WO2015039409A1 - 二乙酰环氧油酸甘油酯的合成工艺 - Google Patents
二乙酰环氧油酸甘油酯的合成工艺 Download PDFInfo
- Publication number
- WO2015039409A1 WO2015039409A1 PCT/CN2014/071177 CN2014071177W WO2015039409A1 WO 2015039409 A1 WO2015039409 A1 WO 2015039409A1 CN 2014071177 W CN2014071177 W CN 2014071177W WO 2015039409 A1 WO2015039409 A1 WO 2015039409A1
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- WIPO (PCT)
- Prior art keywords
- acid
- catalyst
- acetylation
- diacetyl
- synthesis process
- Prior art date
Links
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 20
- 239000004593 Epoxy Substances 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 title claims abstract description 12
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 title claims abstract 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 26
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 18
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005642 Oleic acid Substances 0.000 claims abstract description 18
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000021736 acetylation Effects 0.000 claims abstract description 18
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 13
- 235000011187 glycerol Nutrition 0.000 claims abstract description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 12
- -1 diacetyl glyceryl Chemical group 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 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 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 125000005456 glyceride group Chemical group 0.000 claims description 5
- 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 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012346 acetyl chloride Substances 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 abstract description 19
- 239000004033 plastic Substances 0.000 abstract description 15
- 229920003023 plastic Polymers 0.000 abstract description 15
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 abstract 2
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 229930195734 saturated hydrocarbon Natural products 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 235000013305 food Nutrition 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012345 acetylating agent Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YPHMISFOHDHNIV-FSZOTQKASA-N cycloheximide Chemical compound C1[C@@H](C)C[C@H](C)C(=O)[C@@H]1[C@H](O)CC1CC(=O)NC(=O)C1 YPHMISFOHDHNIV-FSZOTQKASA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- FABAOYOFJNAVHB-KVVVOXFISA-N (z)-octadec-9-enoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O FABAOYOFJNAVHB-KVVVOXFISA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UROFTPKQEUJFCY-UHFFFAOYSA-N C1CC[CH-]CC1 Chemical compound C1CC[CH-]CC1 UROFTPKQEUJFCY-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MWVFCEVNXHTDNF-UHFFFAOYSA-N hexane-2,3-dione Chemical compound CCCC(=O)C(C)=O MWVFCEVNXHTDNF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000041 toxicology testing Toxicity 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
Definitions
- the present invention relates to a process for synthesizing diacetyl oleic oleic acid glyceride.
- plasticizers are widely used in toys, building materials, auto parts, electronic and medical parts as a functional product added to high molecular polymers to increase the plasticity of materials, making them easy to process, and imparting softness to products.
- plasticizers are widely used in toys, building materials, auto parts, electronic and medical parts as a functional product added to high molecular polymers to increase the plasticity of materials, making them easy to process, and imparting softness to products.
- durable and easy-to-shape plastic products such as plasma bags and infusion sets, it is the largest capacity and consumption of plastic processing aids.
- plasticizers Its output accounts for about 60% of the total output of plastic additives.
- traditional plasticizers have been dominated by phthalic acid products containing benzene ring structures such as dioctyl phthalate (DOP) and dibutyl phthalate (DBP).
- DOP dioctyl phthalate
- DBP dibutyl phthalate
- plasticizers in the food and pharmaceutical fields.
- plastic products such as medicine and food packaging, daily necessities, and toys have put forward higher requirements for plasticizers.
- It has become a general trend to replace traditional varieties with green and environmentally friendly new plasticizers.
- epoxy plasticizer has gradually become a hot research topic at home and abroad. It mainly includes epoxidized oil and epoxy fatty acid ester. The most important and most common one is epoxidation. Soybean oil, which has good heat resistance, light resistance and low temperature flexibility, low volatility and no toxicity, is one of the most widely used green plasticizers in China.
- Epoxy fatty acid esters have superior lubricity, compatibility and dispersibility in addition to the advantages of epoxidised oils.
- Epoxy fatty acid methyl ester is a non-toxic plasticizer used in the processing of plastics and rubber. It has good compatibility with products, low volatility and migration, in addition to epoxy vegetable oils and fats as plasticizers and stabilizers.
- Epoxy oils have large molecular weight, high viscosity and poor fluidity, but because of their structure containing epoxy groups, they have good thermal stability and compatibility with plastics; triacetin molecules are small, The viscosity is smaller than that of epoxidized oils. Combining the characteristics and properties of their mutual structure, we hope to find a phthalate plasticizer with a similar plasticizing effect to epoxidized oils but low molecular weight and good fluidity.
- a process for synthesizing diacetyl oleic oleic acid glyceride comprises the following steps: a. Esterification reaction: esterification of raw material glycerol and oleic acid under the action of an esterification catalyst The esterification reaction is carried out at 115 to 190 ° C for 1.5 to 4.5 hours to form oleic acid monoglyceride (A);
- acetylation reaction the oleic acid monoglyceride (A) formed in step a and the acetylation reagent are acetylated at 90 ⁇ 160 ° C for 2 to 10 hours under the action of an acetylation catalyst to form diacetyl oil.
- Epoxidation reaction The diacetyl oleic acid glyceride (B) formed in the step b is reacted with hydrogen peroxide under the catalysis of an epoxidation catalyst and a weak acid at 60 to 80 ° C for 2 to 4 hours to form a diacetyl group.
- Epoxy oleic acid glyceride (C) Epoxy oleic acid glyceride
- the weight ratio of glycerin to oleic acid is 1:3.06 ⁇ 3.07.
- the esterification catalyst is any one of concentrated sulfuric acid, concentrated phosphoric acid, potassium hydrogen sulfate, p-toluenesulfonic acid and [emin]BF4 ionic liquid, and the ester is percentage by weight.
- the amount of the catalyst used is 0.01 to 0.04% of the amount of the esterification raw material.
- the acetylating agent is any one of acetyl chloride, glacial acetic acid and acetic anhydride, and the acetylating agent is used in an amount of 40% by weight of the oleic acid monoglyceride. ⁇ 50%.
- the acetylation catalyst is at least one of concentrated sulfuric acid, concentrated phosphoric acid and NaHS (VH 2 0, and the acetylation catalyst is used in an amount of oleic acid monoglycerin per weight percent The amount of the ester is from 0.3 to 0.6%.
- the water-carrying agent is further added to the step b, and the water-carrying agent is at least one of benzene, cycloheximide and hexanquinone, and is, by weight percent,
- the amount of the water-carrying agent is 35 to 40% of the amount of the oleic acid monoglyceride.
- the epoxidation catalyst is concentrated phosphoric acid and/or concentrated sulfuric acid.
- the weak acid is formic acid and/or acetic acid.
- the concentration of hydrogen peroxide is 50%.
- the weight of the diacetyl oleic acid glyceride, the hydrogen peroxide, the weak acid, and the epoxy catalyst is 1: 04 to 0.7: 0.04 to 0.08: 0.001 to 0.003.
- the invention has the beneficial effects that the diacetyl glycerol glyceride obtained by the process of the invention can be applied as a plasticizer to a plastic, which not only has a plasticizing effect similar to that of an epoxidized oil, but also has a molecular weight ratio epoxidized oil. Lower, also good stability, good fluidity, good compatibility with plastics.
- FIG. 1 shows an infrared spectrum of oleic acid monoglyceride (A) described in the present invention
- Figure 2 is a chart showing the infrared spectrum of the diacetyl oleic acid glyceride (B) described in the present invention
- Figure 3 shows an infrared spectrum of the product diacetyl epoxidized glyceride (C) described in the present invention.
- BEST MODE FOR CARRYING OUT THE INVENTION hereinafter, specific embodiments of the present invention will be further described with reference to specific embodiments, but the present invention is not limited to the embodiments described below.
- the invention prepares diacetyl oleic oleic acid glyceride by using oleic acid and glycerin as raw materials, and the synthetic route comprises the following steps: a. Esterification reaction: esterification raw material glycerol and oleic acid esterification reaction at 115 ⁇ 190 ° C 1.5 ⁇ 4.5 hours to form oleic acid monoglyceride (A);
- acetylation reaction the oleic acid monoglyceride (A) formed in step a and acetylation reagent acetylation reaction at 90 ⁇ 160 ° C for 2 to 10 hours to form diacetyl oleate (B); Acetylation
- Epoxidation reaction The diacetyl oleic acid glyceride (B) formed in the step b is reacted with hydrogen peroxide under the action of a catalyst at 60 to 80 ° C for 2 to 4 hours to form diacetyl oleic oleic acid glyceride. (C);
- step a the weight ratio of the esterified raw material glycerin to oleic acid is 1:3.06 ⁇ 3.07; the esterification catalyst is concentrated sulfuric acid, concentrated phosphoric acid, potassium hydrogen sulfate, p-toluenesulfonic acid and [emin] BF4 ionic liquid, and by weight
- the acetylating reagent is any one of acetyl chloride, glacial acetic acid and acetic anhydride, and the acetylating agent is used in an amount of 40% by weight of the oleic acid monoglyceride (A).
- the acetylation catalyst is at least one of concentrated sulfuric acid, concentrated phosphoric acid and NaHS (VH 2 0, and the amount thereof is 0.3-0.6% by weight of the oleic acid monoglyceride (A);
- a water-carrying agent is further added, and the water-carrying agent is at least one of benzene, cyclohexanide and hexanyl, and the amount thereof is oleic acid monoglyceride (A).
- the epoxidation catalyst is concentrated phosphoric acid and/or concentrated sulfuric acid;
- the weak acid is formic acid and/or acetic acid, and diacetyl oleic acid glyceride (B), hydrogen peroxide, weak acid,
- the weight ratio of the epoxy catalyst is 1: 04 to 0.7: 0.04 to 0.08: 0.001 to 0.003.
- Example 1 Preparation of diacetyl epoxidic acid glyceride using oleic acid and glycerin as raw materials, including the following preparation steps: a, esterification reaction: 754g oleic acid, 246g glycerol, sequentially added to a three-neck round bottom bottle with a stirring device, thermometer, reflux water condensation tube, nitrogen gas and stirring temperature, when the temperature reaches 120 ° C Adding 0.2 g of concentrated phosphoric acid catalyst, and esterification reaction at 190 ° C for 3 hours, and then vacuuming for 25 hours until the acid value reaches 3 or less to complete the reaction, thereby obtaining oleic acid monoglyceride; infrared test of oleic acid monoglyceride The results of (IR(KBr)) are shown in Fig.
- epoxidation reaction in a four-necked bottle equipped with a stirring device, a thermometer, a dropping funnel, and a reflux condenser, 500 g of diacetyl oleic acid glyceride obtained in step b, 30 g of 80 to 85% formic acid, The catalyst concentrated 0.7 g of sulfuric acid, and the temperature was raised to 65 ° C. 250 g of 50% hydrogen peroxide was slowly added dropwise with stirring, and then the temperature was raised to 80 ° C. The epoxidation reaction was carried out for 4 hours to separate the lower layer of acid water, and the upper layer of the oil ester was successively treated with alkali water.
- Washed to neutral when the acid value is below 0.6, the water is removed by distillation under reduced pressure and filtered to obtain a light yellow oil of diacetyl epoxidized glyceryl ester having an epoxy value of 3.0 and an acid value of 1.2.
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Abstract
本发明公开了一种二乙酰环氧油酸甘油酯的合成工艺，包括以下步骤：a、酯化反应：酯化原料甘油与油酸在酯化催化剂作用下于115～190℃下酯化反应1.5～4.5小时，生成油酸单甘油酯，b、乙酰化反应：油酸单甘油酯与乙酰化试剂在在乙酰化催化剂的作用下于 90～160℃下乙酰化反应2～10小时，生成二乙酰油酸甘油酯；c、环氧化反应：二乙酰油酸甘油酯与双氧水在环氧化催化剂及弱酸催化作用下，于60～80℃下反应2～4小时，生成二乙酰环氧油酸甘油酯。制得的二乙酰环氧甘油酯作为增塑剂应用到具有塑料中，具有稳定性好、流动性好、与塑料的相溶性好的优点。
Description
二乙酰环氧油酸甘油酯的合成工艺
技术领域 本发明涉及一种二乙酰环氧油酸甘油酯的合成工艺。 背景技术 近年来塑料产业飞速发展， 拉动了增塑剂等塑料助剂行业以年均 10.9%的速度增长。 增塑剂作为一种添加到高分子聚合物中用以增加材料塑性， 使之易加工， 赋予制品柔软性 的功能性产品， 被广泛应用于玩具、 建筑材料、 汽车配件、 电子与医疗部件如血浆袋、 成 套输液器等大量耐用并且易造型的塑料制品中， 是塑料加工助剂中产能和消费量最大的品 种， 其产量约占塑料助剂总产量的 60%， 是塑料助剂中最大的品种之一。 目前， 全球增塑 剂品种多达 200多种， 每个品种均有各自的物理和化学性能， 应用领域也各不相同。 长期以来， 传统增塑剂一直以邻苯二甲酸二辛酯 （DOP) 、 邻苯二甲酸二丁酯 （DBP) 等含苯环结构的邻苯类产品为主体。 随着这类增塑剂在食品、 医药工业上的应用越来越广 泛， 人们对它的毒性研究也越来越重视。 在生活中， 食物在加工、 加热、 包装、 盛装的过 程中可能会造成塑料制品中的邻苯二甲酸酯的溶出并渗入食物中， 从而对人体存在潜在的 毒性， 因此部分国家已经禁止或限制此类增塑剂在食品、 医药领域的使用。 近年来， 随着 各国环保意识的提高， 医药及食品包装、 日用品、 玩具等塑料制品对增塑剂提出了更高的 要求， 以绿色、 环保的增塑剂新品替代传统品种已成大势所趋。 环氧类增塑剂作为无毒环 保型增塑剂逐渐成为国内外应用研究的热点， 其主要包括环氧油和环氧脂肪酸酯两大类， 其中最重要最常见的就是环氧化大豆油， 它具有良好的耐热性、 耐光性和低温柔韧性， 且 挥发度低， 没有毒性， 是我国应用最为广泛的绿色增塑剂之一。但环氧化大豆油与 PVC 的 相容性有限， 用量大时 （超过 15%) 会从制品中渗出， 当用做稳定剂时， 高温时会发生色 变， 影响制品质量， 因此只能作为辅助增塑剂和辅助稳定剂， 而不能做 PVC 的主增塑剂使 用。 环氧脂肪酸酯除具有环氧油的优点外还具有更优的润滑性、 相容性和分散性。 如环氧 脂肪酸甲酯是一种用于塑料和橡胶加工中的无毒增塑剂， 除具环氧植物油脂作为增塑剂及 稳定剂时与产品相容性好、 挥发性低、 迁移性小、 制品韧性优良、 无毒、 对光和热稳定性 好等优点夕卜，更具优越的润滑性、相容性和分散性，在 PVC制品加工时添加量可达 10%-30%。
有文献报道： 单硬脂酸双乙酰甘油酯 （Fully acetylated glycerol monoester) 和单 12-羟 乙酯硬脂酸双乙酰甘油酉旨 （Fully acetylated glycerol monoester on 12-hydroxystearic acid) 具 有较小的分子量 （约 500左右） ， 较高的沸点 （〉300°C ) 和较高的闪点 （245 °C ) ， 具有 较好的流动性及较低的粘度， 可作为聚氯乙烯塑料的增塑剂。 而环氧油类分子量较大、 粘 性较大、流动性差，但由于其结构中包含环氧基团， 具有较好的热稳性及与塑料的相溶性; 三醋酸甘油酯分子较小， 其粘度较环氧油类小， 我们结合它们相互结构的特征和性质， 希 望能找到一种增塑效果与环氧油类相似， 但分子量低、 流动性好的环氧酸酯类增塑剂。 发明内容 本发明的目的在于克服现有技术的不足， 提供一种二乙酰环氧油酸甘油酯的合成工 艺， 通过此工艺制得的二乙酰环氧甘油酯作为增塑剂应用到具有塑料中， 具有稳定性好、 流动性好、 与塑料的相溶性好的优点。 为实现上述目的， 本发明通过以下技术方案实现： 一种二乙酰环氧油酸甘油酯的合成工艺， 包括以下步骤： a、酯化反应：酯化原料甘油与油酸在酯化催化剂作用下于 115〜190°C下酯化反应 1.5〜 4.5小时， 生成油酸单甘油酯 （A) ；
(A)
b、 乙酰化反应： 步骤 a中生成的油酸单甘油酯 （A) 与乙酰化试剂在在乙酰化催化剂的作 用下于 90〜160°C下乙酰化反应 2〜10小时， 生成二乙酰油酸甘油酯 （B) ；
乙酰化
(A) (B)
c、 环氧化反应： 步骤 b中生成的二乙酰油酸甘油酯 （B) 与双氧水在环氧化催化剂及 弱酸催化作用下， 于 60〜80°C下反应 2〜4小时， 生成二乙酰环氧油酸甘油酯 （C) ；
(B) (C)
优选的是： 所述步骤 a中， 甘油与油酸的重量比为 1 :3.06〜3.07。 优选的是： 所述步骤 a中， 酯化催化剂为浓硫酸、 浓磷酸、 硫酸氢钾、 对甲苯磺酸和 [emin]BF4离子液体中的任一种，且按重量百分比计，所述酯化催化剂的用量为酯化原料用 量的 0.01〜0.04%。 优选的是： 所述步骤 b中， 乙酰化试剂为乙酰氯、 冰醋酸和乙酸酐中的任一种， 且按 重量百分比计， 所述乙酰化试剂的用量为油酸单甘油酯用量的 40〜50%。 优选的是： 所述步骤 b中， 乙酰化催化剂为浓硫酸、 浓磷酸和 NaHS(VH20中的至少一 种， 且按重量百分比计， 所述乙酰化催化剂的用量为为油酸单甘油酯用量的 0.3〜0.6%。 优选的是： 所述步骤 b中还加入了带水剂， 所述带水剂为苯、 环己垸和己垸中的至少 一种， 且按重量百分比计， 所述带水剂的用量为油酸单甘油酯用量的 35〜40%。 优选的是： 所述步骤 c中， 环氧化催化剂为浓磷酸和 /或浓硫酸。 优选的是： 所述步骤 c中， 弱酸为甲酸和 /或乙酸。
优选的是： 所述步骤 c中， 双氧水的浓度为 50%。 优选的是： 所述步骤 c中， 二乙酰油酸甘油酯、 双氧水、 弱酸、 环氧催化剂的重量为 1 : 04〜0.7： 0.04〜0.08： 0.001〜0.003。 本发明的有益效果在于， 通过本发明的工艺制得的二乙酰环氧甘油酯可作为增塑剂应 用到具有塑料中， 不仅具有与环氧油类似的增塑效果， 且分子量比环氧油更低， 还稳定性 好、 流动性好、 与塑料的相溶性好的优点。 附图说明 附图 1示出了本发明中所述的油酸单甘油酯 （A) 的红外光谱图；
附图 2示出了本发明中所述的二乙酰油酸甘油酯 （B) 的红外光谱图；
附图 3示出了本发明中所述的产物二乙酰环氧油酸甘油酯 （C) 的红外光谱图。 具体实施方式 下面结合具体实施例对本发明的具体实施方式做进一步说明， 但本发明并不仅限于下 述实施例。 本发明以油酸和甘油为原料制备二乙酰环氧油酸甘油酯， 其合成路线包括以下步骤： a、 酯化反应： 酯化原料甘油与油酸在 115〜190°C下酯化反应 1.5〜4.5小时， 生成油酸 单甘油酯 （A) ；
CH 7 _〇H 酯化
I 催化剂
- OH +
CH2 _〇H
( A)
b、 乙酰化反应： 步骤 a中生成的油酸单甘油酯 （A) 与乙酰化试剂在 90〜160°C下乙酰化反 应 2〜10小时， 生成二乙酰油酸甘油酯 （B) ；
乙酰化
(A) (B)
c、 环氧化反应： 步骤 b中生成的二乙酰油酸甘油酯 （B) 与双氧水在催化剂作用下， 于 60〜80°C下反应 2〜4小时， 生成二乙酰环氧油酸甘油酯 （C) ；
(B) (C) 其中， 步骤 a中， 酯化原料甘油与油酸的重量比为 1 :3.06〜3.07; 所述酯化催化剂为浓 硫酸、 浓磷酸、 硫酸氢钾、 对甲苯磺酸和 [emin]BF4离子液体中的任一种， 且按重量百分比
步骤 b中， 所述乙酰化试剂为乙酰氯、 冰醋酸和乙酸酐中的任一种， 其按重量百分比 计， 所述乙酰化试剂的用量为油酸单甘油酯 （A) 用量的 40〜50%; 所述乙酰化催化剂为 浓硫酸、 浓磷酸和 NaHS(VH20中的至少一种， 且其用量按重量百分比计， 为油酸单甘油 酯 （A) 用量的 0.3〜0.6%； 所述乙酰化反应中， 还加入了带水剂， 所述带水剂为苯、 环己 垸和己垸中的至少一种， 按重量百分比计， 其用量为油酸单甘油酯 （A) 用量的 35〜40%； 步骤 c中， 所述环氧化催化剂为浓磷酸和 /或浓硫酸； 所述弱酸为甲酸和 /或乙酸， 且二 乙酰油酸甘油酯 （B) 、 双氧水、 弱酸、 环氧催化剂的重量比为 1 : 04〜0.7： 0.04〜0.08： 0.001〜0.003。 实施例 1 以油酸和甘油为原料制备二乙酰环氧油酸甘油酯， 包括以下制备步骤:
a、 酯化反应： 将 754g油酸、 246g甘油、 依次加入到带有搅拌装置、 温度计、 回流分水 冷凝管的三口圆底瓶中，通入氮气并搅拌升温，当温度达到 120°C时，加入浓磷酸催化剂 0.2g， 并于 190°C下酯化反应 3小时后， 再抽真空 25小时至酸值达到 3以下结束反应， 得到油酸单 甘油酯； 油酸单甘油酯的红外测试（IR(KBr))结果如图 1所示： 其中， 3432cm- 1宽峰为 -OH 峰， 3009cm- 1为不饱和烃的 C-H 伸缩振动吸收； 2926cm-1为饱和烃 CH^ C-H不对称伸缩振 动吸收； 2854cm- 1为饱和烃 CH2的 C-H对称伸缩振动吸收； 1742cm- 1为酯的 C=0伸缩振动吸 收； 1463cm- 1为甲基的 C-H不对称弯曲振动； 1378cm- 1为甲基的 C-H对称弯曲振动； 1172cm-1 为 C-O-C非对称伸缩振动； 1120cm- 1为 C-0-C对称伸缩振动； b、 乙酰化反应： 在装有搅拌装置、 温度计、 吊水装置及回流冷凝管的三口圆底瓶 中，依次加入步骤 a中制得的油酸单甘油酯 356g、 乙酰化试剂冰醋酸 160g、 带水剂苯 130g 及催化剂浓硫酸 1.5g， 升温至 120°C带水回流反应 6小时， 当出水量达到理论量时停止反 应，减压抽出未反应冰醋酸及带水剂苯， 得灰黑色油状物为二乙酰油酸甘油酯； 二乙酰油 酸甘油酯的红外测试（IR(KBr 结果如图 2所示： 其中： 3009cm- 1为不饱和烃的 C-H伸缩 振动吸收； 2926cm- 1为饱和烃 CH^ C-H不对称伸缩振动吸收； 2855cm- 1为饱和烃〔¾的 C-H对称伸缩振动吸收； 1748cm- 1为酯的 C=0伸缩振动吸收； 1462cm- 1为甲基的 C-H不对 称弯曲振动； 1371cm- 1为甲基的 C-H对称弯曲振动； 1167cm- 1为 C-0-C非对称伸缩振动； 1119cm- 1为 C-0-C对称伸缩振动；
c、 环氧化反应： 在装有搅拌装置、 温度计、 滴液漏斗、 回流冷凝管的四口瓶中， 依 次加入步骤 b中得到的二乙酰油酸甘油酯 500g、 80〜85%甲酸 30g、 催化剂浓硫酸 0.7g， 升 温至 65°C， 搅拌下慢慢滴入 50%双氧水 250g， 然后升温至 80°C， 环氧化反应 4小时， 分出 下层酸水， 上层油酯先后用碱水、 水洗至中性， 酸值在 0.6以下时， 通过减压蒸馏除水并 过滤得浅黄色油状物二乙酰环氧油酸甘油酯， 其环氧值为 3.0， 酸值为 1.2， 碘值为 2.7; 二乙酰环氧油酸甘油酯的红外测试 （IR(KBr)) 结果如图 3所示： 其中： 2927cm- 1为饱和 烃 CH2的 C-H不对称伸缩振动吸收； 2856cm- 1为饱和烃 CH2的 C-H对称伸缩振动吸收； 1746cm- 1为酯的 C=0伸缩振动吸收； 1463cm- 1为甲基的 C-H不对称弯曲振动； 1372cm- 1为 甲基的 C-H对称弯曲振动； 1168cm- 1为 C-0-C非对称伸缩振动； 1100cm- 1为 C-0-C对称伸 缩振动； 844cm-1为三元环醚 C-0-C非对称伸缩振动； 726cm-1为亚甲基的平面摇摆振动。 本发明所描述的具体实施例只用于对以油酸和甘油为原料制备二乙酰环氧油酸甘油 酯的制备工艺的具体实现过程的详细描述， 而不是对本发明之二乙酰环氧油酸甘油酯的制
备工艺的限定。 任何对此方法进行的修饰与改良， 在专利范围或范畴内同类或相近物质的 替代与使用， 均属于本发明专利保护范围。
Claims
1、 一种二乙酰环氧油酸甘油酯的合成工艺， 其特征在于： 包括以下步骤： a、酯化反应：酯化原料甘油与油酸在酯化催化剂作用下于 115〜190°C下酯化反应 1. 4.5小时， 生成油酸单甘油酯 （A) ；
( A)
b、 乙酰化反应： 步骤 a中生成的油酸单甘油酯 （A) 与乙酰化试剂在乙酰化催化剂的作用 下于 90〜160°C下乙酰化反应 2〜10小时， 生成二乙酰油酸甘油酯 （B) ； 乙酰化
(A) (B)
c、 环氧化反应： 步骤 b中生成的二乙酰油酸甘油酯 （B) 与双氧水在环氧化催化剂及 弱酸催化作用下， 于 60〜80°C下反应 2〜4小时， 生成二乙酰环氧油酸甘油酯 （C) ；
(B) (C)
2、根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 a中， 甘油与油酸的重量比
为 1 :3.06〜3.07。
3、根据权利要求 1所述的合成工艺，其特征在于：所述步骤 a中，酯化催化剂为浓硫酸、 浓磷酸、 硫酸氢钾、 对甲苯磺酸和 [emin]BF4离子液体中的任一种， 且按重量百分比计， 所 述酯化催化剂的用量为酯化原料用量的 0.01〜0.04%。
4、 根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 b中， 乙酰化试剂为乙酰 氯、 冰醋酸和乙酸酐中的任一种， 且按重量百分比计， 所述乙酰化试剂的用量为油酸单甘 油酯用量的 40〜50%。
5、 根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 b中， 乙酰化催化剂为浓 硫酸、 浓磷酸和 NaHS(VH20中的至少一种， 且按重量百分比计， 所述乙酰化催化剂的用 量为油酸单甘油酯用量的 0.3〜0.6%。
6、 根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 b中还加入了带水剂， 所 述带水剂为苯、 环己垸和己垸中的至少一种， 且按重量百分比计， 所述带水剂的用量为油 酸单甘油酯用量的 35〜40%。
7、根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 c中， 环氧化催化剂为浓磷 酸和 /或浓硫酸。
8、 根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 c中， 弱酸为甲酸和 /或乙 酸。
9、根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 c中，双氧水的浓度为 50%。
10、根据权利要求 1所述的合成工艺， 其特征在于： 所述步骤 c中， 二乙酰油酸甘油酯、 双氧水、 弱酸、 环氧催化剂的重量比为 1 : 04—0.7： 0.04—0.08： 0.001〜0.003。
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| CN116768828A (zh) * | 2023-06-14 | 2023-09-19 | 南通海珥玛科技股份有限公司 | 一种乙酰化环氧大豆油及其制备方法和应用、一种聚氯乙烯复合材料 |
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| CN103483296A (zh) * | 2013-09-23 | 2014-01-01 | 广州市海珥玛植物油脂有限公司 | 二乙酰环氧油酸甘油酯的合成工艺 |
| CN104370860B (zh) * | 2014-10-22 | 2017-01-11 | 广州市海珥玛植物油脂有限公司 | 二环氧植物油酸乙酰甘油酯及其合成方法与应用 |
| CN105085442B (zh) * | 2015-07-23 | 2019-01-04 | 广州市海珥玛植物油脂有限公司 | 二元酸双一乙酰环氧植物油酯及其合成方法 |
| CN107641107B (zh) * | 2016-07-20 | 2021-04-13 | 广州市海珥玛植物油脂有限公司 | 二乙酰环氧十一酸甘油酯及其制备方法和应用 |
| CN106751615B (zh) * | 2016-12-19 | 2019-07-26 | 广东波斯科技股份有限公司 | 一种高分散、低吸水率的生物可降解色母粒及其制备方法 |
| CN108299496B (zh) * | 2017-09-27 | 2019-12-06 | 杭州金诚助剂有限公司 | 含有亚磷酸有机酯抗氧剂及合成方法 |
| CN110804029B (zh) * | 2019-11-08 | 2022-04-29 | 浙江工业大学 | 一种环氧类增塑剂及其制备方法 |
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| CN103483296A (zh) * | 2013-09-23 | 2014-01-01 | 广州市海珥玛植物油脂有限公司 | 二乙酰环氧油酸甘油酯的合成工艺 |
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| CN103242558B (zh) * | 2013-05-24 | 2014-05-21 | 河南正通化工有限公司 | 一种柠檬酸酯增塑剂及其制备方法 |
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| CN116768828B (zh) * | 2023-06-14 | 2024-03-15 | 南通海珥玛科技股份有限公司 | 一种乙酰化环氧大豆油及其制备方法和应用、一种聚氯乙烯复合材料 |
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