CN112759792A - Epoxy plasticizer and preparation method thereof - Google Patents
Epoxy plasticizer and preparation method thereof Download PDFInfo
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- CN112759792A CN112759792A CN202110153859.6A CN202110153859A CN112759792A CN 112759792 A CN112759792 A CN 112759792A CN 202110153859 A CN202110153859 A CN 202110153859A CN 112759792 A CN112759792 A CN 112759792A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 60
- 239000004014 plasticizer Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 187
- 238000002156 mixing Methods 0.000 claims abstract description 73
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 54
- 239000003549 soybean oil Substances 0.000 claims abstract description 54
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 47
- 239000000194 fatty acid Substances 0.000 claims abstract description 47
- 229930195729 fatty acid Natural products 0.000 claims abstract description 47
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 47
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- VUSHVKUNOXWQTG-KHPPLWFESA-N methyl (Z)-2-oxooctadec-9-enoate Chemical compound O=C(C(=O)OC)CCCCCC\C=C/CCCCCCCC VUSHVKUNOXWQTG-KHPPLWFESA-N 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000498 ball milling Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 34
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims description 30
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims description 30
- 229940073769 methyl oleate Drugs 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 27
- 235000019698 starch Nutrition 0.000 claims description 27
- 239000008107 starch Substances 0.000 claims description 27
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000600 sorbitol Substances 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000344 soap Substances 0.000 claims description 16
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000006735 epoxidation reaction Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 10
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000007670 refining Methods 0.000 claims description 10
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 10
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000004135 Bone phosphate Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 abstract description 3
- 239000008158 vegetable oil Substances 0.000 abstract description 3
- 208000005623 Carcinogenesis Diseases 0.000 abstract description 2
- 230000036952 cancer formation Effects 0.000 abstract description 2
- 231100000504 carcinogenesis Toxicity 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012760 heat stabilizer Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008035 bio-based plasticizer Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention discloses an epoxy plasticizer and a preparation method thereof, and the epoxy plasticizer comprises a first component, a second component and an additive, wherein the first component comprises epoxy fatty acid triglyceride, epoxy methyl oleate and modified sorbitol; the second component comprises epoxidized soybean oil and modified citric acid; the additive comprises the following components: the cost can be reduced by mixing epoxidized soybean oil with epoxidized fatty acid triglyceride and the like, the effect of the plasticizer is improved by adding the modified citric acid and the modified sorbitol, the problems that the existing epoxy plasticizer uses natural vegetable oil as a production raw material, such as soybean oil, the price is high, and other raw materials are used for some plasticizers, the price is low, but the toxicity is enhanced, the environment is not protected enough, and the carcinogenesis is possible in serious cases are solved, and the catalyst is added in the preparation process, so that the reaction time is shortened.
Description
Technical Field
The invention relates to a plasticizer, in particular to an epoxy plasticizer and a preparation method thereof.
Background
Plasticizers are generally "solvent-like" substances which, when added to plastics, resins or elastomers, improve their processability, increase their plasticity, flexibility, stretchability or expandability. The addition of plasticizers reduces the melt viscosity of the plastic, the glass transition temperature and the elastic modulus of the elastomer without altering the basic chemical characteristics of the plasticized material.
Currently, the epoxy plasticizer mainly takes epoxidized soybean oil as a main raw material, and the epoxidized soybean oil is a bio-based plasticizer prepared by taking soybean oil as a raw material through epoxy modification, and is widely applied to PVC non-toxic products. In addition, the epoxidized soybean oil can also be used as an auxiliary heat stabilizer of PVC, and can generate a synergistic effect with a metal salt heat stabilizer to play a heat stabilizing effect and reduce the dosage of an expensive organic metal salt heat stabilizer.
However, the existing epoxy plasticizer needs oxidation reaction during preparation, the reaction time is long, the preparation time is long, natural vegetable oil is used as a production raw material of the existing epoxy plasticizer, such as soybean oil, the price is high, other raw materials are used as some plasticizers, the price is low, but the toxicity is enhanced, the environment is not protected, and the existing epoxy plasticizer can possibly cause cancer seriously.
Disclosure of Invention
The invention aims to provide an epoxy plasticizer and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
an epoxy plasticizer comprises a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 30-50 parts of epoxy fatty acid triglyceride, 10-20 parts of epoxy methyl oleate and 5-10 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 30-50 parts of epoxidized soybean oil and 3-9 parts of modified citric acid;
the additive comprises the following components in parts by weight: 10-20 parts of tribasic lead sulfate.
As a further scheme of the invention: the epoxy plasticizer comprises a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 35-45 parts of epoxy fatty acid triglyceride, 12-18 parts of epoxy methyl oleate and 6-9 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 35-45 parts of epoxidized soybean oil and 4-8 parts of modified citric acid;
the additive comprises the following components in parts by weight: 12-18 parts of lead sulfate tribasic.
As a still further scheme of the invention: the epoxy plasticizer comprises a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 40 parts of epoxy fatty acid triglyceride, 15 parts of epoxy methyl oleate and 8 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 40 parts of epoxidized soybean oil and 6 parts of modified citric acid;
the additive comprises the following components in parts by weight: 15 parts of tribasic lead sulfate.
As a still further scheme of the invention: the preparation method of the epoxy plasticizer comprises the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water, and the citric acid and the glycerol are taken to prepare modified citric acid;
s2, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s3, preparing modified sorbitol by taking sorbitol, polyethylene, sodium hydroxide and deionized water;
s4: preparing a first component: taking fatty acid triglyceride, methyl oleate and modified sorbitol according to the weight ratio, mixing the fatty acid triglyceride, the methyl oleate and the modified sorbitol, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s5: mixing the first composition and the second composition, adding tribasic lead sulfate, stirring uniformly, cooling and standing.
As a still further scheme of the invention: the preparation method of the modified citric acid comprises the following steps: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain the modified citric acid.
As a still further scheme of the invention: the preparation method of the modified sorbitol comprises the following steps: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; and putting the powder into a muffle furnace, raising the temperature at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving the heat for 1-2 hours.
As a still further scheme of the invention: the catalyst comprises the components of dodecyl trimethyl ammonium chloride, p-methyl benzene sulfonic acid, magnesium sulfate, sodium bisulfate and a stabilizer.
As a still further scheme of the invention: the stabilizer is one or more of zinc soap stabilizer, tin soap stabilizer, calcium soap stabilizer and barium soap stabilizer.
Compared with the prior art, the invention has the beneficial effects that:
according to the epoxy plasticizer and the preparation method thereof, the epoxidized soybean oil and the epoxidized fatty acid triglyceride are mixed, so that the cost can be reduced, the modified citric acid and the modified sorbitol are added, the effect of the plasticizer is improved, the problems that the existing epoxy plasticizer uses natural vegetable oil as a production raw material, such as soybean oil, the price is high, some plasticizers use other raw materials, the price is low, but the toxicity is enhanced, the environment is not protected, and the possibility of carcinogenesis is high in case of serious conditions are solved, and the catalyst is added in the preparation process, so that the reaction time is shortened.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 40 parts by weight of epoxidized soybean oil and 6 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 40 parts by weight of epoxy fatty acid triglyceride, 15 parts by weight of epoxy methyl oleate and 8 parts by weight of modified sorbitol, and standing for later use;
s8, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Example 2
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 30 parts by weight of epoxidized soybean oil and 3 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 30 parts by weight of epoxy fatty acid triglyceride, 10 parts by weight of epoxy methyl oleate and 5 parts by weight of modified sorbitol, and standing for later use;
s8, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Example 3
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 50 parts by weight of epoxidized soybean oil and 9 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 50 parts by weight of epoxy fatty acid triglyceride, 20 parts by weight of epoxy methyl oleate and 10 parts by weight of modified sorbitol, and standing for later use;
s8, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Example 4
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 35 parts by weight of epoxidized soybean oil and 4 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 35 parts by weight of epoxy fatty acid triglyceride, 12 parts by weight of epoxy methyl oleate and 6 parts by weight of modified sorbitol, and standing for later use;
s8, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Example 5
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 45 parts by weight of epoxidized soybean oil and 8 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 45 parts by weight of epoxy fatty acid triglyceride, 18 parts by weight of epoxy methyl oleate and 9 parts by weight of modified sorbitol, and standing for later use;
s8, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Comparative example 1
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2, preparing a second component: carrying out glycerolysis reaction on glycerol and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the reaction liquid and formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s3, taking 40 parts by weight of epoxidized soybean oil and 6 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s4, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s5, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s6, mixing and stirring 40 parts by weight of epoxy fatty acid triglyceride, 15 parts by weight of epoxy methyl oleate and 8 parts by weight of modified sorbitol, and standing for later use;
s7, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Comparative example 2
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, fatty acid triglyceride, methyl oleate;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 40 parts by weight of epoxidized soybean oil and 6 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s6, mixing and stirring 40 parts by weight of epoxy fatty acid triglyceride, 15 parts by weight of epoxy methyl oleate and 8 parts by weight of modified sorbitol, and standing for later use;
s7, mixing the first composition and the second composition according to the parts by weight, adding 15 parts by weight of tribasic lead sulfate, stirring uniformly, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
Comparative example 3
An epoxy plasticizer and a preparation method thereof, comprising the following steps:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water;
s2: preparing modified citric acid: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain modified citric acid;
s3, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s4, taking 40 parts by weight of epoxidized soybean oil and 6 parts by weight of modified citric acid, stirring and mixing, and standing for later use;
s5, preparing modified sorbitol: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; putting the powder into a muffle furnace, heating at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving heat for 1-2 hours;
s6, preparing a first component: taking fatty acid triglyceride and methyl oleate according to the weight ratio, mixing the fatty acid triglyceride and the methyl oleate, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s7, mixing and stirring 40 parts by weight of epoxy fatty acid triglyceride, 15 parts by weight of epoxy methyl oleate and 8 parts by weight of modified sorbitol, and standing for later use;
and S8, mixing the first composition and the second composition according to the parts by weight, uniformly stirring, cooling and standing.
Specifically, the catalyst consists of dodecyl trimethyl ammonium chloride, p-toluenesulfonic acid, magnesium sulfate, sodium bisulfate and zinc soap stabilizer.
The following compatibility tests were carried out after compounding the plasticizers of each example and comparative example with PVC, respectively:
| epoxy value (%) | Acid value (mgKOH/g) | Specific gravity of | Iodine number (g/100 g) | |
| Example 1 | 0.85 | 13.5 | 0.976 | 31 |
| Example 2 | 0.76 | 11.2 | 0.954 | 28 |
| Example 3 | 0.78 | 12.6 | 0.941 | 27 |
| Example 4 | 0.71 | 10.7 | 0.957 | 25 |
| Example 5 | 0.73 | 11.1 | 0.966 | 27 |
| Comparative example 1 | 0.51 | 7.6 | 0.928 | 11 |
| Comparative example 2 | 0.46 | 5.9 | 0.931 | 13 |
| Comparative example 3 | 0.58 | 8.1 | 0.910 | 15 |
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (8)
1. An epoxy plasticizer, which is characterized by comprising a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 30-50 parts of epoxy fatty acid triglyceride, 10-20 parts of epoxy methyl oleate and 5-10 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 30-50 parts of epoxidized soybean oil and 3-9 parts of modified citric acid;
the additive comprises the following components in parts by weight: 10-20 parts of tribasic lead sulfate.
2. The epoxy-based plasticizer according to claim 1, comprising a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 35-45 parts of epoxy fatty acid triglyceride, 12-18 parts of epoxy methyl oleate and 6-9 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 35-45 parts of epoxidized soybean oil and 4-8 parts of modified citric acid;
the additive comprises the following components in parts by weight: 12-18 parts of lead sulfate tribasic.
3. The epoxy-based plasticizer according to claim 1, comprising a first component, a second component and an additive,
the first component comprises the following components in parts by weight: 40 parts of epoxy fatty acid triglyceride, 15 parts of epoxy methyl oleate and 8 parts of modified sorbitol;
the second component comprises the following components in parts by weight: 40 parts of epoxidized soybean oil and 6 parts of modified citric acid;
the additive comprises the following components in parts by weight: 15 parts of tribasic lead sulfate.
4. A method for preparing the epoxy plasticizer according to any one of claims 1 to 3, comprising the steps of:
s1, preparing raw materials, wherein the raw materials comprise: citric acid, soybean oil, glycerol, sorbitol, polyethylene, fatty acid triglyceride, methyl oleate, sodium hydroxide and deionized water, and the citric acid and the glycerol are taken to prepare modified citric acid;
s2, preparing a second component: carrying out glycerolysis reaction on modified citric acid and soybean oil under the catalysis of alkali, after the reaction is finished, carrying out flash evaporation on reaction liquid, filtering, washing with water, carrying out reduced pressure distillation to remove water, taking out, adding a catalyst, carrying out epoxidation reaction on the obtained product with formic acid and hydrogen peroxide to obtain a crude product, and refining to obtain epoxidized soybean oil;
s3, preparing modified sorbitol by taking sorbitol, polyethylene, sodium hydroxide and deionized water;
s4: preparing a first component: taking fatty acid triglyceride, methyl oleate and modified sorbitol according to the weight ratio, mixing the fatty acid triglyceride, the methyl oleate and the modified sorbitol, uniformly stirring, adding a catalyst, and introducing ozone in a sealed environment until the epoxy value reaches the requirement, thus completing the preparation;
s5: mixing the first composition and the second composition, adding tribasic lead sulfate, stirring uniformly, cooling and standing.
5. The method for preparing the epoxy plasticizer according to claim 4, wherein the method for preparing the modified citric acid comprises the following steps: preparing a citric acid aqueous solution, adding starch into the citric acid aqueous solution to react for a period of time to obtain citric acid starch, mixing, adding glycerol into the citric acid starch mixed solution, stirring and mixing, performing microwave treatment, heating at 150 ℃ for 20min, standing and cooling to obtain the modified citric acid.
6. The method for preparing the epoxy plasticizer according to claim 4, wherein the method for preparing the modified sorbitol comprises the following steps: according to the weight ratio of 7: 10 weighing a certain amount of sorbitol and polyvinyl alcohol, putting into a ball milling tank for ball milling, and crushing the raw materials; adding sodium hydroxide and deionized water into a ball milling tank for mixing, and ball milling for 30-60 min after mixing to obtain white powder; and putting the powder into a muffle furnace, raising the temperature at a constant speed for heat treatment, wherein the heat treatment temperature is 550-600 ℃, and preserving the heat for 1-2 hours.
7. The method for preparing the epoxy plasticizer according to claim 4, wherein the catalyst comprises the components of dodecyl trimethyl ammonium chloride, p-methyl benzene sulfonic acid, magnesium sulfate, sodium bisulfate and a stabilizer.
8. The method for preparing the epoxy plasticizer according to claim 7, wherein the stabilizer is one or more of a zinc soap stabilizer, a tin soap stabilizer, a calcium soap stabilizer and a barium soap stabilizer.
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