CN107383417B - 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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- CN107383417B CN107383417B CN201710599593.1A CN201710599593A CN107383417B CN 107383417 B CN107383417 B CN 107383417B CN 201710599593 A CN201710599593 A CN 201710599593A CN 107383417 B CN107383417 B CN 107383417B
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- acid
- methyl esters
- chinese catalpa
- 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
-
- 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
Abstract
The present invention relates to a kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer and preparation method thereof.Epoxy Chinese catalpa oil methyl esters is converted by tallowseed oil first as raw material using Chinese catalpa oil or its fatty acid methyl ester, peroxide, binary acid, then is catalyzed open loop and with dibasic acid ester metaplasia at binary acid epoxyfatty acid ester compounds.This method can effectively reduce Chinese catalpa oil methyl esters Short-Chain Fatty Acids ester 2, and the content of 4- certain herbaceous plants with big flowers dienoic acid methyl ester improves average molecular weight, so that plasticizer product be made to have the features such as low volatility, resistance to migration, preferable durability, 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 technique
Plasticizer is high polymer such as rubber, plastics, coating etc., increases its mobility, plasticity and makes when processing and forming
The low molecular compound that finished product is added with flexibility.It is one of essential additive 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 potential carcinogenicity, the hair such as America and Europe
It has been disabled up to country.Alternatively the exploitation of the epoxyfatty acid esters of product is more and more active, wherein again with epoxy rouge
Fatty acid methyl esters (EFAME) are mostly important, and synthesis technology is that grease esterification is prepared into fatty acid methyl ester, further epoxy
Change can prepare epoxy aliphatic acid methyl ester plasticizer product.But it is more demanding to the grease for being suitable as raw material, it is necessary to have
There is higher iodine number and molecular weight cannot be too low.The grease that usually can be used to synthesizing epoxy methyl esters has soybean oil, sunflower oil, dish
Seed oil etc. has the grease of high degree of unsaturation, but the tallowseed oil (Chinese catalpa oil) equally with high degree of unsaturation is because have small molecule
The fatty 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 unnecessary process and trouble, and increased manufacturing cost can be not only brought.
Summary of the invention
In order to solve that product flash-point is low and existing modification technology existing for technique time-consuming, energy consumption is high, effect is poor the disadvantages of,
The present invention provides a kind of method of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer.
The technical solution of the present invention is as follows: a kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, effective component is binary acid
Epoxy aliphatic ester and a small amount of polyethers, wherein for the gross mass percentage of ester in 5%-70%, polyethers accounts for 1%-30%, remaining is not
Reacted epoxy 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, R2 are the identical or different saturation or unsaturated carbon chain structure of carbon number；R is maleic acid, fumaric acid, right
One of phthalic acid, ethanedioic acid, adipic acid root knot structure, n=1~3.
The method of the preparation 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 be 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 at binary acid epoxyfatty acid ester compounds.
The method for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, specifically:
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 prepares binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer: by epoxy Chinese catalpa oil methyl esters and binary acid, catalyst
Be added in reactor, reaction was completed lower than 2 for stirring temperature reaction to acid value, then be evaporated under reduced pressure, neutralisation treatment obtains binary
Sour modified epoxy Chinese catalpa oil methyl esters plasticizer product.
Epoxy Chinese catalpa oil methyl esters and binary acid are added in the ratio that the ratio between amount of substance is 1:0.2~0.5.
The reaction temperature of second step is 100 DEG C~180 DEG C, and the reaction time is 2~6 hours.
The catalyst charge is 0.1%~1%.
The binary acid includes maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, adipic acid and corresponding acid anhydrides etc.
One of.
Catalysis catalyst used is 2-methylimidazole, 2- imidazolidinone, N, N- dimethyl benzylamine, 2,4- dimethyl miaow
Antioxidant or nitrogen protection can be added as needed in azoles, four butyl bromation amine.
The peroxide is peroxyformic acid, Peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, hydrogen peroxide
In any one.
The utility model has the advantages that
The present invention uses a kind of method modified epoxy Chinese catalpa oil methyl esters of binary acid modified epoxy Chinese catalpa oil methyl esters and has 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 make Chinese catalpa oil be used to produce plasticizer product, and reduce
The performances such as product flash-point, resistance to extractable are also added while modified process.
Detailed description of the invention
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
Absorption peak obviously disappears in two ring methyl esters spectrogram of maleic acid, and two ring methyl esters of maleic acid is in 1042cm-1Place has also appeared ehter bond
C-O absorption peak, this illustrates that maleic acid is all reacted with epoxy bond.
Fig. 2 is molecular weight (exclusion chromatography) comparison diagram of the epoxy Chinese catalpa oil methyl esters of maleic acid modified front and back.It can be in 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
A peak 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, uses Chinese catalpa oil for raw material, passes through transesterification first
It is prepared into epoxy Chinese catalpa oil methyl esters with process for epoxidation, then is reacted with binary acid binary acid ring is made in the presence of a catalyst
Oxygen Chinese catalpa oil methyl esters.Step reaction can effectively less plasticizer components Short-Chain Fatty Acids ester (2,4- certain herbaceous plants with big flowers dienoic acid methyl ester) contain
Amount, thus the whole 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 added in reactor by the ratio between amount of substance for 1:0.2~1:0.5, are then added and are accounted for raw material epoxy Chinese catalpa
The catalyst of oily methyl esters 0.1%~1%.Gradually stirring is warming up to 100 DEG C~180 DEG C, and insulation reaction 2~6 hours low to acid value
Reaction was completed in 2, then carries out the treatment process such as conventional vacuum distillation, neutralization and binary acid modified epoxy Chinese catalpa oil methyl esters can be obtained
Plasticizer product, effective component 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, is also
Plasticizer effective component.Wherein n=1-3.
The raw material is Chinese catalpa oil or Chinese catalpa oil methyl esters；The peroxide is peroxyformic acid, Peracetic acid, m-chloro peroxide
Benzoic acid, tertbutanol peroxide, hydrogen peroxide etc.；The binary acid be maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, oneself
Diacid etc..
The catalyst is 2-methylimidazole, 2- imidazolidinone, N, N- dimethyl benzylamine, 2,4- methylimidazole, 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 benzylamine；
Methanol and Chinese catalpa oil are put into reactor according to the proportion that the ratio between amount of substance is 6:1, and is added and accounts 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 glycerol both obtain Chinese catalpa oil methyl esters；By gained
Chinese catalpa oil methyl esters puts into reactor, adds the p-methyl benzenesulfonic acid of the formic acid and 1% that account for methyl esters quality 15%, is heated to 55 DEG C of dropwise addition methyl esters
The hydrogen peroxide (30%) that 1.1 times of quality, drips off in 40 minutes, then is warming up to 65 DEG C and reacts 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 reaction kettle by the ratio between amount of substance for 1 ︰ 0.1, adds and accounts for the catalyst n that epoxy Chinese catalpa oil methyl esters mass fraction is 1%,
N- dimethyl benzylamine, stirring are warming up to 110 DEG C and react about 3 hours, and measuring acid value is 0.19mgKOH/g, 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 benzylamine；
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 drips off in 1 hour, then reacts 5 hours.Finally both by certain conventional post-processing such as filtering, alkali cleaning, washing, dehydration
Obtain light yellow clear intermediate products epoxy Chinese catalpa oil methyl esters；It is 1 ︰ by the ratio between amount that epoxy Chinese catalpa oil methyl esters and maleic anhydride press substance
0.15 investment reaction kettle, adds and accounts for the catalyst n that epoxy Chinese catalpa oil methyl esters mass fraction is 1%, N- dimethyl benzylamine, and stirring rises
Temperature to 105 DEG C react about 4 hours, measure acid value be 0.32mgKOH/g, 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 benzylamine；
Epoxy Chinese catalpa oil methyl esters and maleic anhydride are put into reaction kettle by the ratio between amount of substance for 1 ︰ 0.29, adds and accounts for epoxy
The catalyst n that Chinese catalpa oil methyl esters mass fraction is 1%, N- dimethyl benzylamine, stirring are warming up to 120 DEG C and react about 4 hours, measure acid
Valence 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 reaction kettle by the ratio between amount of substance for 1 ︰ 0.2, add Zhan Huan
The catalyst 2-methylimidazole that oxygen Chinese catalpa oil methyl esters mass fraction is 1%, stirring are warming up to 150 DEG C and react about 5 hours, measure acid value
When lower than 1mgKOH/g, stop reaction.Crude product is bronzing thick liquid.
Embodiment is only used for statement implementation method, only changes material ratio with this method and remaining unchanged for time is protected in this patent
Protect range.
A kind of table 1: maleic acid modified epoxy Chinese catalpa oil methyl esters front and back performance comparison
Claims (9)
1. a kind of binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized in that effective component is binary acid epoxyfatty acid
Ester and a small amount of polyethers, wherein for the gross mass percentage of ester in 5%-70%, polyethers accounts for 1%-30%, remaining ring complete for 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 of acid, ethanedioic acid, adipic acid root knot structure, n=1~3.
2. the method for preparing binary acid modified epoxy described in claim 1 Chinese catalpa oil methyl esters plasticizer, which is characterized in that with Chinese catalpa oil
Or its fatty acid methyl ester and peroxide, binary acid or the corresponding acid anhydrides of binary acid are raw material, first by Chinese catalpa oil or its fatty acid
Methyl esters is converted into epoxy Chinese catalpa oil methyl esters, then is catalyzed open loop and with dibasic acid ester metaplasia at 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, which is characterized in that tool
Body are as follows:
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
It is catalyzed lower cyclization and obtains epoxy Chinese catalpa oil methyl esters；
Second step prepares binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer: by epoxy Chinese catalpa oil methyl esters and binary acid or binary acid phase
Acid anhydrides, the catalyst answered are added in reactor, and lower than 2mgKOH/g, reaction was completed for stirring temperature reaction to acid value, then is depressurized
Distillation, neutralisation treatment obtain binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer product.
4. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized in that ring
Oxygen Chinese catalpa oil methyl esters and binary acid or the corresponding acid anhydrides of binary acid are added in the ratio that the ratio between amount of substance is 1:0.2~0.5.
5. the method according to claim 3 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized 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 3 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized 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, which is characterized in that urge
Changing catalyst used is 2-methylimidazole, 2- imidazolidinone, N, N- dimethyl benzylamine, 2,4- methylimidazole, tetrabutyl bromine
Change amine, antioxidant or nitrogen protection can be added as needed.
8. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized in that institute
The peroxide stated is peroxyformic acid, Peracetic acid, metachloroperbenzoic acid, tertbutanol peroxide, any one in hydrogen peroxide
Kind.
9. the method according to claim 2 for preparing binary acid modified epoxy Chinese catalpa oil methyl esters plasticizer, which is characterized in that institute
The binary acid stated includes one of maleic acid, fumaric acid, terephthalic acid (TPA), ethanedioic acid, adipic acid.
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| 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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| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxy fatty acid methyl ester |
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| CN106146431A (en) * | 2016-06-30 | 2016-11-23 | 中国林业科学研究院林产化学工业研究所 | A kind of epoxy low calorie fats plasticizer and preparation method thereof |
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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 |
| CN101891713A (en) * | 2010-07-09 | 2010-11-24 | 南京工业大学 | Method for preparing epoxy fatty acid methyl ester |
| 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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