid replaces formic acid with acetate, and other technologies parameter and operation steps obtain the epoxy aliphatic acid methyl ester finished product with embodiment 1.
Product synthesizes embodiment 3: catalyzer changes Tai-Ace S 150 into by sulfuric acid, and the hydrogen peroxide dropping time was controlled at 3.0-4.0 hour, dropwises and is incubated 4-5 hour again, and other technologies parameter and operation steps obtain the epoxy aliphatic acid methyl ester finished product with embodiment 1.
The chemical reaction mechanism of synthesizing epoxy fatty acid methyl ester: the epoxidation of fatty acid methyl ester is the epoxidation of the carbon-carbon double bond in the fatty acid methyl ester, is example when making oxygen carrier with formic acid, and its mechanism can be represented with following chemical equation:
Epoxy aliphatic acid methyl ester end-use: as the novel softening agent stablizer of holding concurrently, be mainly used in polyvinyl chloride resin, make nontoxic PVC product, be used for the upper hose of packaging material for food, medical article material, building trade etc., PVC product properties (comprising machining property, weather resistance and the plasticizing capacity) requirement that meets international standards of producing, but should not be used in the high temperature electric wire cable.
Product application embodiment 1: produce PVC hardboard, hard tube, hard toy etc., the epoxy aliphatic acid methyl ester usage quantity is 3-8%;
Product application embodiment 2: produce PVC leatheroid, sandals, soft toy, record compound, medicine equipment, automotive floor panel material, agricultural jet pipe, fire hose, printed matter, gloves etc., the epoxy aliphatic acid methyl ester usage quantity is 10-20%;
Product application embodiment 3: produce PVC film, flexible pipe etc., the epoxy aliphatic acid methyl ester usage quantity is 20-30%;
Product application embodiment 4: the epoxy aliphatic acid methyl ester usage quantity is 10-20% in rubber item production.
In the above Application Example, according to soft, the hard degree of goods, addition is between 5-30%, and the big more goods of addition are soft more, and desirable following effect:
The tough and tensile softness that 1, in low temperature, can keep goods, the folding endurance of increase product, the work-ing life of prolongation product.Adding proportion and tortuous number of times corresponding relation are as follows:
Add epoxy aliphatic acid methyl ester ratio % 05 10
Tortuous number of times (fracture) 200 1,200 3600
2, goods stability is improved greatly, reduces the consumption of barium cadmium zinc stabilizer, and as add the epoxy aliphatic acid methyl ester that adds 10-15% in the PVC goods, the usage quantity that can reduce barium cadmium zinc stabilizer is more than 30%;
3, the PVC goods that add epoxy aliphatic acid methyl ester use out of doors, and unique fast light, hot, aging resistance are arranged.
Claims (2)
1, general formula is
Biomass compound epoxy aliphatic acid methyl ester, R, R ' are C in the formula
nH
2n+1, n=0～15.
2, the described biomass compound of a kind of claim 1 epoxy aliphatic acid methyl ester, it is characterized in that: it is used for plastics and Rubber processing as non-toxic plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610068817 CN1966497A (en) | 2006-09-11 | 2006-09-11 | Epoxy fatty acid methyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610068817 CN1966497A (en) | 2006-09-11 | 2006-09-11 | Epoxy fatty acid methyl ester |
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| Publication Number | Publication Date |
|---|---|
| CN1966497A true CN1966497A (en) | 2007-05-23 |
Family
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxy fatty acid methyl ester |
| CN101948449A (en) * | 2010-09-15 | 2011-01-19 | 广州大学 | Method for preparing chloro-epoxy fatty acid methyl ester plasticizer |
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
| CN102993133A (en) * | 2013-01-08 | 2013-03-27 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester with microreactor one-step method |
| CN103224672A (en) * | 2013-04-17 | 2013-07-31 | 无锡哈威新材料科技有限公司 | Non-toxic polyvinyl chloride resin material |
| CN103930477A (en) * | 2011-09-30 | 2014-07-16 | 陶氏环球技术有限责任公司 | Plasticizer for color retention during heat aging |
| CN104718248A (en) * | 2012-10-18 | 2015-06-17 | 陶氏环球技术有限公司 | Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers |
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN106519081A (en) * | 2016-09-22 | 2017-03-22 | 深圳立山环保材料有限公司 | Epoxy plasticizer and preparation method |
| CN107200957A (en) * | 2017-06-06 | 2017-09-26 | 滁州市宏源喷涂有限公司 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
| CN110144242A (en) * | 2019-05-21 | 2019-08-20 | 安徽星鑫化工科技有限公司 | A kind of Modified Chlorinated Paraffin and preparation method thereof, application |
-
2006
- 2006-09-11 CN CN 200610068817 patent/CN1966497A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891713B (en) * | 2010-07-09 | 2012-02-29 | 南京工业大学 | Method for preparing epoxy fatty acid methyl ester |
| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxy fatty acid methyl ester |
| CN101948449A (en) * | 2010-09-15 | 2011-01-19 | 广州大学 | Method for preparing chloro-epoxy fatty acid methyl ester plasticizer |
| CN102285946A (en) * | 2011-06-28 | 2011-12-21 | 广州市海珥玛植物油脂有限公司 | Diacetyl epoxy glyceryl oleates and synthesis method thereof |
| CN103930477A (en) * | 2011-09-30 | 2014-07-16 | 陶氏环球技术有限责任公司 | Plasticizer for color retention during heat aging |
| CN103930477B (en) * | 2011-09-30 | 2015-08-19 | 陶氏环球技术有限责任公司 | The fluidizer of color is kept in Heat Ageing |
| CN104718248B (en) * | 2012-10-18 | 2018-04-13 | 陶氏环球技术有限公司 | Epoxidized fat acid alkyl ester plasticizer and the method for manufacturing epoxidized fat acid alkyl ester plasticizer |
| CN104718248A (en) * | 2012-10-18 | 2015-06-17 | 陶氏环球技术有限公司 | Epoxidized fatty acid alkyl ester plasticizers and methods for making epoxidized fatty acid alkyl ester plasticizers |
| CN102993133A (en) * | 2013-01-08 | 2013-03-27 | 南京工业大学 | Method for preparing epoxidized fatty acid methyl ester with microreactor one-step method |
| CN102993133B (en) * | 2013-01-08 | 2015-09-02 | 南京工业大学 | The method of epoxy aliphatic acid methyl ester is prepared by microreactor single stage method |
| CN103224672A (en) * | 2013-04-17 | 2013-07-31 | 无锡哈威新材料科技有限公司 | Non-toxic polyvinyl chloride resin material |
| CN103224672B (en) * | 2013-04-17 | 2016-02-17 | 无锡哈威新材料科技有限公司 | A kind of Non-toxic polyvinyl chloride resin material |
| CN104817521A (en) * | 2015-03-03 | 2015-08-05 | 中国林业科学研究院林产化学工业研究所 | Epoxy dimeric fatty acid methyl ester, preparation method and applications thereof |
| CN106519081A (en) * | 2016-09-22 | 2017-03-22 | 深圳立山环保材料有限公司 | Epoxy plasticizer and preparation method |
| CN106519081B (en) * | 2016-09-22 | 2018-06-26 | 深圳立山环保材料有限公司 | A kind of epoxy plasticiser and preparation method thereof |
| CN107200957A (en) * | 2017-06-06 | 2017-09-26 | 滁州市宏源喷涂有限公司 | A kind of method of epoxy aliphatic acid methyl ester resistance to migration in raising flexible PVC |
| CN110144242A (en) * | 2019-05-21 | 2019-08-20 | 安徽星鑫化工科技有限公司 | A kind of Modified Chlorinated Paraffin and preparation method thereof, application |
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