CN114989489A - Epoxy plasticizer and preparation method and application thereof - Google Patents
Epoxy plasticizer and preparation method and application thereof Download PDFInfo
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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
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Abstract
The invention relates to C11C3, in particular to an epoxy plasticizer and a preparation method and application thereof. The raw materials for preparing the plasticizer comprise epoxy fatty acid ester, alcohol and a transesterification catalyst. The invention provides a plasticizer which has plasticizing effect almost completely replacing DOP, is nontoxic, environment-friendly, degradable, good in compatibility, high in plasticizing efficiency, simple in production process and low in cost by using a method for performing ester exchange between epoxy fatty acid ester with proper size and alcohol, and a preparation method thereof, and can be used for multiple fields of PVC films such as gloves, pipes, foaming materials and the like. The epoxy fatty acid ester is modified by controlling the carbon atom number and the hydroxyl number of alcohol in the plasticizer, and the modified plasticizer has a chemical structure containing both epoxy groups and a plurality of ester bonds, and has better low volatility and low mobility on the basis of keeping the excellent performance of the original epoxy plasticizer.
Description
Technical Field
The invention relates to C11C3, in particular to an epoxy plasticizer and a preparation method and application thereof.
Background
The PVC resin can be used in a plurality of fields such as daily use, chemical industry and the like, wherein a plasticizer is required to be used for improving the processing and use performance of PVC in the PVC processing process, and the phthalate plasticizer is mainly used at present because of the effect of polar phenyl and ester groups and has high compatibility and migration resistance with PVC, but is limited by partial fields due to the toxic influence.
The epoxy fatty acid ester plasticizer is one of the development directions of the current plasticizers as a safe and environment-friendly plasticizer, but the migration resistance and the precipitation resistance are poor due to low polarity, small molecules and the like, and the epoxy fatty acid ester plasticizer is mainly used as an auxiliary plasticizer at present. CN112126529A discloses a preparation method of a polyalcohol epoxy fatty acid ester plasticizer, which comprises the step of esterifying polyalcohol and epoxy fatty acid to obtain the polyalcohol fatty acid ester, and the polyalcohol fatty acid ester plasticizer has good plasticizing effect and migration resistance, and is safe and nontoxic.
However, the esterification method requires excessive acid for reaction, the yield and purity of the esterification product are difficult to control, the post-treatment is complicated, the application of the esterification process is influenced, and the prepared epoxy plasticizer has poor compatibility with PVC compared with phthalate, and the plasticizing effect and the mechanical property of the obtained PVC material are influenced.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides an epoxy plasticizer, which is prepared from raw materials including an epoxy fatty acid ester, an alcohol and a transesterification catalyst.
In a preferred embodiment of the present invention, the epoxy fatty acid ester is an epoxy C10-C22 fatty acid C1-C8 alkyl ester.
In a preferred embodiment of the present invention, the epoxy fatty acid ester is selected from epoxy C10-C22 fatty acid C1-C4 alkyl esters, and examples thereof include epoxy C10-C22 fatty acid methyl esters, epoxy C10-C22 fatty acid ethyl esters, and epoxy C10-C22 fatty acid butyl esters.
The epoxy fatty acid ester is obtained by oxidizing unsaturated double bonds of fatty acid ester into epoxy bonds, is not particularly limited in the invention, can be one or a mixture of oleate, linoleate and linolenate, and is preferably a mixture, and can be prepared or purchased by self, and when purchased, can be purchased from Guangzhou Fuzhou Nongcheng chemical engineering Co., Ltd (mixture of epoxy C10-C22 fatty acid C1-C4 alkyl ester).
As a preferable technical scheme of the invention, the epoxy fatty acid ester has 1-3 epoxy groups, preferably 1 epoxy group.
In a preferred embodiment of the present invention, the number of hydroxyl groups in the alcohol is 1 to 3, and examples thereof include 1, 2, and 3.
As a preferred technical scheme of the invention, the structural formula of the alcohol is (OH) n R and n are 1-3, and R is alkyl or an alkyl derivative.
In a preferred embodiment of the present invention, the alkyl derivative is obtained by substituting O, S, C ═ O or C ═ OO for a methylene group in the alkyl group. The number of substituted methylene groups in the alkyl derivative is not particularly limited.
In a preferred embodiment of the present invention, the alcohol has 4 to 10 carbon atoms, and examples thereof include 4, 5, 6, 7, 8, 9 and 10.
As examples of the alcohol, there may be mentioned monohydric alcohols such as triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, n-butanol, n-hexanol and n-heptanol, dihydric alcohols such as triethylene glycol, diethylene glycol, tetraethylene glycol, dibutylene glycol and hexanediol, trihydric alcohols such as trimethylolpropane, trimethylolethane and hexanetriol.
In a preferred embodiment of the present invention, the molar ratio of the ester group of the epoxidized fatty acid ester to the hydroxyl group of the alcohol is 1: (1.05 to 1.3) and there may be mentioned, for example, 1: 1.05, 1: 1.1, 1: 1.15, 1: 1.2, 1: 1.25, 1: 1.3. the specific amounts of the epoxy fatty acid ester and the alcohol are not limited in the present invention, and may be selected according to the ester group of the epoxy fatty acid ester and the hydroxyl group of the alcohol.
The present invention is not particularly limited to the transesterification catalyst, and there may be mentioned strong base catalysts such as potassium hydroxide and sodium hydroxide; ionic liquid catalyst, soluble salt catalyst such as sodium methoxide (CH) 3 ONa)、K 2 CO 3 (ii) a Ion exchange resin catalysts, such as Lewatit K1221 ion exchange resin catalyst; organometallic catalysts, e.g. dibutyltin oxide Bu 2 SnO, samarium trifluoromethanesulfonate; tetraalkyl titanates, such as: tetraisopropyl titanate, etc.; the basic molecular sieve catalyst is a preferable technical scheme of the invention, and the ester exchange catalyst accounts for 0.5-5 wt% of the total weight of the epoxy fatty acid ester and the alcohol, and can be enumerated by 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt%. The amount of the catalyst used in the present invention is not particularly limited, and may be selected according to the kind of the catalyst. And when the catalyst such as ion exchange resin is selected, the catalyst can be recycled.
In a second aspect, the present invention provides a method for preparing the epoxy plasticizer, comprising: and reacting epoxy fatty acid ester, alcohol and an ester exchange catalyst at the temperature of 90-200 ℃ under normal pressure or reduced pressure to-101.325-0 kPa, washing and drying to obtain the epoxy plasticizer.
The reaction is heated by an oil bath, and the heating temperature of the oil bath is 160-200 ℃. According to the invention, the heating temperature of the oil bath is controlled to be higher than the boiling point of the alcohol, a reflux system is formed for reaction, the nuclear yield of the reaction can be improved, and the high-chroma and turbid products are avoided. Wherein the reaction of the invention is carried out in an inert gas environment, such as nitrogen, helium, argon, etc., and the reaction end point is detected by chromatography.
In a preferred embodiment of the present invention, the washing is performed by an aqueous solution of an inorganic salt. The inorganic salt aqueous solution may be, but not particularly limited to, an aqueous sodium chloride solution, an aqueous ammonium chloride solution, an aqueous sodium bicarbonate solution, and the like, and the inorganic salt in the inorganic salt aqueous solution accounts for 5 to 15 wt% of the inorganic salt aqueous solution, and may be exemplified by 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, and 15 wt%.
The second aspect of the invention provides an application of the epoxy plasticizer, which is used for PVC films, PVC artificial leather, PVC gloves, PVC pipes and PVC foaming materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a plasticizer which has plasticizing effect almost completely replacing DOP, is nontoxic, environment-friendly, degradable, good in compatibility, high in plasticizing efficiency, simple in production process and low in cost by using a method for performing ester exchange between epoxy fatty acid ester with proper size and alcohol, and a preparation method thereof, and can be used for multiple fields of PVC films such as gloves, pipes, foaming materials and the like.
(2) The epoxy fatty acid ester is modified by controlling the carbon atom number and the hydroxyl number of alcohol in the plasticizer, and the modified plasticizer has a chemical structure containing both epoxy groups and a plurality of ester bonds, and has better low volatility and low migration on the basis of keeping the excellent performance of the original epoxy plasticizer.
(3) Generally, the plasticizing effect of a small molecular weight linear epoxy plasticizer is greater than that of a large molecular weight branched chain epoxy plasticizer, and the inventor surprisingly finds that the epoxy fatty acid ester is subjected to chain extension by using an alcohol with a proper carbon chain length, so that on one hand, the polarity is increased by using the epoxy and ester groups of the plasticizer, and on the other hand, a low-polarity chain segment is provided by a fatty acid long chain and the carbon chain of the alcohol, so that when the plasticizer is used for PVC processing, the plasticizer and a PVC polar chain partially enter the middle of a PVC chain while acting, and therefore, the plasticizer, the compatibility and the elongation at break are high, high tensile strength is achieved, and the comprehensive performance of a PVC material is improved.
(4) In addition, the invention can promote the smooth proceeding of the reaction by using proper catalyst and reaction temperature to carry out the ester exchange reaction and controlling the structures of the epoxy fatty acid ester and the alcohol, thereby obtaining the product with high yield, easily removing the excessive alcohol and the like, having simple post-treatment and obtaining the product with lower chroma.
(5) The inventor finds that the epoxy plasticizer can be obtained at higher temperature under normal pressure and lower temperature under reduced pressure, and can prepare clear and high-yield plasticizer products, and has high compatibility and plasticizing effect with PVC.
Detailed Description
Examples
Example 1
This example provides an epoxy resin plasticizer prepared from the following raw materials: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether, K 2 CO 3 9g of a mixture; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether, K 2 CO 3 9g (3% wt) of the mixture was put into a 500ml three-necked flask, which was placed in an oil bath with magnetic stirring, the oil bath was heated to 180 ℃ and N was introduced thereinto 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is light yellow clear liquid, and the yield is 94.5%.
Example 2
This example provides an epoxy resin plasticizer prepared from the following raw materials: 250g of epoxy fatty acid methyl ester, 66.08g of triethylene glycol monomethyl ether and 2.53g of dibutyltin oxide; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 250g of epoxy fatty acid methyl ester, 66.08g of triethylene glycol monomethyl ether and 2.53g (0.8 wt%) of dibutyltin oxide are mixed and put into a 500ml three-neck flask, the flask is placed into an oil bath kettle with magnetic stirring, the oil bath is heated to 180 ℃, and N is introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. To the end of the reactionAfter this point, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is a light yellow clear liquid, and the yield is 93.7%.
Example 3
This example provides an epoxy resin plasticizer prepared from the following raw materials: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether, and CH 3 ONa 3 g; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether, and CH 3 ONa 3g (1% wt) was mixed and charged into a 500ml three-necked flask, which was placed in an oil bath with magnetic stirring, heated to 180 ℃ in an oil bath, and N was introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, and then distilling under reduced pressure to remove water to obtain the target product, wherein the product is a light yellow clear liquid, and the yield is 90%.
Example 4
This example provides an epoxy resin plasticizer prepared from the following raw materials: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether and 9g of Lewatit K1221 ion exchange resin catalyst; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 190.11g of epoxy fatty acid methyl ester, 109.82g of triethylene glycol monomethyl ether and 9g (3 percent by weight) of Lewatit K1221 ion exchange resin catalyst are mixed and put into a 500ml three-neck flask, the flask is placed into an oil bath kettle with magnetic stirring, the oil bath is heated to 180 ℃, and N is introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. Cooling to room temperature, washing with 8% NaCl solution for three times, and steaming under reduced pressureDistilling to remove water, and finally filtering under reduced pressure to obtain a target product, wherein the product is light yellow clear liquid, the yield is 85.9 percent, and the catalyst can be repeatedly utilized for three times.
Example 5
This example provides an epoxy resin plasticizer prepared from the following raw materials: 250g of epoxy fatty acid methyl ester, 66.08g of triethylene glycol and 2.43g of dibutyltin oxide; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 250g of epoxidized fatty acid methyl ester, 66.08g of triethylene glycol and 2.43g (0.8 wt%) of dibutyltin oxide were mixed and put into a 500ml three-necked flask, the flask was placed in an oil bath kettle with magnetic stirring, the oil bath was heated to 180 ℃, and N was introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is a light yellow clear liquid, and the yield is 93.7%.
Example 6
This example provides an epoxy resin plasticizer prepared from the following raw materials: 262.49g of epoxy fatty acid methyl ester, 41.33g of trimethylolpropane and 2.42g of dibutyltin oxide; the epoxidized fatty acid methyl ester was purchased from Guangzhou rich non-chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 262.49g of epoxidized fatty acid methyl ester, 41.33g of trimethylolpropane and 2.42g (0.8% wt) of dibutyltin oxide were mixed and put into a 500ml three-necked flask, the flask was put into an oil bath pot with magnetic stirring, the oil bath was heated to 180 ℃ and N was introduced thereinto 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is light yellow clear liquid, and the yield is 90.8%.
Example 7
This example provides an epoxy resin plasticizer prepared from the following raw materials: 195.89g of epoxy fatty acid ethyl ester, 108.37g of triethylene glycol monomethyl ether, 2.43g (0.8% wt) of dibutyl tin oxide; the epoxidized fatty acid ethyl ester was purchased from Guangzhou Feichi chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 195.89g of epoxy fatty acid ethyl ester, 108.37g of triethylene glycol monomethyl ether and 2.43g (0.8 wt%) of dibutyltin oxide are mixed and put into a 500ml three-neck flask, the flask is placed into an oil bath kettle with magnetic stirring, the oil bath is heated to 190 ℃, and N is introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is light yellow clear liquid, and the yield is 89.3%.
Example 8
This example provides an epoxy resin plasticizer prepared from the following raw materials: 212.69g of epoxy fatty acid butyl ester, 108.37g of triethylene glycol monomethyl ether and 2.41g of dibutyl tin oxide; the epoxidized butyl fatty acid ester was purchased from Guangzhou Fufic science and technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 212.69g of epoxy fatty acid butyl ester, 108.37g of triethylene glycol monomethyl ether and 2.41g (0.8 percent by weight) of dibutyltin oxide are mixed and put into a 500ml three-neck flask, the flask is placed into an oil bath kettle with magnetic stirring, the oil bath is heated to 180 ℃, and N is introduced 2 Condensing and refluxing, and detecting by chromatography to judge the reaction end point. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is a light yellow clear liquid, and the yield is 86.6%.
Example 9
This example provides an epoxy resin plasticizer prepared from the following raw materials: 212.69g of epoxy fatty acid butyl ester, 108.37g of triethylene glycol monomethyl ether and 2.41g of dibutyl tin oxide; the epoxidized butyl fatty acid ester was purchased from Guangzhou Fufic science and technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: mixing 212.69g of epoxy fatty acid butyl ester, 108.37g of triethylene glycol monomethyl ether and 2.41g (0.8 wt%) of dibutyl tin oxide, putting the mixture into a 500ml three-neck flask, putting the flask into an oil bath kettle with magnetic stirring, heating the flask to 90 ℃ in an oil bath, and introducing N 2 Reducing the pressure to-101.325 kpa for reaction for 4 hours, raising the temperature to 150 ℃, keeping the pressure reduced, continuing the reaction for 4 hours, condensing and refluxing, and judging the reaction end point by chromatographic detection. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is light yellow clear liquid, and the yield is 88.7%.
Example 10
The embodiment provides an epoxy resin plasticizer, and the raw materials for preparing the plasticizer comprise: 195.89g of epoxy fatty acid ethyl ester, 108.37g of triethylene glycol monomethyl ether, 2.43g (0.8% wt) of dibutyl tin oxide; the epoxidized fatty acid ethyl ester was purchased from Guangzhou Feichi chemical technology, Inc.
This example also provides a method of preparing the epoxy resin plasticizer described above, comprising: 195.89g of epoxy fatty acid ethyl ester, 108.37g of triethylene glycol monomethyl ether and 2.43g (0.8 wt%) of dibutyltin oxide are mixed and put into a 500ml three-neck flask, the flask is placed in an oil bath pot with magnetic stirring, the oil bath is heated to 90 ℃, the pressure is reduced to-101.325 kpa for reaction for 4 hours, the temperature is increased to 150 ℃, the pressure is maintained for reaction for 4 hours, the reaction is continued for condensation and reflux, and the reaction end point is judged by chromatographic detection. After the reaction end point was reached, heating and stirring were stopped. After cooling to normal temperature, washing with 8% NaCl for three times, then distilling under reduced pressure to remove water, and finally filtering under reduced pressure to obtain the target product, wherein the product is light yellow clear liquid, and the yield is 90.8%.
Evaluation of Performance
1. And (3) testing comprehensive performance: the plasticizer (code number E234) provided in example 2 and the plasticizer (code number E235) provided in example 5 were used as experimental groups, several plasticizers DOTP dioctyl terephthalate, EM bis (2-methoxyethyl) phthalate, ESO epoxidized soybean oil, which are commercially used in relatively large amounts, were used as control groups for PVC processing, and the properties of the resulting PVC products were tested, wherein the formulation of the PVC products was PVC (commercially available powder) plasticizer: liquid composite heat stabilizer is 100: 40: 3 (mass ratio), the results are shown in table 1.
TABLE 1
From table 1, it is found that the plasticizer provided by the present invention has high tensile strength, and also has good elongation at break, volatilization resistance and migration resistance.
2. And (3) application performance testing:
the plasticizer of the present invention can be used in various fields such as PVC films, PVC artificial leathers, PVC gloves, PVC pipes, PVC foams, etc., and the inventors found that the following tests were performed using the plasticizer (code No. E234) provided in example 2 as an experimental group and DOTP plasticizer as a control group, when used in gloves, to have outstanding advantages:
(1) compatibility: respectively adding E234 and DOTP into the Tangshan PVC gloves to prepare a corresponding formula, observing whether the film is transparent after the film is prepared, if so, the film has good compatibility, and observing the maximum dosage of the plasticizer when the film has good compatibility, and finding that the mass ratio of the E234 can reach 30 percent, and the mass ratio of the DOTP can reach 20 percent at most. It can be found that: in PVC gloves, E234 compatibility is stronger than DOTP compatibility.
(2) Tensile property: PVC gloves were prepared and tested with E234 and DOTP being added at 20%, wherein the results of the PVC gloves with E234 and DOTP added are shown in tables 2 and 3, respectively.
TABLE 2
TABLE 3
As can be seen from the test results in tables 2 and 3, the plasticizer provided by the present invention has high tensile strength and elongation when used in PVC glove processing, compared to the conventional plasticizers such as DOTP at present.
From the above, by using the plasticizer and the preparation method thereof provided by the invention, the plasticizer with high safety and high yield can be obtained, and when the plasticizer is used for plasticizing PVC, a PVC material with high mechanical property and low migration can be obtained, and the plasticizer can be used in various fields such as gloves, films, pipes, foam materials and the like.
It is to be understood that the embodiments described herein are to be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features, advantages, or aspects within various embodiments should be considered as available for other similar features, advantages, or aspects in other embodiments.
Claims (10)
1. An epoxy plasticizer is characterized in that raw materials for preparing the plasticizer comprise epoxy fatty acid ester, alcohol and a transesterification catalyst;
the molar ratio of the ester group of the epoxy fatty acid ester to the hydroxyl group of the alcohol is 1: (1.05-1.3).
2. The epoxy plasticizer according to claim 1, wherein the epoxy fatty acid ester is an epoxy C10-C22 fatty acid C1-C8 alkyl ester.
3. The epoxy plasticizer according to claim 2, wherein the epoxy fatty acid ester is an epoxy C10-C22 fatty acid C1-C4 alkyl ester.
4. The epoxy plasticizer according to claim 1, wherein the epoxy fatty acid ester has 1 to 3 epoxy groups.
5. The epoxy plasticizer according to any one of claims 1 to 4, wherein the number of hydroxyl groups in the alcohol is 1 to 3.
6. The epoxy plasticizer according to claim 5, wherein the alcohol has a structural formula of (OH) n R and n are 1-3, and R is alkyl or an alkyl derivative.
7. The epoxy plasticizer according to claim 6, wherein the alkyl derivative is obtained by substituting O, S, C ═ O or C ═ OO for methylene in the alkyl group.
8. The epoxy plasticizer according to claim 5, wherein the alcohol has 4 to 10 carbon atoms.
9. A method for preparing the epoxy plasticizer according to any one of claims 1 to 8, comprising: and reacting epoxy fatty acid ester, alcohol and an ester exchange catalyst at the temperature of 90-200 ℃ under normal pressure or reduced pressure to-101.325-0 kPa, washing and drying to obtain the epoxy plasticizer.
10. The use of the epoxy plasticizer according to any one of claims 1 to 8 for PVC films, PVC artificial leather, PVC gloves, PVC pipes, PVC foams.
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CN110041195A (en) * | 2019-01-22 | 2019-07-23 | 中国林业科学研究院林产化学工业研究所 | A kind of fatty acid poleysters PVC plasticizer and preparation method thereof |
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