CN113121877A - Plasticizer and preparation method thereof - Google Patents
Plasticizer and preparation method thereof Download PDFInfo
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- CN113121877A CN113121877A CN201911424123.7A CN201911424123A CN113121877A CN 113121877 A CN113121877 A CN 113121877A CN 201911424123 A CN201911424123 A CN 201911424123A CN 113121877 A CN113121877 A CN 113121877A
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- methyl ester
- plasticizer
- epoxy
- acid methyl
- fatty acid
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 43
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 28
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 150000004702 methyl esters Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000002285 corn oil Substances 0.000 claims description 4
- 235000005687 corn oil Nutrition 0.000 claims description 4
- 235000012343 cottonseed oil Nutrition 0.000 claims description 4
- 239000002385 cottonseed oil Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- IMYZYCNQZDBZBQ-SJORKVTESA-N (9S,10R)-epoxyoctadecanoic acid Chemical compound CCCCCCCC[C@H]1O[C@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-SJORKVTESA-N 0.000 claims 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims 1
- QYDYPVFESGNLHU-KHPPLWFESA-N Methyl oleate Natural products CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 claims 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 claims 1
- WTTJVINHCBCLGX-NQLNTKRDSA-N methyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OC WTTJVINHCBCLGX-NQLNTKRDSA-N 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 21
- 230000005012 migration Effects 0.000 abstract description 21
- -1 phthalate ester Chemical class 0.000 description 14
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 14
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000006735 epoxidation reaction Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 2
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 2
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 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 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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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
-
- 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
- C07C69/73—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 unsaturated acids
- C07C69/734—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to a plasticizer and a preparation method thereof, wherein the plasticizer comprises at least one of compounds shown in a formula (I). The invention also provides a preparation method of the plasticizer, which comprises the steps of mixing the sodium phenolate, the epoxy fatty acid methyl ester and the polyethylene glycol, reacting at room temperature, washing with water after the reaction is finished, and performing rotary evaporation to obtain a plasticizer product. The plasticizer provided by the invention can effectively inhibit the migration of the plasticizer and has excellent plasticizing performance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a plasticizer and a preparation method thereof.
Background
Plasticizers are additives for polymer materials, also known as plasticizers, which are widely used in industrial production. The use of the plasticizer can improve the performance of the high polymer material, reduce the production cost and improve the production benefit. The phthalate ester is generally applied to materials such as plastic products, concrete, mud ash, cement, gypsum, cosmetics, cleaning agents and the like as an auxiliary agent, particularly polyvinyl chloride plastic products, and phthalate ester is required to be added in order to increase the plasticity of the plastic and improve the strength of the plastic, and the content of the phthalate ester can reach 50% of the product. The plasticizer mainly has the effects of weakening the secondary valence bonds among resin molecules, increasing the mobility of the molecular bonds of the resin, reducing the crystallinity of the resin molecules, increasing the plasticity of the resin molecules and enhancing the flexibility of the resin molecules.
At present, thousands of plasticizers are developed and produced, the applications of the plasticizers are more 300-400, and the number of plasticizers produced in China is about 100-110. At present, the o-benzene plasticizer is used in the market in the largest amount, but the o-benzene plasticizer has the problems of health hazard, environmental pollution and the like and has potential carcinogenic risk, and related regulatory laws are set by many countries to limit the production and use of the o-benzene plasticizer.
The epoxy fatty acid methyl ester is a novel environment-friendly plasticizer and can effectively replace dioctyl phthalate (DOP), dibutyl phthalate (DBP) and the like as the plasticizer. The epoxy fatty acid methyl ester has good compatibility, low volatility and good stabilizing effect on light and heat. However, researches find that in the process of processing and using the PVC product added with the epoxy fatty acid methyl ester plasticizer, the plasticizer can migrate and diffuse into a contact medium, so that the phenomena of oil bleeding, yellowing and the like of the PVC product occur, the quality of the PVC product is reduced, and the service performance of the PVC product is influenced.
Jia Mao Lin et al (modified swill-cooked dirty oil for preparing epoxy fatty acid methyl ester plasticizer [ J ] for PVC]China plastics 2014, 28(11): 82-87) takes illegal cooking oil as a raw material, adopts a stepwise methyl esterification and acid catalysis-epoxidation method to prepare the epoxidized fatty acid methyl ester plasticizer, and characterizes the chemical structure and the performance of the product. The results showed that the product was 839.2cm-1The characteristic peak of epoxy group appears; the content of unsaturated fatty acid methyl ester in the raw material after epoxidation reaction is obviously reduced, and simultaneouslyEpoxy fatty acid methyl ester is generated; the epoxidation degree of the product increased gradually with increasing epoxidation time, reaching a maximum of 3.9% at 8h and a corresponding decrease in iodine value from 87.7g to 8.7 g. Compared with dioctyl phthalate (DOP), the flash point of the epoxy fatty acid methyl ester plasticizer is higher than 197 ℃, the plasticizer efficiency is similar to that of PVC resin, and 50 percent of the plasticizer can reduce the glass transition temperature of PVC from 87 ℃ to-10 ℃, but the migration resistance is lower than that of DOP.
Wang Fang et al (preparation and performance research of epoxy oleic acid diester plasticizer, Chinese leather 2017 (10)) aims at the problem that the traditional epoxy fatty acid methyl ester plasticizer is not resistant to migration, takes oleic acid, ethylene glycol and acetic anhydride as raw materials, synthesizes an epoxy oleic acid diester plasticizer by adopting a step-by-step esterification and acid catalytic epoxidation method, characterizes the compatibility, plasticizing efficiency, migration resistance and the like of the epoxy oleic acid diester plasticizer with polyvinyl chloride resin, and compares the epoxy oleic acid diester plasticizer with the traditional epoxy fatty acid methyl ester (with similar epoxy value) and dioctyl phthalate. The results show that: the epoxy oleic acid diester plasticizer has good plasticizing performance, the migration resistance of the epoxy oleic acid diester plasticizer is improved to a certain extent compared with the traditional epoxy fatty acid methyl ester, and the epoxy oleic acid diester plasticizer has reference value for development of novel environment-friendly and efficient plasticizers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a plasticizer and a preparation method thereof. The plasticizer provided by the invention can effectively inhibit the migration of the plasticizer and has excellent plasticizing performance.
The invention provides a plasticizer, which comprises at least one of compounds shown as a formula (I):
wherein R is1-R5Is H, or R1、R2、R3、R4Is H, R5Is methoxy, or R2、R3、R4Is H, R1、R5Is methoxy;
r and R' are C1-C8R and R' are the same or different; preferably, R is C5Straight chain alkyl group of (1), C8A linear alkyl or linear monoalkenyl group of (a); r' is C10Linear monoalkenyl or C7The linear alkyl group of (1); more preferably, R is C5The linear alkyl radical of (1), R' is C10The linear monoalkenyl group of (1); r is C8R' is C7The linear alkyl group of (1); r is C8The linear alkyl radical of (1), R' is C7Linear alkyl group of (1).
The invention also provides a preparation method of the plasticizer, which comprises the following steps: mixing sodium phenolate, epoxy fatty acid methyl ester and polyethylene glycol, reacting at room temperature, washing with water after the reaction is finished, and performing rotary evaporation to obtain the plasticizer.
In the method, the sodium phenolate is any one or more of sodium phenolate, sodium phenolate with more than one substituent group on a benzene ring, and the like, and preferably at least one ortho position of-OH is substituted by methoxy.
In the method of the invention, the epoxy fatty acid methyl ester is at least one of epoxy vegetable oil methyl ester with the sum of the contents of epoxy methyl oleate and epoxy methyl linoleate higher than 65%, specifically at least one of epoxy soybean oil methyl ester, epoxy corn oil methyl ester, epoxy cottonseed oil methyl ester and the like.
In the method, the mass ratio of the sodium phenolate to the epoxy fatty acid methyl ester is 1:1-5, preferably 1: 2-4.
In the method of the present invention, the polyethylene glycol is selected from low molecular weight polyethylene glycol, such as at least one of PEG200, PEG400, PEG600, etc., preferably PEG 400. The dosage of the polyethylene glycol accounts for 10-40% of the mass of the epoxy fatty acid methyl ester.
In the method, the reaction is carried out at the speed of 100-300r/min, and the reaction time is 1-5 h.
The plasticizer is prepared by modifying epoxy fatty acid methyl ester with sodium phenolate and polyethylene glycol. The prepared plasticizer can be used in the processing process of PVC resin, PLA resin and epoxy resin products with the plasticizer content higher than 10%. Compared with the epoxy fatty acid methyl ester plasticizer, the migration resistance is improved, and the migration rate is reduced to below 1 percent.
Aiming at the problem of poor migration resistance of the epoxy fatty acid methyl ester plasticizer, the inventor finds that after the epoxy fatty acid methyl ester plasticizer and sodium phenolate or sodium phenolate with more than one methoxyl substituent group at the ortho position of benzene ring-OH are subjected to specific ring-opening reaction, the prepared plasticizer has excellent plasticizing performance, and particularly can obviously improve the migration resistance of the plasticizer. Due to the introduction of methoxy groups and the like on the benzene ring of the sodium phenolate, the migration resistance of the plasticizer is improved, the flash point of the plasticizer is improved, and the plasticizing efficiency is basically not influenced.
Drawings
FIG. 1 is a reaction structure of the plasticizer prepared in example 1;
FIG. 2 is a drawing of epoxidized soybean oil methyl ester1H NMR spectrum;
FIG. 3 shows the compound of example 11H NMR spectrum.
Detailed Description
The following examples are provided to further illustrate the plasticizers of the present invention and the methods and effects of making the same. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
Preparing a PVC plasticized film: 100 parts of PVC, 50 parts of plasticizer, 1.5 parts of calcium stearate and 0.5 part of zinc stearate are mixed, uniformly stirred in a high-speed mixer for 5min, then mixed by a mixing roll at 165 ℃ for 5-10min, and respectively prepared into PVC plasticized films with the thickness of 1mm and 2mm, and stored in a dryer for later use.
In the present invention, the plasticizer mobility, plasticizing efficiency, and flash point are measured as follows: plasticizer mobility determination: the mass change fraction of the sample withdrawn in distilled water was determined according to HG/T4459-2012, at 60 ℃ for 72 h. And (3) measurement of plasticizing efficiency: from the glass transition temperature (T) of the sampleg) Showing that T of the sample was measured according to GB/T19466.2-2004gTaking the inflection point of the measurement as Tg. Flash point: according to GB/T1671-2008, the diameter of the end of the flame nozzle is about 1.6mm, the diameter of the orifice is 0.8mm, the scanning radius is 120mm, and the distance between the scanning surface of the orifice and the cross section of the cup is 2 mm.
Example 1
Adding 116g of sodium phenolate into a reaction kettle, adding 300g of epoxidized soybean oil methyl ester and 60g of polyethylene glycol-400, starting stirring, and reacting at 200r/min for 4 h. And after the reaction is finished, washing and rotary steaming the product at the temperature of 80 ℃ under the pressure of 5hPa for 0.5h to obtain the plasticizer, wherein the structure is shown in the attached figure 1. Wherein R is C5The linear alkyl radical of (1), R' is C10The content of the linear monoalkenyl is 32%; r is C8R' is C733% of linear alkyl groups; r is C8The linear alkyl radical of (1), R' is C7The content of the straight-chain alkyl is 35 percent; r1-R5Is H.
The nuclear magnetic resonance analysis is carried out on the product,1the H NMR spectrum is shown in FIGS. 2 and 3. In the raw material1In the H NMR spectrum, an absorption peak near 3.0ppm is a chemical shift peak of hydrogen on the epoxy bond carbon, and in the plasticizer product, the absorption peak disappears, indicating that the epoxy bond is reacted. Plasticizer product1The absorption peak at 5.4ppm in the H NMR spectrum is the chemical shift peak of hydrogen on-OH, and the absorption peak near 6.9ppm is the chemical shift peak of hydrogen on benzene ring, which indicates that the epoxy bond in the raw material reacts with sodium phenolate to generate a new substance. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 2
The difference from example 1 is that: sodium phenolate with a methoxyl group at the-OH ortho-position on the benzene ring of the sodium phenolate is adopted. Wherein R and R' are the same as in example 1, wherein R1、R2、R3、R4Is H, R5Is methoxy. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 3
The difference from example 1 is that: sodium phenolate with two methoxyl groups at-OH ortho-positions on a benzene ring of the sodium phenolate is adopted. Wherein R and R' are the same as in example 1, wherein R2、R3、R4Is H, R1、R5Is methoxy. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 4
The difference from example 1 is that: the epoxy fatty acid methyl ester is epoxy corn oil methyl ester. Wherein R is C5The linear alkyl radical of (1), R' is C10The content of the linear monoalkenyl is 31 percent; r is C8R' is C7The content of the straight-chain alkyl group is 34%; r is C8The linear alkyl radical of (1), R' is C7The content of the straight-chain alkyl is 35 percent; r1-R5Is H. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 5
The difference from example 1 is that: the epoxy fatty acid methyl ester is epoxy cottonseed oil methyl ester. Wherein R is C5The linear alkyl radical of (1), R' is C10The content of the linear monoalkenyl is 27 percent; r is C8R' is C7The content of the straight-chain alkyl is 36%; r is C8The linear alkyl radical of (1), R' is C7The content of the straight-chain alkyl is 37%; r1-R5Is H. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 6
The difference from example 1 is that: polyethylene glycol PEG200 is used. Wherein R and R' have the same structures and contents as those in example 1, and R1-R5Is H. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Example 7
The difference from example 1 is that: the polyethylene glycol is PEG 600. Wherein R and R' have the same structures and contents as those in example 1, and R1-R5Is H. The flash point, plasticization efficiency and migration resistance of the product were measured, and the results are shown in table 1.
Comparative example 1
The difference from example 1 is that: the epoxy fatty acid methyl ester is epoxy palm oil methyl ester, and the sum of the contents of epoxy methyl oleate and epoxy methyl linoleate is 54%.
Comparative example 2
The difference from example 1 is that: phenol is used to replace sodium phenolate, and hot water at 70 ℃ is used for washing.
Comparative example 3
The difference from example 1 is that: ethylene glycol is used instead of polyethylene glycol.
The products of examples 1 to 7 and comparative examples 1 to 3 were used in combination with epoxidized soybean oil methyl ester, epoxidized corn oil methyl ester and epoxidized cottonseed oil methyl ester, and the methyl ester flash point, plasticizing efficiency and migration resistance were measured to obtain the results shown in Table 1.
TABLE 1 Main Properties of the plasticizers
As can be seen from Table 1, the flash point of the plasticizer prepared by the invention is higher than that of epoxy fatty acid methyl ester, the glass transition temperature is slightly reduced, the migration rate in PVC resin is reduced to below 1%, and the plasticizer has a remarkable migration resistant effect. The method which does not adopt the complete technical scheme of the invention has poor comprehensive performance.
Claims (12)
1. A plasticizer characterized by comprising at least one of the compounds represented by formula (i):
wherein R and R' are C1-C8R and R' are the same or different; r1-R5Is H, or R1、R2、R3、R4Is H, R5Is methoxy, or R2、R3、R4Is H, R1、R5Is methoxy.
2. A plasticizer according to claim 1, characterized in that: r is C5Straight chain alkyl group of (1), C8Straight chain alkyl or C8A linear monoalkenyl group.
3. A plasticizer according to claim 1, characterized in that: r' is C10Linear monoalkenyl or C7Linear alkyl group of (1).
4. A plasticiser according to claim 1, 2 or 3, characterised in that: r is C5The linear alkyl radical of (1), R' is C10The linear monoalkenyl group of (1); r is C8R' is C7The linear alkyl group of (1); r is C8The linear alkyl radical of (1), R' is C7Linear alkyl group of (1).
5. A process for the preparation of the plasticizer according to any of claims 1 to 4, characterized by comprising the following steps: mixing sodium phenolate, epoxy fatty acid methyl ester and polyethylene glycol, reacting at room temperature, washing with water after the reaction is finished, and performing rotary evaporation to obtain the plasticizer.
6. The method of claim 5, wherein: the sodium phenolate is any one or more of sodium phenolate or sodium phenolate with more than one substituent group on a benzene ring, and preferably at least one ortho position of-OH is substituted by methoxy.
7. The method of claim 6, wherein: the epoxy fatty acid methyl ester is at least one of epoxy vegetable oil methyl ester with the sum of the contents of epoxy oleic acid methyl ester and epoxy linoleic acid methyl ester higher than 65%.
8. The production method according to claim 5 or 7, characterized in that: the epoxy fatty acid methyl ester is at least one of epoxy soybean oil methyl ester, epoxy corn oil methyl ester and epoxy cottonseed oil methyl ester.
9. The method of claim 5, wherein: the mass ratio of the sodium phenolate to the epoxidized fatty acid methyl ester is 1:1-5, preferably 1: 2-4.
10. The method of claim 5, wherein: the polyethylene glycol is at least one selected from PEG200, PEG400 and PEG600, preferably PEG 400.
11. The production method according to claim 5 or 10, characterized in that: the dosage of the polyethylene glycol accounts for 10-40% of the mass of the epoxy fatty acid methyl ester.
12. The method of claim 5, wherein: the reaction is carried out at 100-300r/min for 1-5 h.
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| WO2017018741A1 (en) * | 2015-07-24 | 2017-02-02 | 주식회사 엘지화학 | Plasticizer composition, resin composition, and preparation methods therefor |
| CN108101832A (en) * | 2017-10-09 | 2018-06-01 | 河南聚硒农业科技有限公司 | A kind of preparation method of selenium-rich aliphatic ester |
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| WO2017018741A1 (en) * | 2015-07-24 | 2017-02-02 | 주식회사 엘지화학 | Plasticizer composition, resin composition, and preparation methods therefor |
| CN108101832A (en) * | 2017-10-09 | 2018-06-01 | 河南聚硒农业科技有限公司 | A kind of preparation method of selenium-rich aliphatic ester |
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| CN115536820A (en) * | 2022-09-28 | 2022-12-30 | 广东科云诚新材料有限公司 | High-performance environment-friendly polyester plasticizer and preparation method thereof |
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