CN107383417A - A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof - Google Patents
A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof Download PDFInfo
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- CN107383417A CN107383417A CN201710599593.1A CN201710599593A CN107383417A CN 107383417 A CN107383417 A CN 107383417A CN 201710599593 A CN201710599593 A CN 201710599593A CN 107383417 A CN107383417 A CN 107383417A
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- acid
- chinese catalpa
- methyl esters
- catalpa oil
- oil methyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof.Using Chinese catalpa oil or its fatty acid methyl ester, peroxide, binary acid as raw material, tallowseed oil is converted into epoxy Chinese catalpa oil methyl esters first, then is catalyzed open loop and with dibasic acid ester metaplasia into binary acid epoxyfatty acid ester compounds.This method can effectively reduce the content of the certain herbaceous plants with big flowers dienoic acid methyl ester of Chinese catalpa oil methyl esters Short-Chain Fatty Acids ester 2,4, improve mean molecule quantity, so that plasticizer product has a low volatility, resistance to migration, and preferable durability, the features such as high-flash.This product is suitable as extender plasticizer use.
Description
Technical field
The present invention relates to a kind of method of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, belongs to Lipid use and plasticizer is opened
Hair field.
Background technology
Plasticizer is high polymer such as rubber, plastics, coating etc., to increase its mobility, plasticity and make during processing and forming
The low molecular compound that finished product has pliability and added.It is one of additive essential in the plastic processings such as PVC, and uses
Measure huge, China is the first in the world production and consumption state, and 2015 annual capacities are up to 4,000,000 tons, and sustainable growth year by year.It is wherein adjacent
Phthalates account for exhausted large scale.But research shows that O-phthalic acids plasticizer has the hair such as potential carcinogenicity, America and Europe
Disabled up to country.Alternatively the exploitation of the epoxyfatty acid esters of product is more and more active, wherein again with epoxy fat
Fatty acid methyl esters (EFAME) are mostly important, and its synthesis technique is that grease esterification is prepared into fatty acid methyl ester, further epoxy
Change can prepare epoxy aliphatic acid methyl ester plasticizer product.But its requirement to being suitable as the grease of raw material is higher, it is necessary to has
There is higher iodine number and molecular weight can not be too low.Generally can be used to the grease of synthesizing epoxy methyl esters has soybean oil, sunflower oil, dish
Seed oil waits the grease with high degree of unsaturation, but the tallowseed oil (Chinese catalpa oil) equally with high degree of unsaturation is because with small molecule
The aliphatic acid of amount and be not easy to prepare epoxy methyl esters, the flash-point that this is primarily due to product is too low.To solve this problem, it is necessary to right
Product is purified or is modified, and can not only bring unnecessary process and trouble, and increased manufacturing cost.
The content of the invention
In order to solve that product flash-point is low and existing modification technology existing for technique time-consuming, high energy consumption, effect difference the shortcomings of,
The present invention provides a kind of method of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer.
The technical scheme is that：A kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, active ingredient is binary acid
The gross mass percentage of epoxy aliphatic ester and a small amount of polyethers, wherein ester accounts for 1%-30% in 5%-70%, polyethers, and remaining is not
The epoxy Chinese catalpa oil methyl esters reacted；The structural formula of binary acid epoxy aliphatic ester is as follows：
The structural formula of polyethers is as follows：
Wherein：R1, R2 are the identical or different saturation or unsaturated carbon chain structure of carbon number；R is maleic acid, fumaric acid, right
One kind in phthalic acid, ethanedioic acid, adipic acid root architecture, n=1~3.
The method for preparing described binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, with Chinese catalpa oil or its fatty acid methyl ester and mistake
Oxide, binary acid are raw material, first by Chinese catalpa oil or its fatty acid methyl ester be converted into epoxy Chinese catalpa oil methyl esters, then be catalyzed open loop and with
Dibasic acid ester metaplasia is into binary acid epoxyfatty acid ester compounds.
The described method for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is specially：
The first step, prepare epoxy Chinese catalpa oil methyl esters：Chinese catalpa oil and methanol react to obtain Chinese catalpa oil methyl esters, Chinese catalpa oil methyl esters and peroxide
Cyclization obtains epoxy Chinese catalpa oil methyl esters under acid catalysis；
Second step, prepare binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer：By epoxy Chinese catalpa oil methyl esters and binary acid, catalyst
Add reactor in, stirring temperature reaction to acid value less than 2 terminate react, then be evaporated under reduced pressure, neutralisation treatment obtains binary
Sour modified epoxy Chinese catalpa oil methyl esters plasticizer product.
It is 1 that epoxy Chinese catalpa oil methyl esters and binary acid, which press the ratio between amount of material,:0.2~0.5 ratio adds.
The reaction temperature of second step is 100 DEG C~180 DEG C, and the reaction time is 2~6 hours.
Described catalyst charge is 0.1%~1%.
Described binary acid includes maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, adipic acid and corresponding acid anhydrides etc.
In one kind.
Catalysis catalyst used is 2-methylimidazole, 2- imidazolidinones, N, N- dimethyl benzylamines, 2,4- dimethyl miaows
Azoles, four butyl bromation amine, antioxidant or nitrogen protection can be added as needed on.
Described peroxide is peroxyformic acid, Peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, hydrogen peroxide
In any one.
Beneficial effect：
The present invention using a kind of binary acid modified epoxy Chinese catalpa oil methyl esters method modified epoxy Chinese catalpa oil methyl esters and obtained one
NEW TYPE OF COMPOSITE plasticizer of the kind containing polyester and ether structure.This method can effectively reduce the content of rudimentary epoxy aliphatic ester, hence it is evident that
Improve the relative molecular weight of final products.This method can not only cause Chinese catalpa oil to be used for producing plasticizer product, and reduce
The performances such as product flash-point, resistance to extractable are also add while modified process.
Brief description of the drawings
Fig. 1 is the infrared spectrum of maleic acid epoxy Chinese catalpa oil methyl esters.Epoxy aliphatic acid methyl ester is in 829cm in figure-1The epoxy at place
Absworption peak substantially disappears in the ring methyl esters spectrogram of maleic acid two, and the ring methyl esters of maleic acid two is in 1042cm-1Place have also appeared ehter bond
C-O absworption peaks, this illustrate maleic acid all with epoxy bond react.
Fig. 2 is molecular weight (exclusion chromatography) comparison diagram of maleic acid modified front and rear epoxy Chinese catalpa oil methyl esters.Can be with figure
It is clear that, epoxy Chinese catalpa oil methacrylate compound is more single, and molecular weight is relatively low；Product after maleic acid modified, hence it is evident that occur three
Individual peak, it is binary acid epoxy aliphatic ester (polyester) at 921 wherein being long-chain epoxy aliphatic acid methyl ester at 347, and more blunt peak
For the polyethers of low polymerization degree.
Specific implementation method
A kind of method of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, Chinese catalpa oil is used to pass through ester exchange first for raw material
Epoxy Chinese catalpa oil methyl esters is prepared into process for epoxidation, then binary acid ring is made with binary acid reaction in the presence of a catalyst
Oxygen Chinese catalpa oil methyl esters.Step reaction effectively less plasticizer components Short-Chain Fatty Acids ester (2,4- certain herbaceous plants with big flowers dienoic acid methyl ester) can contain
Amount, so as to the overall volatility for improving plasticizer product, resistance to migration, durability and flash-point.By epoxy Chinese catalpa oil methyl esters and to benzene
The binary acid such as dioctyl phthalate are 1 by the ratio between amount of material:0.2~1:0.5 adds in reactor, then adds and accounts for raw material epoxy Chinese catalpa
The catalyst of oily methyl esters 0.1%~1%.Progressively stirring is warming up to 100 DEG C~180 DEG C, and insulation reaction 2~6 hours is low to acid value
Terminate reaction in 2, then carry out the treatment process such as conventional vacuum distillation, neutralization and can obtain binary acid modified epoxy Chinese catalpa oil methyl esters
Plasticizer product, active ingredient are binary acid epoxy aliphatic ester and a small amount of polyethers, and wherein the gross mass percentage of ester is in 5%-
70%, polyethers accounts for 1%-30%, and structural formula is as follows：
Structural formula above is the structure of binary acid epoxy Chinese catalpa oil methyl esters, and following structural formula is polyether structure, and it is also
Plasticizer active ingredient.Wherein n=1-3.
Described raw material is Chinese catalpa oil or Chinese catalpa oil methyl esters；Described peroxide is peroxyformic acid, Peracetic acid, m-chloro peroxide
Benzoic acid, tertbutanol peroxide, hydrogen peroxide etc.；Described binary acid be maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, oneself
Diacid etc..
Described catalyst is 2-methylimidazole, 2- imidazolidinones, N, N- dimethyl benzylamines, 2,4- methylimidazoles, four
Butyl amine bromide etc..
Embodiment 1：
Raw material：Chinese catalpa oil, methanol, hydrogen peroxide, potassium hydroxide, p-methyl benzenesulfonic acid, maleic acid, N, N- dimethyl benzylamines；
According to the ratio between amount of material it is 6 by methanol and Chinese catalpa oil：1 proportioning input reactor, and add and account for Chinese catalpa oil quality point
The potassium hydroxide of number 0.6%, is stirred at reflux reaction 3 hours at 65 DEG C, and methanol removal and glycerine both obtain Chinese catalpa oil methyl esters；By gained
Chinese catalpa oil methyl esters input reactor, adds the formic acid for accounting for methyl esters quality 15% and 1% p-methyl benzenesulfonic acid, is heated to 55 DEG C of dropwise addition methyl esters
The hydrogen peroxide (30%) that 1.1 times of quality, was dripped off in 40 minutes, then was warming up to 65 DEG C and is reacted 4 hours.Liquid separation removes water again after cooling
Light yellow clear liquid epoxy Chinese catalpa oil methyl esters is both obtained through conventional post processings such as alkali cleaning washing distillations；By epoxy Chinese catalpa oil methyl esters and Malaysia
Acid puts into reactor by the ratio between amount of material for 1 ︰ 0.1, adds the catalyst n for accounting for that epoxy Chinese catalpa oil methyl esters mass fraction is 1%,
N- dimethyl benzylamines, stirring are warming up to 110 DEG C and reacted about 3 hours, and it is 0.19mgKOH/g to measure acid value, stops reaction.Crude product
For bronzing clear viscous shape liquid.
Embodiment 2：
Raw material：Chinese catalpa oil methyl esters, metachloroperbenzoic acid, p-methyl benzenesulfonic acid, maleic anhydride, N, N- dimethyl benzylamines；
Chinese catalpa oil methyl esters is put into reactor, it is molten by the metachloroperbenzoic acid of quality to maintain the temperature at 0-30 DEG C of dropwise addition 1.2
Liquid, dripped off, then react 5 hours in 1 hour.Finally the post processing by certain conventional such as filtering, alkali cleaning, washing, dehydration both
Obtain light yellow clear intermediate products epoxy Chinese catalpa oil methyl esters；It is 1 ︰ that epoxy Chinese catalpa oil methyl esters and maleic anhydride are pressed to the ratio between amount of material
0.15 input reactor, adds the catalyst n for accounting for that epoxy Chinese catalpa oil methyl esters mass fraction is 1%, N- dimethyl benzylamines, and stirring rises
Warm to 105 DEG C are reacted about 4 hours, and it is 0.32mgKOH/g to measure acid value, stop reaction.Crude product is bronzing clear viscous shape
Liquid.
Embodiment 3：
Raw material：Epoxy Chinese catalpa oil methyl esters, maleic anhydride, N, N- dimethyl benzylamines；
Epoxy Chinese catalpa oil methyl esters and maleic anhydride are put into reactor for 1 ︰ 0.29 by the ratio between amount of material, adds and accounts for epoxy
Chinese catalpa oil methyl esters mass fraction be 1% catalyst n, N- dimethyl benzylamines, stirring be warming up to 120 DEG C react about 4 hours, measure acid
Valency is 0.51mgKOH/g, stops reaction.Crude product is bronzing clear viscous shape liquid.
Embodiment 4：
Raw material：Epoxy Chinese catalpa oil methyl esters, terephthalic acid (TPA), 2-methylimidazole；
Epoxy Chinese catalpa oil methyl esters and terephthalic acid (TPA) are put into reactor for 1 ︰ 0.2 by the ratio between amount of material, adds and accounts for ring
Oxygen Chinese catalpa oil methyl esters mass fraction is 1% catalyst 2-methylimidazole, and stirring is warming up to 150 DEG C and reacted about 5 hours, measures acid value
During less than 1mgKOH/g, stop reaction.Crude product is bronzing thick liquid.
Embodiment is only used for stating implementation, only changes material ratio with this method and remaining unchanged for time is protected in this patent
Protect scope.
Table 1：Performance comparison before and after a kind of maleic acid modified epoxy Chinese catalpa oil methyl esters
Claims (9)
1. a kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that active ingredient is binary acid epoxyfatty acid
The gross mass percentage of ester and a small amount of polyethers, wherein ester accounts for 1%-30% in 5%-70%, polyethers, and remaining is the complete ring of unreacted
Oxygen Chinese catalpa oil methyl esters；The structural formula of binary acid epoxy aliphatic ester is as follows：
The structural formula of polyethers is as follows：
Wherein：R1、R2For the identical or different saturation of carbon number or unsaturated carbon chain structure；R is maleic acid, fumaric acid, terephthaldehyde
One kind in acid, ethanedioic acid, adipic acid root architecture, n=1~3.
2. prepare the method for the binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer described in claim 1, it is characterised in that with Chinese catalpa oil
Or its fatty acid methyl ester and peroxide, binary acid are raw material, Chinese catalpa oil or its fatty acid methyl ester are converted into epoxy Chinese catalpa oil first
Methyl esters, then it is catalyzed open loop and with dibasic acid ester metaplasia into binary acid epoxyfatty acid ester compounds.
3. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that tool
Body is：
The first step, prepare epoxy Chinese catalpa oil methyl esters：Chinese catalpa oil and methanol react to obtain Chinese catalpa oil methyl esters, and Chinese catalpa oil methyl esters and peroxide are in acid
The lower cyclization of catalysis obtains epoxy Chinese catalpa oil methyl esters；
Second step, prepare binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer：Epoxy Chinese catalpa oil methyl esters and binary acid, catalyst are added
In reactor, stirring temperature reaction terminate to react less than 2mgKOH/g to acid value, then be evaporated under reduced pressure, neutralisation treatment obtains two
The sour modified epoxy Chinese catalpa oil methyl esters plasticizer product of member.
4. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that ring
It is 1 that oxygen Chinese catalpa oil methyl esters and binary acid, which press the ratio between amount of material,:0.2~0.5 ratio adds.
5. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that the
The reaction temperature of two steps is 100 DEG C~180 DEG C, and the reaction time is 2~6 hours.
6. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that institute
The catalyst charge stated is 0.1%~1%.
7. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that urge
Change catalyst used as 2-methylimidazole, 2- imidazolidinones, N, N- dimethyl benzylamines, 2,4- methylimidazoles, tetrabutyl bromine
Change amine, antioxidant or nitrogen protection can be added as needed on.
8. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that institute
The peroxide stated is any one in peroxyformic acid, Peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, hydrogen peroxide
Kind.
9. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, it is characterised in that institute
The binary acid stated includes one kind in maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, adipic acid and corresponding acid anhydrides etc..
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277611A (en) * | 2021-12-31 | 2022-04-05 | 佛山荷韵特种材料有限公司 | Special explosion-proof flower cover oil for ceramic stained paper, production process of special explosion-proof flower cover oil and ceramic stained paper |
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| CN1058604A (en) * | 1990-08-02 | 1992-02-12 | 岳阳石油化工总厂研究院 | The preparation method of stillingia oil toughening agent for epoxy resin and modified epoxy thereof |
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| CN102517157A (en) * | 2011-12-31 | 2012-06-27 | 中国林业科学研究院林产化学工业研究所 | Rubber seed oil-based epoxy fatty acid methyl ester and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277611A (en) * | 2021-12-31 | 2022-04-05 | 佛山荷韵特种材料有限公司 | Special explosion-proof flower cover oil for ceramic stained paper, production process of special explosion-proof flower cover oil and ceramic stained paper |
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