CN115594590A - Bio-based plasticizer and preparation method thereof - Google Patents
Bio-based plasticizer and preparation method thereof Download PDFInfo
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- CN115594590A CN115594590A CN202211359679.4A CN202211359679A CN115594590A CN 115594590 A CN115594590 A CN 115594590A CN 202211359679 A CN202211359679 A CN 202211359679A CN 115594590 A CN115594590 A CN 115594590A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
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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
- C08K5/101—Esters; Ether-esters of monocarboxylic 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
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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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 & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a bio-based plasticizer, which is prepared by reacting epoxy fatty acid ester with a hydroxyl compound under the catalysis of a first catalyst to obtain a first product, and then reacting the first product with a carboxyl compound under the catalysis of a second catalyst. The plasticizer has strong interaction force with the polymer, so that the plasticizer has better compatibility, the plasticizer can better interpenetrate among molecular chains of the polymer to improve the flexibility of the polymer, the volatility of the plasticizer is low, the forming loss is reduced, and the migration resistance is strong, so that the precipitation in the use process is avoided.
Description
Technical Field
The invention relates to the field of plastic plasticizers, in particular to a bio-based plasticizer and a preparation method thereof.
Background
The plasticizer is also called plasticizer, and is a processing aid widely used for modifying high polymer materials. Phthalate plasticizers are PVC plasticizers with the largest amount in the market, have excellent plasticizing effect and mature process, but researches show that phthalate constitutes a potential threat to the environment and human health, countries strictly limit the use of phthalate plasticizers against the problem, and specific applications prohibit the use of such plasticizers, such as materials of medical equipment, toys for children, food packages, water supply pipelines and the like. Therefore, it is a hot point to develop a PVC plasticizer which is non-toxic, excellent in plasticizing effect, and harmless to the environment, to replace the o-benzene plasticizer.
Epoxy fatty acid ester plasticizer uses epoxy fatty acid methyl ester as the main, and is nontoxic, and the raw materials can be regenerated, and can effectively replace o-benzene plasticizer, however, researches show that if epoxy fatty acid methyl ester is used too much in PVC products, plasticizer migration and diffusion can occur in the use process, so that the PVC products generate oil, and the product quality and the customer experience are influenced.
Disclosure of Invention
The invention aims to provide a bio-based plasticizer which has strong interaction force with a polymer so as to have better compatibility, can be better inserted among molecular chains of the polymer so as to improve the flexibility of the polymer, has low volatility, reduces molding loss, and has strong mobility resistance so as to avoid precipitation in the using process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a bio-based plasticizer is prepared from the following raw materials: reacting epoxy fatty acid ester with a hydroxyl compound under the catalysis of a first catalyst to obtain a first product, and then reacting the first product with a carboxyl compound under the catalysis of a second catalyst to obtain the bio-based plasticizer; wherein:
the epoxy fatty acid ester is one or a combination of several of epoxy fatty acid methyl ester, epoxy fatty acid ethyl ester and epoxy fatty acid butyl ester;
the hydroxyl compound is one or a combination of more of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether and triethylene glycol monobutyl ether;
the first catalyst is one or a combination of more of sodium hydroxide, potassium hydroxide, dibutyltin oxide, potassium carbonate and sodium methoxide;
the carboxyl compound is one or a combination of more of benzoic acid, terephthalic acid, malonic acid, adipic acid, succinic acid, glutaric acid, pimelic acid, suberic acid and azelaic acid;
the second catalyst is one or a combination of more of tetrabutylammonium chloride, tetrabutylammonium bromide, triphenylphosphine and dimethylimidazole.
Preferably, the epoxy value of the epoxidized fatty acid methyl ester is 3 to 6 percent; the epoxy value of the epoxy fatty acid ethyl ester is 2 to 5 percent; the epoxy value of the epoxy fatty acid butyl ester is 3-5%.
Preferably, the molar amount of the hydroxyl compound is 0.5 to 1.5 times of the molar amount of the epoxy in the epoxidized fatty acid ester; the molar weight of the carboxyl compound is 0.3-0.8 times of the molar weight of the epoxy in the first product, and the amount of the first catalyst is 0.1-1% of the mass of the epoxy fatty acid ester; the dosage of the second catalyst is 0.1-1% of the mass of the first product.
Another object of the present invention is to provide a method for preparing the above bio-based plasticizer, comprising the steps of:
step S1: weighing the epoxy fatty acid ester, the hydroxyl compound and the first catalyst in a reaction bottle, heating the epoxy fatty acid ester, the hydroxyl compound and the first catalyst to 130-160 ℃ from 80 ℃ gradually under-0.1 to-0.08 MPa, heating the epoxy fatty acid ester, the hydroxyl compound and the first catalyst to 8-10 ℃ every 1 hour, keeping the temperature at the highest temperature, reacting for 2-4 hours, cooling, washing with water, dehydrating and filtering to obtain a first product;
step S2: and weighing the first product, the carboxyl compound and the second catalyst, placing the first product, the carboxyl compound and the second catalyst in a reaction bottle, reacting for 5-8 hours at the temperature of 90-170 ℃, and measuring the acid value to be lower than 0.5mg KOH/g to obtain the bio-based plasticizer.
Preferably, the molar amount of the hydroxyl compound is 0.5 to 1.5 times of the molar amount of the epoxy in the epoxidized fatty acid ester; the molar weight of the carboxyl compound is 0.3-0.8 times of the molar weight of the epoxy in the first product, and the amount of the first catalyst is 0.1-1% of the mass of the epoxy fatty acid ester; the dosage of the second catalyst is 0.1-1% of the mass of the first product.
The molecular structure of the bio-based plasticizer contains ester groups and benzene rings, and the bio-based plasticizer can interact with polymer molecular chains, so that better compatibility is brought, fatty chains can be inserted among the polymer molecular chains, the mobility of the molecular chains is increased, and the flexibility of the polymer is improved; the higher molecular weight can reduce the volatility, reduce the loss during processing and forming, and simultaneously has better migration resistance, thereby avoiding the precipitation phenomenon in the using process.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments.
1. Preparation examples
Example 1
The method comprises the following steps: weighing 100g of epoxy fatty acid methyl ester (epoxy value is 4 percent), 54g of triethylene glycol monomethyl ether and 0.7g of dibutyltin oxide in a reaction bottle, gradually heating from 80 ℃ to 130 ℃ under-0.1 MPa, heating to 10 ℃ every 1 hour, keeping the temperature of 130 ℃ for reaction for 3 hours, cooling, washing with water, dehydrating and filtering to obtain a product a1;
step two: weighing 100g of the product a1, 15.3g of benzoic acid and 0.2g of tetrabutylammonium chloride, placing the weighed products in a reaction bottle, reacting for 5 hours at 130 ℃, measuring the acid value to be 0.2mg KOH/g, and cooling to obtain the plasticizer 1.
Example 2
The method comprises the following steps: weighing 100g of epoxy fatty acid methyl ester (epoxy value is 4.2%), 67g of triethylene glycol monobutyl ether and 1g of potassium carbonate in a reaction bottle, gradually heating from 80 ℃ to 140 ℃ under-0.1 MPa, heating to 10 ℃ every 1 hour, keeping the temperature to 140 ℃ for reaction for 3 hours, and cooling, washing, dehydrating and filtering to obtain a product a2;
step two: 100g of the product a2, 8.5g of adipic acid and 0.2g of tetrabutylammonium bromide are weighed into a reaction bottle, reacted for 6 hours at 140 ℃, the acid value is measured to be 0.1mg KOH/g, and the plasticizer 2 is obtained after cooling.
Example 3
The method comprises the following steps: weighing 100g of epoxy fatty acid butyl ester (the epoxy value is 3.5 percent), 46.5g of triethylene glycol monomethyl ether and 0.62g of dibutyltin oxide in a reaction bottle, gradually heating from 80 ℃ to 140 ℃ under-0.09 MPa, heating to 10 ℃ every 1 hour, keeping the temperature at 140 ℃ for reaction for 3 hours, cooling, washing with water, dehydrating and filtering to obtain a product a3;
step two: 100g of the product a3, 9.4g of terephthalic acid and 0.2g of triphenylphosphine are weighed in a reaction bottle, reacted for 5 hours at 160 ℃, the acid value is measured to be 0.1mg KOH/g, and the plasticizer 3 is obtained after cooling.
Example 4
The method comprises the following steps: weighing 100g of epoxy fatty acid ethyl ester (epoxy value is 4%), 18g of diethylene glycol and 0.7g of sodium methoxide in a reaction bottle, gradually heating from 80 ℃ to 140 ℃ under-0.1 MPa, heating to 10 ℃ every 1 hour, keeping the temperature at 140 ℃ for reaction for 3 hours, cooling, washing with water, dehydrating and filtering to obtain a product a4;
step two: 100g of the product a4, 18.5.3g of benzoic acid and 0.2g of tetrabutylammonium chloride are weighed in a reaction bottle, reacted for 5 hours at 130 ℃, the acid value is measured to be 0.1mg KOH/g, and the plasticizer 4 is obtained after cooling.
2. Performance verification
1. PVC film fabrication and testing
100 parts of polyvinyl chloride powder, 40 parts of plasticizer and 3 parts of heat stabilizer (1.5 parts of zinc stearate and 1.5 parts of calcium stearate), uniformly stirring at a high speed, mixing for about 6min by a 180 ℃ double-roll open mill, and pressing into a 1mm slice by using a universal sampling machine.
Determination of the mobility the determination was made according to HG/T4459-2012, test conditions: extracting mass change fractions of the sample in water at 60 ℃ for 48 hours; tensile strength and elongation at break were determined according to GB/T1040-2006, test conditions: the specimen is of type II, the stretching rate is 10mm/min and the temperature is 25 ℃.
The performance data for all examples and comparative epoxidized fatty acid methyl esters, dioctyl phthalate are shown in table 1.
As can be seen from the data in table 1, the present invention provides a plasticizer having better migration resistance and elongation at break than epoxidized fatty acid methyl ester and dioctyl phthalate, while maintaining excellent tensile strength.
Table 1 test data for PVC films
2. Manufacture of PVC gloves
100 parts of polyvinyl chloride powder, 60 parts of plasticizer and 3 parts of heat stabilizer (1.5 parts of zinc stearate and 1.5 parts of calcium stearate), uniformly stirring at a high speed, defoaming in vacuum, immersing a hand mould in the mixture, taking out the hand mould, rotating the hand mould to enable the materials to be uniform, placing the hand mould with the uniformly-adhered materials at 220 ℃ for baking, and curing and forming.
Tensile strength and elongation at break were determined according to GB/T1040-2006, test conditions: the sample strip type is II, the stretching speed is 10mm/min, and the temperature is 25 ℃; stability is sensory test, test method: the glove is placed at room temperature for 6 months, and the phenomenon of oil bleeding is sensed by touching the hand; the heat loss test method comprises the following steps: the plasticizer was left to bake at 220 ℃ for 10min and the mass loss percentage was calculated.
The performance data for all examples and comparative examples of PVC gloves made with epoxidized fatty acid methyl ester and octyl phthalate are shown in Table 2.
The data in the table 2 show that the plasticizer provided by the invention is used for manufacturing PVC gloves, and compared with epoxy fatty acid methyl ester, the plasticizer has better mechanical property and stability and less loss in hot processing; compared with dioctyl phthalate, the composite material has higher elongation at break and similar tensile strength.
TABLE 2 PVC gloves test data
Claims (5)
1. A bio-based plasticizer is characterized by being prepared from the following raw materials: reacting epoxy fatty acid ester with a hydroxyl compound under the catalysis of a first catalyst to obtain a first product, and then reacting the first product with a carboxyl compound under the catalysis of a second catalyst to obtain the bio-based plasticizer; wherein:
the epoxy fatty acid ester is one or a combination of several of epoxy fatty acid methyl ester, epoxy fatty acid ethyl ester and epoxy fatty acid butyl ester;
the hydroxyl compound is one or a combination of more of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether and triethylene glycol monobutyl ether;
the first catalyst is one or a combination of more of sodium hydroxide, potassium hydroxide, dibutyltin oxide, potassium carbonate and sodium methoxide;
the carboxyl compound is one or a combination of more of benzoic acid, terephthalic acid, malonic acid, adipic acid, succinic acid, glutaric acid, pimelic acid, suberic acid and azelaic acid;
the second catalyst is one or a combination of more of tetrabutylammonium chloride, tetrabutylammonium bromide, triphenylphosphine and dimethyl imidazole.
2. The bio-based plasticizer according to claim 1, wherein said epoxidized fatty acid methyl ester epoxy value is 3% to 6%; the epoxy value of the epoxy fatty acid ethyl ester is 2 to 5 percent; the epoxy value of the epoxy fatty acid butyl ester is 3-5%.
3. The biobased plasticizer of claim 1, wherein a molar amount of said hydroxy compound is 0.5 to 1.5 times a molar amount of epoxy in said epoxidized fatty acid ester; the molar weight of the carboxyl compound is 0.3-0.8 times of the molar weight of the epoxy in the first product, and the amount of the first catalyst is 0.1-1% of the mass of the epoxy fatty acid ester; the dosage of the second catalyst is 0.1-1% of the mass of the first product.
4. A method of preparing a bio-based plasticizer according to claim 1, 2 or 3, comprising the steps of:
step S1: weighing the epoxy fatty acid ester, the hydroxyl compound and the first catalyst in a reaction bottle, heating the epoxy fatty acid ester, the hydroxyl compound and the first catalyst to 130-160 ℃ from 80 ℃ gradually under-0.1 to-0.08 MPa, heating the epoxy fatty acid ester, the hydroxyl compound and the first catalyst to 8-10 ℃ every 1 hour, keeping the temperature at the highest temperature, reacting for 2-4 hours, cooling, washing with water, dehydrating and filtering to obtain a first product;
step S2: weighing the first product, the carboxyl compound and the second catalyst, placing the first product, the carboxyl compound and the second catalyst in a reaction bottle, reacting for 5-8 hours at 90-170 ℃, and measuring the acid value to be lower than 0.5mg KOH/g to obtain the bio-based plasticizer.
5. The method of preparing a bio-based plasticizer according to claim 4, wherein the molar amount of said hydroxy compound is 0.5 to 1.5 times the molar amount of epoxy in said epoxidized fatty acid ester; the molar weight of the carboxyl compound is 0.3-0.8 times of the molar weight of the epoxy in the first product, and the amount of the first catalyst is 0.1-1% of the mass of the epoxy fatty acid ester; the dosage of the second catalyst is 0.1-1% of the mass of the first product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211359679.4A CN115594590A (en) | 2022-11-02 | 2022-11-02 | Bio-based plasticizer and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211359679.4A CN115594590A (en) | 2022-11-02 | 2022-11-02 | Bio-based plasticizer and preparation method thereof |
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| Publication Number | Publication Date |
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| CN115594590A true CN115594590A (en) | 2023-01-13 |
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| CN202211359679.4A Pending CN115594590A (en) | 2022-11-02 | 2022-11-02 | Bio-based plasticizer and preparation method thereof |
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| CN (1) | CN115594590A (en) |
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- 2022-11-02 CN CN202211359679.4A patent/CN115594590A/en active Pending
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