CN114394896A - Glyceryl ester plasticizer, preparation method thereof and nontoxic environment-friendly polyvinyl chloride - Google Patents
Glyceryl ester plasticizer, preparation method thereof and nontoxic environment-friendly polyvinyl chloride Download PDFInfo
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- CN114394896A CN114394896A CN202210051887.1A CN202210051887A CN114394896A CN 114394896 A CN114394896 A CN 114394896A CN 202210051887 A CN202210051887 A CN 202210051887A CN 114394896 A CN114394896 A CN 114394896A
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- glyceryl ester
- ester plasticizer
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- polyvinyl chloride
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 119
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 90
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 90
- 125000005908 glyceryl ester group Chemical group 0.000 title claims abstract description 72
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 20
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 78
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 14
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 claims description 11
- UAXOELSVPTZZQG-UHFFFAOYSA-N tiglic acid Natural products CC(C)=C(C)C(O)=O UAXOELSVPTZZQG-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 238000013508 migration Methods 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 239000008031 plastic plasticizer Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 30
- VLPFTAMPNXLGLX-UHFFFAOYSA-N trioctanoin Chemical compound CCCCCCCC(=O)OCC(OC(=O)CCCCCCC)COC(=O)CCCCCCC VLPFTAMPNXLGLX-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 22
- 235000011187 glycerol Nutrition 0.000 description 22
- -1 glycerol tri (2-methylbutyric acid) ester Chemical class 0.000 description 19
- 239000007983 Tris buffer Substances 0.000 description 18
- 229940093609 tricaprylin Drugs 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- WLAMNBDJUVNPJU-UHFFFAOYSA-M 2-methylbutyrate Chemical compound CCC(C)C([O-])=O WLAMNBDJUVNPJU-UHFFFAOYSA-M 0.000 description 11
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 10
- DGSZGZSCHSQXFV-UHFFFAOYSA-N 2,3-bis(2-ethylhexanoyloxy)propyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(OC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DGSZGZSCHSQXFV-UHFFFAOYSA-N 0.000 description 8
- 230000036541 health Effects 0.000 description 7
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 125000005456 glyceride group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000008029 phthalate plasticizer Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- OLEWRQVKIUHEJP-UHFFFAOYSA-N methyl 3-hydroxy-2-phenylpropanoate Chemical compound COC(=O)C(CO)C1=CC=CC=C1 OLEWRQVKIUHEJP-UHFFFAOYSA-N 0.000 description 4
- 239000012454 non-polar solvent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- HZGMZSCMYSGJTL-UHFFFAOYSA-N 2,3-bis(3-methylbutanoyloxy)propyl 3-methylbutanoate Chemical compound CC(C)CC(=O)OCC(OC(=O)CC(C)C)COC(=O)CC(C)C HZGMZSCMYSGJTL-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 2
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940093633 tricaprin Drugs 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- COPFWAGBXIWZNK-UHFFFAOYSA-N 2,3-bis(6-methylheptanoyloxy)propyl 6-methylheptanoate Chemical compound CC(C)CCCCC(=O)OCC(OC(=O)CCCCC(C)C)COC(=O)CCCCC(C)C COPFWAGBXIWZNK-UHFFFAOYSA-N 0.000 description 1
- IKYNLTMLACBIBG-UHFFFAOYSA-N 2,3-dihydroxypropyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OCC(O)CO IKYNLTMLACBIBG-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- 206010074268 Reproductive toxicity Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 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
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 230000002452 interceptive effect Effects 0.000 description 1
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- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/30—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with trihydroxylic compounds
-
- 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
Abstract
The application relates to the technical field of plastic plasticizers, in particular to a glyceryl ester plasticizer, a preparation method thereof and nontoxic environment-friendly polyvinyl chloride. The glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 19-21 parts of glycerol, 70-145 parts of monobasic acid, 3.5-8.5 parts of cyclohexane and 0.18-0.90 part of tetra-n-butyl titanate. The preparation method comprises the following steps: (1) preparing: preparing raw materials; (2) esterification reaction: mixing the raw materials and heating for the second time; (3) and (3) post-treatment: deacidifying and drying. The glyceryl ester plasticizer disclosed by the application has the effects of protecting environment, being non-toxic and improving the mechanical property and migration resistance of polyvinyl chloride.
Description
Technical Field
The application relates to the technical field of plastic plasticizers, in particular to a glyceryl ester plasticizer, a preparation method thereof and nontoxic environment-friendly polyvinyl chloride.
Background
The plasticizer is an indispensable fine chemical additive for producing high-quality plastics, and is one of the plastic additives with the largest yield and consumption in the world. The plasticizer has the advantages of reducing the glass transition temperature of the high polymer material and improving the plasticity of the material, so the plasticizer is widely applied to the fields of plastics and rubber products, medical materials, building materials and the like.
At present, the plasticizer consumed in China is about 500 million tons every year, wherein 72 percent of the plasticizer used in the polyvinyl chloride products is phthalate plasticizer. However, because the anti-migration performance of the phthalate plasticizer is poor, the phthalate plasticizer is easy to migrate out of the PVC matrix, and the migrated phthalate plasticizer can be used as a secretion interfering substance to poison the liver, heart, kidney, lung, testis and other organs of the human body, so that the health of people is influenced.
Disclosure of Invention
In order to reduce the influence of the plasticizer on the health of people, the application provides the glyceryl ester plasticizer, the preparation method thereof and the nontoxic environment-friendly plasticizer.
In a first aspect, the present application provides a glyceryl ester plasticizer, which adopts the following technical scheme:
the glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 19-21 parts of glycerol, 70-145 parts of monobasic acid, 3.5-8.5 parts of cyclohexane and 0.18-0.90 part of tetra-n-butyl titanate.
By adopting the technical scheme, the glycerol (1,2, 3-glycerol) contains three hydroxyl groups, so that the glycerol can be subjected to esterification reaction with acid to obtain the glyceryl ester plasticizer, the glyceryl ester plasticizer can be used as a plasticizer to be applied to PVC and other plastics, and the glycerol is colorless, odorless, nontoxic and sweet sticky liquid, so that the glyceryl ester plasticizer prepared from the glycerol also has the advantages of environmental protection and no toxicity, and the influence of the plasticizer on the health of people is effectively reduced.
In addition, the glyceryl ester plasticizer also has the advantages of small migration, high temperature resistance and extraction resistance, so that the glyceryl ester plasticizer is difficult to migrate out of the PVC matrix, and the influence of the plasticizer on the health of people is further reduced. In addition, the glyceryl ester plasticizer also has the effect of improving the mechanical property of PVC, so that the use strength and the service life of PVC are effectively prolonged.
Preferably, the monoacid is one or a mixture of several of capric acid, caprylic acid, 2-ethylhexanoic acid, isooctanoic acid, valeric acid, isovaleric acid and 2-methylbutyric acid.
Through adopting above-mentioned technical scheme, compare with o-benzene class plasticizer, the branching degree of glyceryl ester class plasticizer is higher, simultaneously the staff can also control the carbon chain length with the sour of hydroxyl reaction on the glycerine molecule, when selecting the unit acid that carbon chain length lies in between 5-10, the interaction force between glyceryl ester class plasticizer that the reaction obtained and the PVC is stronger, and is better with the compatibility between the PVC, thereby reduce the possibility that glyceryl ester class plasticizer shifts from the PVC base member and goes out, and effectively increase glyceryl ester class plasticizer to the promotion effect of PVC mechanical properties.
Preferably, the monobasic acid is 2-methylbutyric acid.
By adopting the technical scheme, when the unit acid is 2-methylbutyric acid, the 2-methylbutyric acid and glycerol are subjected to esterification reaction to obtain the glycerol tri (2-methylbutyric acid) ester plasticizer, and the glycerol tri (2-methylbutyric acid) ester plasticizer has a branched chain, so that compared with the plasticizer with a linear chain structure, the plasticizer with the branched chain structure has better extraction resistance, the possibility that the plasticizer migrates from the PVC matrix is reduced, and the influence of the plasticizer on the health of people is effectively reduced.
Preferably, the feed is prepared from the following raw materials in parts by weight: 19.983 parts of glycerol, 71.492 parts of 2-methylbutyric acid, 5.537 parts of cyclohexane and 0.274 part of tetra-n-butyl titanate.
By adopting the technical scheme, when the glycerin, the 2-methylbutyric acid, the cyclohexane and the tetrabutyl titanate are subjected to esterification reaction according to the weight ratio, three hydroxyl groups contained in the glycerin can be more simply and stably reacted with the 2-methylbutyric acid, the preparation difficulty of the glycerin tri (2-methylbutyric acid) ester plasticizer is effectively reduced, and the yield of the glycerin tri (2-methylbutyric acid) ester plasticizer is improved.
Preferably, the monobasic acid is 2-ethylhexanoic acid.
By adopting the technical scheme, when the unit acid is 2-ethylhexanoic acid, the 2-ethylhexanoic acid is esterified with glycerol to obtain the glycerol tri (2-ethylhexanoic acid) ester plasticizer, and the glycerol tri (2-ethylhexanoic acid) ester plasticizer has a branched chain and has higher tensile strength compared with the plasticizer with a linear chain structure. In addition, compared with the o-benzene plasticizer, the glycerol tri (2-ethyl hexanoate) plasticizer also has better elongation at break, so that the glycerol tri (2-ethyl hexanoate) plasticizer has the effects of improving the strength and flexibility of PVC and indirectly improving the service life of PVC.
Preferably, the feed is prepared from the following raw materials in parts by weight: 19.983 parts of glycerol, 140.224 parts of 2-ethylhexanoic acid, 5.537 parts of cyclohexane and 0.481 parts of tetra-n-butyl titanate.
By adopting the technical scheme, when the glycerin, the 2-ethylhexanoic acid, the cyclohexane and the tetra-n-butyl titanate are subjected to esterification reaction according to the weight ratio, three hydroxyl groups contained in the glycerin can be more simply and stably reacted with the 2-ethylhexanoic acid, the preparation difficulty of the triglyceride (2-ethylhexanoic acid) ester plasticizer is effectively reduced, and the yield of the triglyceride (2-ethylhexanoic acid) ester plasticizer is increased.
In a second aspect, the present application provides a method for preparing a glyceryl ester plasticizer, which adopts the following technical scheme: a method for preparing a glyceryl ester plasticizer comprises the following steps:
(1) preparing: adding glycerol, monoacid and cyclohexane into a three-neck flask, then assembling a condenser and a water separator on the three-neck flask, and adding a proper amount of cyclohexane into the water separator;
(2) esterification reaction: stirring and mixing glycerol, monoacid and cyclohexane, heating, adding tetra-n-butyl titanate when the temperature is raised to 130-plus-150 ℃, continuing to raise the temperature to 170-plus-190 ℃ for constant-temperature reaction, and stopping the reaction when the reaction is carried out until no water is generated in the water separator to obtain a crude glyceryl ester plasticizer;
(3) and (3) post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding sodium hydroxide solution into the glyceryl ester plasticizer, and then performing deacidification reaction at the temperature of 35-50 ℃ for 30-45 min; then, the glyceryl ester plasticizer was washed to neutrality by adding a saturated saline solution, and finally dried and centrifuged to remove water and cyclohexane in the glyceryl ester plasticizer, thereby obtaining the glyceryl ester plasticizer.
By adopting the technical scheme, in the step (1), because a proper amount of cyclohexane is added into the water separator, the cyclohexane in the water separator and water generated by the esterification reaction can form a low-boiling-point azeotrope in the process of preparing the glyceryl ester plasticizer, so that the low-boiling-point azeotrope of the water and the cyclohexane is gradually evaporated and condensed in the water separator in the reaction process, and the water is continuously positioned at the lower layer due to the oil-water separation, thereby achieving the effect of water separation and water carrying.
In addition, because a large amount of water is generated when glycerin is esterified with monobasic acid, tetra-n-butyl titanate is very soluble in water, thereby affecting the catalytic effect of tetra-n-butyl titanate. In the step (2), the tetra-n-butyl titanate is added after the temperature is raised to 130-150 ℃ and then raised to 170-190 ℃, so that the influence of water on the tetra-n-butyl titanate is effectively reduced, and the preparation efficiency of the glyceryl ester plasticizer is indirectly improved.
And the glyceryl ester plasticizer is deacidified after the esterification reaction, so that the purity of the glyceryl ester plasticizer is effectively improved, and the plasticizing effect of the glyceryl ester plasticizer is indirectly improved.
In a third aspect, the present application provides a nontoxic and environment-friendly polyvinyl chloride, which adopts the following technical scheme:
the nontoxic environment-friendly polyvinyl chloride is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin powder and 40-60 parts of glyceryl ester plasticizer.
By adopting the technical scheme, when the glyceryl ester plasticizer is adopted in the polyvinyl chloride resin powder, the glyceryl ester plasticizer has the advantages of small migration, high temperature resistance and extraction resistance, so that the glyceryl ester plasticizer is difficult to migrate out of a PVC matrix, and the influence of the plasticizer on the health of people is further reduced.
A preparation method of nontoxic environment-friendly polyvinyl chloride comprises the following steps:
firstly, adding polyvinyl chloride resin powder and a glyceryl ester plasticizer into a tetrahydrofuran solvent, and then uniformly mixing and stirring until the mixture is transparent and clear to obtain a raw material mixture;
and secondly, standing the raw material mixture for 2-4 days, then keeping the temperature at 30-50 ℃ for 3-5 days, and taking out the mixture after the solvent is completely volatilized to obtain the nontoxic environment-friendly polyvinyl chloride.
By adopting the technical scheme, the preparation method has fewer steps and is simple to operate, so that the operation difficulty of preparing the nontoxic environment-friendly polyvinyl chloride is effectively reduced, and the yield of the nontoxic environment-friendly polyvinyl chloride is indirectly improved.
In summary, the present application has the following beneficial effects:
1. the glyceryl ester plasticizer prepared from the glycerol has the advantages of environmental protection and no toxicity, so that the influence of the plasticizer on the health of people is effectively reduced.
2. Part of the glyceryl ester plasticizer also has the advantages of low migration, high temperature resistance and extraction resistance, so that the possibility of the glyceryl ester plasticizer migrating from the PVC matrix is effectively reduced, and the glyceryl ester plasticizer has certain reproductive toxicity and potential carcinogenic risk to human bodies, so that if the glyceryl ester plasticizer is difficult to migrate from the PVC matrix, the glyceryl ester plasticizer has relatively small harm to the human bodies, and can be further suitable for some higher-end plastic products.
3. The glyceryl ester plasticizer also has the effect of improving the mechanical property of PVC, so that the use strength of PVC is effectively prolonged, and the glyceryl ester plasticizer has the potential capability of replacing the traditional PVC plasticizer formula which mainly comprises the phthalate plasticizer; in addition, the glyceryl ester plasticizer also has the effect of improving the plasticity of PVC, so that the processing requirements of various plastic products can be met, and the glyceryl ester plasticizer is further suitable for different occasions.
Drawings
FIG. 1 is an infrared spectrum of glyceryl ester plasticizers of examples 1-7;
FIG. 2 is a graph showing mechanical properties of application examples 1 to 4 and application comparative example 1;
FIG. 3 is a TG spectrum of application examples 1 to 4 and application comparative example 1;
FIG. 4 is a DSC spectra of application examples 1 to 4 and application comparative example 1;
FIG. 5 is a graph showing migration resistance of application examples 1 to 4 and application comparative example 1.
Detailed Description
The present application will be described in further detail below with reference to the drawings, examples, comparative examples, application examples, and application comparative examples.
Raw materials
The raw material components in the application are shown in a table 1:
TABLE 1 sources of the raw material components
Examples
Example 1
A glyceryl ester plasticizer is prepared by the following steps:
(1) preparing: 0.217mol (92.09g/mol × 0.217mol ═ 19.983g) of glycerol, 0.7mol (172.26g/mol × 0.7mol ═ 120.582g) of decanoic acid were charged into a three-necked flask, 5ml of cyclohexane (5ml × 0.791g/ml ═ 3.955g) were subsequently added to the three-necked flask as a water-carrying agent, after which a serpentine condenser and a water separator were fitted to the three-necked flask and 2ml of cyclohexane were added to the water separator (2ml × 0.791g/ml ═ 1.582 g);
(2) esterification reaction: continuously stirring glycerin, capric acid and cyclohexane at a stirring speed of 400r/min by magnetic force, gradually heating, adding tetra-n-butyl titanate (19.983g +120.582 g). times.0.3% ═ 0.422g) with the total mass of 0.3% when the temperature is raised to 140 ℃, continuously heating to 180 ℃ for constant-temperature reaction, measuring the acid value of the reaction liquid in the reaction process, observing the progress of the esterification reaction, and stopping the reaction when the reaction is carried out until no water is generated in a water separator to obtain crude glycerol tricaprate;
(3) and (3) post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding 15 wt% sodium hydroxide solution into the glyceryl ester plasticizer, and then performing deacidification reaction at the temperature of 45 ℃ for 40 min; then, the glyceryl ester plasticizer is washed to be neutral by adding saturated saline solution, cyclohexane and residual water are removed by using a rotary evaporator, anhydrous sodium sulfate is added for drying, and finally, the glycerol tricaprate is obtained by centrifugation;
in (3), the change of the acid value in the plasticizer synthesis process is measured with reference to the standard GB/T1668-; and because of experimental error, three parallel tests are carried out during each measurement, and the average value is taken as the final acid value.
Example 2
The difference from example 1 was that 0.7mol of capric acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of caprylic acid (144.21g/mol × 0.7mol ═ 100.947g), and the amount of tetra-n-butyl titanate added was ((19.983g +100.947g) × 0.3%: 0.363g), to obtain a glycerol tricaprylate plasticizer.
Example 3
The difference from example 1 was that 0.7mol of decanoic acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of 2-ethylhexanoic acid (200.32g/mol × 0.7mol ═ 140.224g), and the amount of tetra-n-butyl titanate added was ((19.983g +140.224g) × 0.3% ═ 0.481g), to obtain a glycerol tris (2-ethylhexanoic acid) ester plasticizer.
Example 4
The difference from example 1 was that 0.7mol of decanoic acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of isooctanoic acid (144.204g/mol × 0.7mol ═ 100.943g), and the amount of tetra-n-butyl titanate added was ((19.983g +100.943g) × 0.3%: 0.363g), to obtain a glycerol triisooctanoate plasticizer.
Example 5
The difference from example 1 was that 0.7mol of decanoic acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of pentanoic acid (102.1317g/mol × 0.7mol ═ 71.492g), and the amount of tetra-n-butyl titanate added was ((19.983g +71.492g) × 0.3%: 0.274g), to give a glycerol pivalate plasticizer.
Example 6
The difference from example 1 was that 0.7mol of decanoic acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of isovaleric acid (102.1243g/mol × 0.7mol ═ 71.487g), and the amount of tetra-n-butyl titanate added was ((19.983g +71.487g) × 0.3%: 0.274g), to obtain a glycerol triisovalerate plasticizer.
Example 7
A difference from example 1 was that 0.7mol of decanoic acid (172.26g/mol × 0.7mol ═ 120.582g) was replaced with 0.7mol of 2-methylbutyric acid (102.1317g/mol × 0.7mol ═ 71.492g), and the amount of tetra-n-butyl titanate added was ((19.983g +71.492g) × 0.3%: 0.274g), to obtain a glycerol tris (2-methylbutyric acid) ester plasticizer.
Application examples
Application example 1
The preparation method of the nontoxic environment-friendly polyvinyl chloride comprises the following steps:
firstly, adding 12g of polyvinyl chloride resin powder and 6g of example 2 into 150ml (150ml × 0.88g/ml ═ 132g) of tetrahydrofuran solvent, and then uniformly mixing and stirring at a stirring speed of 400r/min until the mixture is transparent and clear to obtain a raw material mixture;
and secondly, pouring the raw material mixture into a culture dish with the diameter of 15cm, standing for 3 days at room temperature, then placing the culture dish in a constant-temperature drying oven with the temperature of 40 ℃ for 4 days, and taking out the culture dish after the solvent is completely volatilized to obtain the glycerol tricaprylate plasticized nontoxic environment-friendly polyvinyl chloride.
Application examples 2 to 4
The difference from application example 1 is that example 1 was replaced with examples 3, 5, and 7 having the same weight.
Comparative application
Application comparative example 1
The difference from application example 1 was that example 1 was replaced with DOP of the same weight.
Performance test
Detection method
First, Infrared Spectroscopy test
Three samples were taken from examples 1-7 and comparative example 1, respectively, followed by total reflection Fourier Infrared Spectroscopy (FT-IR), scanning 32 times, resolution set at 4cm-1The scanning range is set to 500-4000cm-1And finally obtaining an infrared spectrogram, which is specifically shown in figure 1.
Test II, tensile Property test
With reference to ISO 527-5-2009, determination of tensile Properties of plastics, three samples were taken from application examples 1-4 and application comparative example 1 and prepared as test pieces having a length of 10mm, a width of 2mm and a thickness of 1mm, and then the above samples were subjected to a tensile strength test and an elongation at break test (tensile rate of 50mm/min) and averaged, as shown in FIG. 2 and Table 3.
Wherein, the Young's modulus is calculated according to the formula (1-1)
E=σ/ε (1-1)
Wherein E represents the Young's modulus of the sample in Pa; σ represents the tensile strength of the sample in Pa; ε represents the elongation at break of the sample in%.
Test III, thermal stability test
Thermogravimetric (TG) analysis: 10mg of samples were taken from application examples 1 to 4 and application comparative example 1, and the thermal stability of the samples was tested and TG spectra and thermogravimetric analysis tables were obtained under nitrogen atmosphere at a nitrogen flow rate of 50mL/min and a temperature rise rate of 20 ℃/min from 50 ℃ to 600 ℃, as shown in FIGS. 3 and 4.
Differential Scanning Calorimeter (DSC) analysis: in nitrogen atmosphere, 8mg of sample is taken for testing, the heating rate is 10 ℃/min, the testing temperature range is-20-120 ℃, the thermal stability of the sample is tested, and a DSC spectrogram is obtained, which is shown in figure 4.
Test four, migration resistance test
Volatility resistance test: the volatility resistance of the samples was tested by means of activated carbon, according to ISO 176-. The specific operation is as follows:
samples were taken from application examples 1 to 4 and application comparative example 1, cut into several square pieces of 30mm × 30mm × 1mm in specification, dried in a desiccator for 6h, and the mass of the sample (to the nearest 0.0001g) was weighed as m0(ii) a Then taking a 50ml ceramic crucible, putting a proper amount of activated carbon powder in the crucible, putting the weighed sample into activated carbon to enable the sample to be completely embedded by the activated carbon, putting the sample into a constant-temperature drying oven at 100 ℃, taking out the sample every 20min, wiping the activated carbon on the surface of the sample by using filter paper, and accurately weighing the mass of the sample by using an analytical balance to be recorded as m.
To reduce the effect of error, each sample was tested in triplicate and the average was taken as the final result, as shown in figure 5. The volatility resistance of the sample was expressed by the mass loss rate, and the specific results are shown in FIG. 5, and the mass loss rate was calculated by the following equation (1-2):
wherein eta is1Represents the mobility loss rate in%; m is0Representing the mass of the sample before the experiment, and the unit is g; m represents the post-test mass of the sample in g.
And (3) testing extraction resistance: referring to ISO 175-2011 Experimental method for measuring the immersion effect of plastic-liquid chemicals, a sample is tested by distilled water, a polar solvent anhydrous ethanol and a non-polar solvent petroleum ether, and the specific operations are as follows:
samples were taken from application examples 1 to 4 and application comparative example 1, cut into several square pieces of 30mm × 30mm × 1mm in specification, placed in a desiccator and dried for 6h, and then the mass of the sample was accurately weighed with an analytical balance, and recorded as W0(ii) a And then immersing the sample in a 50ml ground conical flask containing the solution with the same volume, placing the conical flask in a constant temperature box at 30 ℃, taking out the sample every 20min, wiping the solvent on the surface of the sample by using filter paper, then putting the sample in an oven at 40 ℃, drying the sample, taking out the dried sample, cooling the sample to room temperature, and weighing the mass of the sample as W.
In order to reduce the experimental operation error, the mass loss rate of each sample is tested three times, and finally, the average value is taken as the final result, the specific result is shown in fig. 5, and the mass loss rate of the sample is calculated according to the formula (1-3):
wherein eta is2Represents the mobility loss rate in%; w0Represents the mass of the sample before soaking, and the unit is g; w represents the mass of the sample after soaking in g.
And (3) detection results: the results of the tests of application examples 1 to 4 and application comparative example 1 are shown in Table 3.
TABLE 3 tables of test results of application examples 1 to 4 and application comparative example 1
TABLE 4 thermogravimetric data of application examples 1 to 4 and application comparative example 1
(Ti、T10%And T50%The corresponding temperature of 5%, 10% and 50% mass loss of the PVC test piece respectively
As can be seen by combining examples 1 to 7 and comparative example 1 with FIG. 1, the glyceryl ester plasticizers glyceryl tricaprylate, glyceryl tri (2-ethylhexanoate), glyceryl triisocaprylate, glyceryl tripentalate, glyceryl tri (2-methylbutyrate) and glyceryl triisovalerate and glyceryl tricaprate were present at 3500cm-1There is no broad peak of hydroxyl (-OH), indicating that 3 (-OH) on glycerol have undergone esterification reaction and esterification reaction is complete.
In addition, the glyceryl ester plasticizers glycerol tricaprylate, glycerol tri (2-ethylhexanoate), glycerol triisocaprylate, glycerol tri valerate, glycerol tri (2-methylbutyrate) and glycerol tri valerate and glycerol tri caprate were added at 1728cm-1The peak is obvious expansion vibration peak of C ═ O, which indicates the existence of ester group, which indicates that the reaction in the preparation process of the plasticizer is thorough, and 7 glyceryl ester plasticizers are successfully synthesized and have better purity.
In combination with application examples 1-4 and application comparative example 1, and in combination with fig. 2 and table 3, it can be seen that elongation at break of the polyvinyl chloride test piece plasticized by glycerol tricaprylate, glycerol trioleate, glycerol tris (2-ethylhexanoate) and glycerol tris (2-methylbutyrate) is improved compared with that of the PVC test piece plasticized by DOP, wherein the elongation at break of the polyvinyl chloride test piece plasticized by glycerol tricaprylate and glycerol tricaprylate is improved to a greater extent, thereby demonstrating that the flexibility of nontoxic environmentally friendly polyvinyl chloride can be effectively improved by glycerol tricaprylate and glycerol tricaprylate with linear structures.
Compared with the PVC test piece plasticized by the glycerol tri-valerate with a straight chain structure, the PVC test piece plasticized by the glycerol tri (2-methylbutyrate) with a branched chain structure has reduced tensile strength and elongation at break.
Compared with the PVC test piece plasticized by glycerol tricaprylate with a straight chain structure, the PVC test piece plasticized by glycerol tri (2-ethyl hexanoate) with a branched chain structure has slightly higher tensile strength, but the elongation at break is obviously reduced.
However, compared with the poly (vinyl chloride) test piece plasticized by DOP, the poly (vinyl chloride) test pieces plasticized by glycerol tricaprylate, glycerol trioleate and glycerol tris (2-methylbutyrate) ester have relatively lower tensile strength, the poly (vinyl chloride) test piece plasticized by glycerol tris (2-ethylhexanoate) ester has relatively higher tensile strength, and the poly (vinyl chloride) test piece plasticized by glycerol tris (2-ethylhexanoate) ester has higher elongation at break than the poly (vinyl chloride) plasticized by DOP, thereby showing that the effect of improving the overall mechanical property of the nontoxic environment-friendly poly (vinyl chloride) by glycerol tris (2-ethylhexanoate) ester is more excellent.
As can be seen by combining application examples 1 to 4, application comparative example 2 and FIG. 3, polyvinyl chloride plasticized by tricaprylin, tris (2-ethylhexanoate) and tris (2-methylbutyrate) glyceride had no mass loss at 100 ℃ and thus it was demonstrated that tetrahydrofuran had completely volatilized during the preparation of polyvinyl chloride plasticized by tricaprylin, tris (2-ethylhexanoate) and tris (2-methylbutyrate) glyceride.
Referring to fig. 3 and table 4, it can be seen that there are two major thermal weight loss stages in application examples 1-4 and application comparative example 2, and the thermal weight loss in stage I (110-. Wherein the mass loss rate of the polyvinyl chloride plasticized by DOP, tricaprylin, tris (2-ethylhexanoate) glycerolate and tris (2-methylbutyrate) glycerolate is between 75 and 76 percent.
The reason for the thermal weight loss in the stage II (390 ℃ C. and 550 ℃ C.) is the structural reformation of polyvinyl chloride macromolecules and the breakage of carbon skeletons. In the stage, the mass loss rate of the polyvinyl chloride plasticized by the glycerol tri (2-methylbutyrate) ester is 16.4%, and the mass loss rate of the polyvinyl chloride test piece plasticized by other plasticizers is between 18% and 19%.
However, in general, polyvinyl chloride plasticized with tricaprylin has more excellent thermal stability than polyvinyl chloride plasticized with DOP, because tricaprylin has a slightly larger relative molecular mass than DOP, and tricaprylin has a linear structure, has a higher boiling point, has better compatibility with polyvinyl chloride, is more difficult to migrate from polyvinyl chloride, and thus exhibits better thermal stability.
As can be seen by combining the use examples 1 to 4 and the use comparative example 2 with FIG. 4, the glass transition temperatures of polyvinyl chloride plasticized with DOP, tricaprylin, tris (2-ethylhexanoate) and tris (2-methylbutyrate) are substantially the same and are all around 53.3 ℃. The glass transition temperature is one of the weight indexes for measuring the plasticizing effect of the plasticizer, and the lower the glass transition temperature, the better the plasticizing effect of the plasticizer, thereby showing that DOP, tricaprylin, triglycolate, tris (2-ethylhexanoate) and tris (2-methylbutyrate) are basically the same in plasticizing effect on PVC.
As can be seen by combining the application examples 1 to 4 and the application comparative example 2 with FIG. 5, the mass loss rates of polyvinyl chloride plasticized by DOP, tricaprylin, triglycolate, tris (2-ethylhexanoate) and tris (2-methylbutyrate) glyceride were all 0.5% or less in distilled water, and substantially no migration occurred, thereby indicating that polyvinyl chloride plasticized by DOP, tricaprylin, triglycolate, tris (2-ethylhexanoate) and tris (2-methylbutyrate) glyceride maintained good stability in distilled water.
In polar solvent absolute ethyl alcohol, the mass loss rate of polyvinyl chloride plasticized by DOP, tricaprylin, tri (2-ethyl hexanoate) and tri (2-methyl butyrate) is below 5%. Among them, the mass loss rate of polyvinyl chloride plasticized by glycerol tri (2-ethylhexanoate) and glycerol tri (2-methylbutyrate) ester having a branched structure is relatively low, even lower than that of polyvinyl chloride plasticized by DOP, compared to polyvinyl chloride plasticized by glycerol tricaprylate and glycerol tri-valerate having a linear structure, thereby demonstrating that the branched structure can improve the stability improvement effect of plasticizer on polyvinyl chloride in a polar solvent.
In the non-polar solvent petroleum ether, the mass loss rate of polyvinyl chloride plasticized by tricaprylin and tris (2-ethylhexanoate) glycerolate was significantly greater than that of polyvinyl chloride plasticized by tricaprylin and tris (2-methylbutyrate) glycerolate.
Compared with polyvinyl chloride plasticized by tricaprylin and tricaprylin, the mass loss rate of the polyvinyl chloride plasticized by the tricaprin and the tricaprin is relatively lower, so that the branched chain structure can improve the stability improvement effect of the plasticizer on the polyvinyl chloride in a non-polar solvent, and the polyvinyl chloride plasticized by the plasticizer with smaller molecular weight has better stability under the condition that the molecular structure of the plasticizer is similar.
Further, the mass loss rate of polyvinyl chloride plasticized with glycerol tris (2-methylbutyrate) ester in a polar solution or a nonpolar solvent was even smaller than that of polyvinyl chloride plasticized with DOP, thereby showing that polyvinyl chloride plasticized with glycerol tris (2-methylbutyrate) ester had more excellent pull-out resistance.
In the activated carbon, the mass loss rate of polyvinyl chloride plasticized by tricaprylin and tris (2-ethylhexanoate) glyceride was relatively smaller than that of polyvinyl chloride plasticized by tricaprylin and tris (2-methylbutyrate). Whereas the mass loss rate of polyvinyl chloride plasticized by glyceryl tricaprylate is relatively smaller compared to polyvinyl chloride plasticized by glyceryl tri (2-ethylhexanoate).
Therefore, in the activated carbon, the branched chain structure can improve the stability improvement effect of the plasticizer on the polyvinyl chloride, and the polyvinyl chloride plasticized by the plasticizer with larger molecular weight has more excellent stability under the condition that the molecular structure of the plasticizer is similar.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The glyceryl ester plasticizer is characterized by being prepared from the following raw materials in parts by weight: 19-21 parts of glycerol, 70-145 parts of monobasic acid, 3.5-8.5 parts of cyclohexane and 0.18-0.90 part of tetra-n-butyl titanate.
2. The glyceryl ester plasticizer according to claim 1, wherein: the monoacid is one or a mixture of several of capric acid, caprylic acid, 2-ethylhexanoic acid, isooctanoic acid, valeric acid, isovaleric acid and 2-methylbutyric acid.
3. The glyceryl ester plasticizer according to claim 2, wherein: the monobasic acid is 2-methylbutyric acid.
4. The glyceryl ester plasticizer according to claim 3, wherein the glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 19.983 parts of glycerol, 71.492 parts of 2-methylbutyric acid, 5.537 parts of cyclohexane and 0.274 part of tetra-n-butyl titanate.
5. The glyceryl ester plasticizer according to claim 2, wherein: the monobasic acid is 2-ethylhexanoic acid.
6. The glyceryl ester plasticizer according to claim 5, wherein the glyceryl ester plasticizer is prepared from the following raw materials in parts by weight: 19.983 parts of glycerol, 140.224 parts of 2-ethylhexanoic acid, 5.537 parts of cyclohexane and 0.481 parts of tetra-n-butyl titanate.
7. A process for the preparation of glyceryl ester plasticizers according to any one of claims 1 to 6 comprising the steps of:
(1) preparing: adding glycerol, monoacid and cyclohexane into a three-neck flask, then assembling a condenser and a water separator on the three-neck flask, and adding a proper amount of cyclohexane into the water separator;
(2) esterification reaction: stirring and mixing glycerol, monoacid and cyclohexane, heating, adding tetra-n-butyl titanate when the temperature is raised to 130-plus-150 ℃, continuing to raise the temperature to 170-plus-190 ℃ for constant-temperature reaction, and stopping the reaction when the reaction is carried out until no water is generated in the water separator to obtain a crude glyceryl ester plasticizer;
(3) and (3) post-treatment: when the acid value of the crude glyceryl ester plasticizer is too high, firstly adding sodium hydroxide solution into the glyceryl ester plasticizer, and then performing deacidification reaction at the temperature of 35-50 ℃ for 30-45 min; then, the glyceryl ester plasticizer was washed to neutrality by adding a saturated saline solution, and finally dried and centrifuged to remove water and cyclohexane in the glyceryl ester plasticizer, thereby obtaining the glyceryl ester plasticizer.
8. The nontoxic environment-friendly polyvinyl chloride is characterized by being prepared from the following raw materials in parts by weight: 100 parts of a polyvinyl chloride resin powder and 40 to 60 parts of a glyceryl ester plasticizer according to any one of claims 1 to 6.
9. The nontoxic environment-friendly polyvinyl chloride according to claim 8, characterized in that the preparation method comprises the following steps:
firstly, adding polyvinyl chloride resin powder and the glyceryl ester plasticizer as defined in any one of claims 1 to 6 into a tetrahydrofuran solvent, and then uniformly mixing and stirring until the mixture is transparent and clear to obtain a raw material mixture;
and secondly, standing the raw material mixture for 2-4 days, then keeping the temperature at 30-50 ℃ for 3-5 days, and taking out the mixture after the solvent is completely volatilized to obtain the nontoxic environment-friendly polyvinyl chloride.
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