CN109970556A - One vegetable oil chitin alcohol ether-ether and its preparation method and application - Google Patents
One vegetable oil chitin alcohol ether-ether and its preparation method and application Download PDFInfo
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- CN109970556A CN109970556A CN201910136307.7A CN201910136307A CN109970556A CN 109970556 A CN109970556 A CN 109970556A CN 201910136307 A CN201910136307 A CN 201910136307A CN 109970556 A CN109970556 A CN 109970556A
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- vegetable oil
- ether
- chitin
- reaction
- alcohol
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- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 96
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 96
- 229920002101 Chitin Polymers 0.000 title claims abstract description 84
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004626 polylactic acid Substances 0.000 claims abstract description 45
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 25
- 239000004014 plasticizer Substances 0.000 claims abstract description 25
- 239000008157 edible vegetable oil Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 20
- -1 alcohol monoalky lether Chemical class 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000032050 esterification Effects 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000005292 vacuum distillation Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012024 dehydrating agents Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 235000013305 food Nutrition 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 6
- 239000010773 plant oil Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 230000021615 conjugation Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims 1
- 239000011877 solvent mixture Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 20
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 125000001033 ether group Chemical group 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 31
- 229920000915 polyvinyl chloride Polymers 0.000 description 26
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 22
- 239000008162 cooking oil Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 5
- 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 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000008116 calcium stearate Substances 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
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002383 tung oil Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 235000018927 edible plant Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 1
- YWNYZQTZOONLGU-UHFFFAOYSA-N C(CC)Cl.[O] Chemical compound C(CC)Cl.[O] YWNYZQTZOONLGU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
Abstract
The invention discloses vegetable oil chitin alcohol ether-ethers and its preparation method and application, for this method using discarded edible vegetable oil, maleic anhydride and dihydric alcohol monoalky lether as raw material, the mode by hydrolysis, isomerization, Diels-Alder addition, esterification synthesizes vegetable oil chitin alcohol ether-ether.Big containing polarized in the vegetable oil chitin alcohol ether ester molecular structure, flexibility is good ester, ether group, therefore have many advantages, such as and polylactic acid and PVC compatibility are good, plasticizing efficiency is high, additive amount is few, conventional petroleum base plasticizer dioctyl terephthalate can be substituted completely, it is the plasticizer of polylactic acid and PVC function admirable, realizes the resource utilization of waste.In addition, the PVC material after the plasticising of vegetable oil chitin alcohol ether-ether has excellent uvioresistant performance, there is good practicability.
Description
Technical field
The invention belongs to new plasticizer and its preparation technical fields, are related to a kind of utilize and recycle discarded edible vegetable oil
Prepare the method for biology base plasticizer and its application in polylactic acid plastic and PVC material more particularly to a kind of using discarded
Edible vegetable oil prepares answering for preparation method of vegetable oil chitin alcohol ether-ether and products thereof and the materials such as plasticized poly lactic acid, PVC
Use method.
Background technique
Waste cooking oils are a kind of recycling greases that can not be eaten again, are mainly derived from catering industry.The whole world is every according to statistics
Year, the amount of waste cooking oils was more than 5,000,000 tons, and effectively recycling, safety, which are stored, simultaneously efficiently recycles these waste greases to have
Highly important meaning.The feed of poultry is often used as in these recycled wood materials of developing country.But these are discarded
Grease may have some harmful substances, and the mankind are transferred to by way of food chain transport due to passing through applied at elevated temperature
With.Therefore, the developed economies such as European Union have just forbidden this recycling mode of waste vegetable oil in 2002
(Kulkarni et al.Ind.Eng.Chem.Res.2006,45 (9), 2901-2913.).In this case, Hen Duogong
Author attempts waste cooking oils being converted into valuable lubricating grease, synthesis gas and biodiesel.Wherein utilize discarded food
It is successfully applied in industrial production with oil preparation biodiesel since added value is higher.However, the structure group of waste grease
The quality tool of pairs of biodiesel has a significant impact, and which has limited the large-scale application of waste cooking oils (Gui et
Al.Energy, 2008,33,1646-1653.).
It is one feasible using waste cooking oils preparation high-quality, renewable, nontoxic and degradable biological base plasticizer
And effective method.On the one hand, the annual requirement of plasticizer is more than 64,000,000 tons.On the other hand, traditional petroleum base plasticizer
(such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP)), exists
The disadvantages of toxic, non-renewable and degradation is difficult, prepare it is renewable, can degrade and the biology base plasticizer of low (nothing) poison be must
So selection.
Have much using the research that fresh vegetable oil prepares high-quality plasticizer as raw material at present.Such as Li et al. people
(Material&Design.2017,122 (15), 366-375.) are reported using the double bond in tung oil, with maleic anhydride addition
Then it is esterified to obtain corresponding tung oil-methyl maleate with methanol again.Chen et al. (ACS Sustainable
Chem.Eng., 2018,6 (1), 642-651.) report using the double bond and maleic anhydride addition in tung oil, then again with ring
Oxygen chloropropane is reacted to obtain the base of the tung oil with good thermal stability-Malaysia acid glycidyl ester.And with discarded edible plant
Object oil is that raw material is then relatively fewer come the research for preparing biology base plasticizer.Because the ingredient after applied at elevated temperature in edible oil is more
Add complexity, and double bond content is lower (conjugated double bond is lower), this increases difficulty for further study on the modification.Nearest Feng etc.
People (J.Clean.Prod.189,334343.), which reports, prepares polycarboxylate using waste cooking oils, and is used in PVC material
To substitute traditional dioctyl phthalate (DOP) on material.Result of study shows that the plasticizer has good plasticity
Can, but its synthetic technological condition is harsher, needs at 250 DEG C, and distillation obtains intermediate product fatty acid methyl under vacuum condition
Ester.In addition, Zheng et al. (J.Clean.Prod.186,10211030.) is by by waste cooking oils methyl esters and epoxidation
Mode obtain new plasticizer and apply in PVC material.But the compatibility of the epoxy waste cooking oils methyl esters and PVC are poor,
The toxic DOP of petroleum base can only partially be substituted.More importantly these plasticizer are all merely used to the increasing in PVC material
Modeling, and the application in poly-lactic acid material then has no that pertinent literature is reported.
Summary of the invention
Goal of the invention: being directed to above-mentioned problems of the prior art, and the purpose of the present invention is to provide a kind of using useless
The method that edible vegetable oil prepares vegetable oil chitin alcohol ether-ether is abandoned, there is the features such as easy to operate, environmental protection, waste utilization.This
The another object of invention is to provide a kind of vegetable oil chitin alcohol ether-ether that the above method prepares, increasing good with compatibility
Mould the features such as high-efficient.Further object of the present invention is to provide a kind of above-mentioned vegetable oil chitin alcohol ether-ether and answers as plasticizer
With in the plasticising of polylactic acid and PVC material.
Technical solution: in order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A method of vegetable oil chitin alcohol ether-ether being prepared using discarded edible vegetable oil, to discard edible vegetable oil
For raw material, hydrolysis, isomerization reaction are first passed through, then carries out Diels-Alder addition reaction with maleic anhydride and obtains plant oil base
Polyacid, vegetable oil chitin is reacted with the esterification of dihydric alcohol monoalky lether synthesizes vegetable oil chitin alcohol ether-ether；Wherein, plant
The molar ratio of oil base polyacid and dihydric alcohol monoalky lether are as follows: 1: 1~5；The general structure of the dihydric alcohol monoalky lether are as follows:
In formula, n are as follows: 1~5, R1For H or CH3, R2For C1-6Alkyl.
The method that edible vegetable oil prepares vegetable oil chitin alcohol ether-ether is discarded in the utilization, and steps are as follows:
1) sodium hydroxide, ethanol-water solution are taken, reactor is added, stirs and is heated to 60-70 DEG C, is then added dropwise discarded
Edible vegetable oil is into reaction system, after reacting 2-5h, with 0.5-1mol/L hydrochloric acid regulation system pH to 2~3, and continues anti-
Answer after 1-5h that reaction was completed；Hydrolysis temperature is too high, flows back excessively violent, causes part ethyl alcohol to volatilize, results in waste of resources；Water
Solution temperature is too low, then hydrolysis is not thorough, and causes mono-acid yield relatively low.Reaction mixture solvent (ether, acetic acid
One of ethyl ester, n-hexane) extraction mixture, organic phase is obtained, and be washed with deionized；Finally by vacuum distillation
Mode remove solvent and water, obtain sticky adopting dark liquid；
2) sticky adopting dark liquid, potassium hydroxide, ethylene glycol are taken, 10-12 h is first reacted under 165-190 DEG C of stirring, then
Deionized water is added after 90-110 DEG C of reaction 0.5-1h, reaction temperature is down to room temperature.Isomerisation temperature is too high or isomerization
Time, too long meeting side reaction increased, and product color is caused to be deepened；Isomerisation temperature is too low or reaction time too short then mixture in
It is relatively low to be conjugated acid content；With hydrochloric acid acid system pH to 2~3；Use solvent (one of ether, ethyl acetate, n-hexane) again
Extraction organic phase is simultaneously washed with deionized；Solvent and water are removed finally by vacuum distillation, the discarded edible plant being conjugated
Object oleic acid；
3) discarded food plant oil base acid, maleic anhydride, hydroquinone and the acetic acid for taking conjugation, at 105-130 DEG C, nitrogen
5-7h is reacted under gas shielded, and after deionized water the reaction was continued under reflux conditions 0.5-1h then is added, system temperature is down to
Room temperature.Addition temperature is too high or the time is too long, easily leads to side reaction increase；Temperature is too low or time too short then addition reaction not
Thoroughly, polyacid yield is relatively low.Reaction mixture organic phase is extracted with solvent (one of ether, ethyl acetate, n-hexane),
And spend ion-cleaning；Solvent and water finally are removed with the mode of vacuum distillation, obtains discarded edible vegetable oil chitin；
4) discarded edible vegetable oil chitin, dihydric alcohol monoalky lether, catalyst (p-methyl benzenesulfonic acid, sulfuric acid, metatitanic acid are taken
One of four butyl esters, stannous chloride, cation exchange resin, dosage are 0.5~5wt% (in terms of vegetable oil chitin quality
Calculate)), dehydrating agent (one of toluene or hexamethylene, 40~70wt% (with vegetable oil chitin Mass Calculation)), in 120-
At 150 DEG C, reaction was completed after 5-8h；Temperature is too high or reaction time too long then product color is deepened, and side reaction increases；Temperature
The too low or reaction time is too short, then esterification is incomplete, and target product yield is caused to be lower.It was removed by refinement treatment
The dihydric alcohol monoalky lether and dehydrating agent of amount, then use NaHCO again3Solution washs remaining liq to system pH to neutrality；Finally
By vacuum distillation dehydration, vegetable oil chitin alcohol ether-ether is obtained.
The method vegetable oil obtained that the discarded edible vegetable oil of the utilization prepares vegetable oil chitin alcohol ether-ether is more
Acidic group alcohol ether-ether；Its component includes:
Wherein, R1=H or CH3, R2=C1-C6Alkyl, n=1~5.
Application of the vegetable oil chitin alcohol ether-ether as plasticizer.
Vegetable oil chitin alcohol ether-ester plasticizers provided by the present application, there are two types of typical purposes, one of which is plasticising
Polylactic acid plastic: polylactic acid and vegetable oil chitin alcohol ether-ether are subjected to mixing extrusion molding in extruding machine；Then plant will be mixed with
The polylactic acid sample of oil base polyacid alcohol ether-ether prepares the product of needs on injection molding machine as needed；Wherein, plant oil base alcohol ether
The mass ratio of ester and polylactic acid are as follows: 5~20: 100.
Another kind is plasticized PVC materials: using vegetable oil polyacid alcohol ether-ether as plasticizer, PVC powder and heat stabilizer is added,
Mechanical premix is first carried out, mixture is then subjected to mixing extrusion molding, prepares the PVC material with uvioresistant performance
The utility model has the advantages that compared with prior art, the present invention is that raw material prepares high-performance plant using the waste cooking oils of recycling
Object oil base polyacid alcohol ether-ether has the features such as environmental protection, waste utilization.Synthesized vegetable oil chitin alcohol ether ester molecular structure
In, ester that flexibility good big containing polarized, ether group, therefore have that compatibilities are good, plasticizing efficiency is high etc. with polylactic acid, PVC etc.
Advantage can substitute conventional petroleum base plasticizer dioctyl terephthalate completely, be polylactic acid and PVC material function admirable
Plasticizer realizes the resource utilization of waste.In addition, the PVC material after the plasticising of vegetable oil chitin alcohol ether-ether is with excellent
Different uvioresistant performance has good practicability.
Detailed description of the invention
Fig. 1 is discarded food plant oleic acid1H NMR spectra；
Fig. 2 is the discarded food plant oleic acid of conjugation1H NMR spectra；
Fig. 3 is waste cooking oils polyacid1H NMR spectra；
Fig. 4 is the product WFOPA-1 after waste cooking oils polyacid and ethylene glycol monomethyl ether esterification1H NMR spectra；In figure
φ represent in WFOPA go out carboxyl other than other structures；
Fig. 5 is WFOPA-3 additive amount and glass transition temperature (Tg) relational graph；
Fig. 6 is the ultraviolet spectrogram of PVC sample after plasticising.
Specific embodiment
The invention is further illustrated by the following examples, but is not limited to lifted embodiment.
Raw material in following embodiment discards edible vegetable oil, is provided by Darling Ingredients company；Second two
Alcohol methyl ether, diethylene glycol dimethyl ether, butyl, triethylene glycol methyl ether, butyl, propylene glycol monomethyl ether are work
Industry grade, is produced by Jiangsu Yida Chemical Co., Ltd.；Potassium hydroxide (90%), maleic anhydride (99%), terephthalic acid (TPA)
Dioctyl ester (DOTP) (>=96.0%), p-methyl benzenesulfonic acid (>=98.5%), hexamethylene (>=99.5) is by Sigma-Aldrich public affairs
Department provides；Stannous chloride, butyl titanate, toluene provide for Sinopharm Chemical Reagent Co., Ltd.；Acetic acid, hydroquinone,
Sodium hydroxide is provided by Fisher Scientific company；Hydrochloric acid is provided by EMD Millipore company；Polylactic acid
(3052D) is provided by Nature works company；PVC powder (DG-1000K) is provided by Dajie Chemical Co., Ltd., Tianjin.
Embodiment 1
The method for synthesizing vegetable oil chitin alcohol ether-ether, steps are as follows:
1) it discards edible vegetable oil and is hydrolyzed into vegetable oil acid:
16.0g sodium hydroxide, 140mL ethanol-water solution (1: 1, V/V), put into three mouthfuls of round-bottomed bottles of 1L, magnetic force
It stirs and is heated to 70 DEG C, 100.0g is then discarded into edible vegetable oil and is added drop-wise in reaction system, after reacting 2h, use hydrochloric acid
(1mol/L) regulation system pH to 2~3, and reaction was completed after the reaction was continued 1h.Mixture is extracted with ether, obtains organic phase,
And it is washed with deionized 3~5 times.Ether and water are removed finally by the mode of vacuum distillation, obtains sticky adopting dark liquid,
It is marked with WFOA, nuclear-magnetism figure is as shown in Figure 1；Gas chromatograph results show the composition of the WFOA are as follows: C16:0 (0.8%),
C18:0 (14.9%), C18:1 (43.0%), C18:2 (34.6%), C18:3 (6.7%), W (C18:1)+W in mixture
(C18:2) content is greater than 77%, is the main component in mixed plant oleic acid, it is seen that and the WFOA prepared is mixture,
The structural formula of main compound are as follows:
2) vegetable oil acid isomerization:
Vegetable oil acid, 50g potassium hydroxide, the 200mL ethylene glycol of 50g step 1) preparation are put into 500mL round-bottomed bottle,
10h is reacted under 180 DEG C of magnetic agitations.Then 50mL deionized water is added after 100 DEG C of reaction 30min, reaction temperature is dropped
To room temperature.With hydrochloric acid (1mol/L) acid system pH to 2~3.Organic phase is extracted with ether again and is washed with deionized.Most
Ether is removed by vacuum distillation afterwards and water, the vegetable oil acid being conjugated are marked with CWFOA, nuclear-magnetism figure is as shown in Figure 2；
Yield is 87.3%, and primary structure is as follows:
3) synthesis of vegetable oil chitin:
By step 2) preparation 50g conjugation plant oil base acid, 42.0g maleic anhydride, 917.0mg hydroquinone and
150mL acetic acid is put into round-bottomed bottle, reacts 5h under 120 DEG C, nitrogen protection.Then 25mL deionized water is added to flow back
Under the conditions of after the reaction was continued 30min, system temperature is down to room temperature.Organic phase is extracted with ether, and spends ion-cleaning.Most
Ether and water are removed with the mode of vacuum distillation afterwards, obtains vegetable oil polyacid, acid value 309.7mg/g is mixture, uses
WFOPA indicates that the nuclear-magnetism figure of main component is as shown in figure 3, its headformulae is as follows:
4) synthesis of vegetable oil chitin (ethylene glycol monomethyl ether) ester:
The vegetable oil chitin of 30g step 3) preparation, 38.1g ethylene glycol monomethyl ether, 0.3g p-methyl benzenesulfonic acid, 21.0g hexamethylene
Alkane is added in four-hole bottle, and at 130-150 DEG C, reaction was completed after 5h.By vacuum distillation recycling dehydrating agent hexamethylene and not
Then the ethylene glycol monomethyl ether of reaction uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally lead to
The mode for crossing vacuum distillation dehydrates, and obtains vegetable oil chitin (L glycol methyl ether) ester (WFOPA-1), 38.4mPa.s；ρ
(20 DEG C): 0.92g/cm3, nuclear-magnetism figure as shown in figure 4, its main component structural formula are as follows:
Embodiment 2
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (diethylene glycol dimethyl ether) ester is synthesized, process is such as
Under:
30g above-mentioned vegetable oil chitin, 60.1g diethylene glycol dimethyl ether, 0.3g p-methyl benzenesulfonic acid, 21.0g hexamethylene add
Enter into four-hole bottle, the azeotropic dehydration at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent hexamethylene is recycled by vacuum distillation
With unreacted diethylene glycol dimethyl ether, the NaHCO of 10wt% is then used again3Solution washs remaining liq to system pH to neutrality；
It is dehydrated finally by the mode of vacuum distillation, obtains vegetable oil chitin (diethylene glycol dimethyl ether) ester (WFOPA-2), η
(25 DEG C): 37.8mPa.s；ρ (20 DEG C): 0.93 g/cm3, the structural formula of main component are as follows:
Embodiment 3
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (triethylene glycol methyl ether) ester is synthesized, process is such as
Under:
30g above-mentioned vegetable oil chitin, 82.1g triethylene glycol methyl ether, 0.3g p-methyl benzenesulfonic acid, 21.0g hexamethylene add
Enter into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent hexamethylene and unreacted are removed by vacuum distillation
Triethylene glycol methyl ether, then again use 10wt% NaHCO3Solution washs remaining liq to system pH to neutrality；Finally by
The mode of vacuum distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), η (25 DEG C):
36.6mPa.s；ρ (20 DEG C): 0.94g/cm3, the structural formula of main component are as follows:
Embodiment 4
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (triethylene glycol methyl ether) ester is synthesized, process is such as
Under:
30g above-mentioned vegetable oil chitin, 82.1g triethylene glycol methyl ether, 0.15g p-methyl benzenesulfonic acid, 21.0g hexamethylene
It is added in four-hole bottle, at 130-150 DEG C, reaction was completed after 8h.By vacuum distillation remove dehydrating agent hexamethylene and not instead
Then the triethylene glycol methyl ether answered uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally lead to
The mode for crossing vacuum distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), yield
79.3%.
Embodiment 5
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (three second are synthesized under butyl titanate catalysis
Glycol methyl ether) ester, process is as follows:
30g above-mentioned vegetable oil chitin, 82.1g triethylene glycol methyl ether, 0.9g butyl titanate, 21.0g hexamethylene add
Enter into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent hexamethylene and unreacted are removed by vacuum distillation
Triethylene glycol methyl ether, then again use 10wt% NaHCO3Solution washs remaining liq to system pH to neutrality；Finally by
The mode of vacuum distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), and yield is
85.2%.
Embodiment 6
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (three second two are synthesized under Sold Stannous Chloride Catalyzes
Alcohol methyl ether) ester, process is as follows:
30g above-mentioned vegetable oil chitin, 82.1g triethylene glycol methyl ether, 1.5g stannous chloride, 21.0g hexamethylene are added
Into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent hexamethylene and unreacted is removed by vacuum distillation
Then triethylene glycol methyl ether uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally by subtracting
The mode of pressure distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), yield 88.0%.
Embodiment 7
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (triethylene glycol methyl ether) ester is synthesized, process is such as
Under:
30g above-mentioned vegetable oil chitin, 27.2g triethylene glycol methyl ether, 0.3g p-methyl benzenesulfonic acid, 21.0g toluene are added
Into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent toluene and unreacted three is removed by vacuum distillation
Then ethylene glycol monomethyl ether uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally by decompression
The mode of distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), yield 80.7%.
Embodiment 8
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (triethylene glycol methyl ether) ester is synthesized, process is such as
Under:
60g above-mentioned vegetable oil chitin, 164.2g triethylene glycol methyl ether, 0.6g p-methyl benzenesulfonic acid, 24.0g toluene add
Enter into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent toluene and unreacted is removed by vacuum distillation
Then triethylene glycol methyl ether uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally by subtracting
The mode of pressure distillation dehydrates, and obtains vegetable oil chitin (triethylene glycol methyl ether) ester (WFOPA-3), yield 78.6%.
Embodiment 9
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (butyl) ester is synthesized, process is such as
Under:
30g above-mentioned vegetable oil chitin, 80.7g butyl, 0.3g p-methyl benzenesulfonic acid, 21.0g hexamethylene add
Enter into four-hole bottle, at 130-150 DEG C, reaction was completed after 5h.Dehydrating agent hexamethylene and unreacted are removed by vacuum distillation
Butyl then again use 10wt% NaHCO3Solution washs remaining liq to system pH to neutrality；Finally by
The mode of vacuum distillation dehydrates, and obtains vegetable oil chitin (butyl) ester (WFOPA-DEB), η (25 DEG C):
37.2mPa.s；ρ (20 DEG C): 0.93g/cm3, the structural formula of main component are as follows:
Embodiment 10
Using the vegetable oil chitin in embodiment 1, vegetable oil chitin (propylene glycol monomethyl ether) ester is synthesized, process is as follows:
30g above-mentioned vegetable oil chitin, 74.6g propylene glycol monomethyl ether, 0.3g p-methyl benzenesulfonic acid, 21.0g hexamethylene are added
Into four-hole bottle, at 120-130 DEG C, reaction was completed after 8h.Dehydrating agent hexamethylene and unreacted is removed by vacuum distillation
Then propylene glycol monomethyl ether uses the NaHCO of 10wt% again3Solution washs remaining liq to system pH to neutrality；Finally by decompression
The mode of distillation dehydrates, and obtains vegetable oil chitin (propylene glycol monomethyl ether) ester (WFOPA-MP), η (25 DEG C):
42.3mPa.s；ρ (20 DEG C): 0.93g/cm3, the structural formula of main component are as follows:
Embodiment 11
By WFOPA-1 and polylactic acid (PLA) according to mass ratio, m (WFOPA-1): m (PLA)=20: 100 formula is used
Haake extruding machine is kneaded 5min at 175 DEG C, then again with Haake injection molding machine (Haake MiniJet II, Karlsruhe,
Germany it) at 155 DEG C, under conditions of 600bars, needs to prepare 5 parallel PLA/WFOPA-1 (20%) according to test and tries
Sample.
By WFOPA-2 and polylactic acid (PLA) according to mass ratio, m (WFOPA-2): m (PLA)=20: 100 formula is used
Haake extruding machine is kneaded 5min at 175 DEG C, then again with Haake injection molding machine (Haake MiniJet II, Karlsruhe,
Germany it) at 155 DEG C, under conditions of 600bars, needs to prepare 5 parallel PLA/WFOPA-2 (20%) according to test and tries
Sample.
By WFOPA-3 and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-3): m (PLA)=5: 100 formula,
According to above-mentioned extrusion molding and injecting condition, it is molded to obtain the sample of 5 parallel PLA/WFOPA-3 (5%).
By WFOPA-3 and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-3): m (PLA)=10: 100, match
Side, according to above-mentioned extrusion molding and injecting condition, is molded to obtain the sample of 5 parallel PLA/WFOPA-3 (10%).
By WFOPA-3 and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-3): m (PLA's)=15: 100 matches
Side, according to above-mentioned extrusion molding and injecting condition, is molded to obtain the sample of 5 parallel PLA/WFOPA-3 (15%).
By WFOPA-3 and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-3): m (PLA's)=20: 100 matches
Side, according to above-mentioned extrusion molding and injecting condition, is molded to obtain the sample of 5 parallel PLA/WFOPA-3 (20%).
By WFOPA-DEB and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-DEB): m (PLA)=20: 100
Formula, according to above-mentioned extrusion molding and injecting condition, is molded to obtain the sample of 5 parallel PLA/WFOPA-DEB (20%).
By WFOPA-MP and polylactic acid (PLA) respectively according to mass ratio, m (WFOPA-MP): m (PLA's)=20: 100 matches
Side, according to above-mentioned extrusion molding and injecting condition, is molded to obtain the sample of 5 parallel PLA/WFOPA-MP (20%).
Contrast sample preparation.By DOTP and polylactic acid (PLA) according to mass ratio, m (DOTP): m (PLA)=20: 100
Formula, 5min is kneaded at 175 DEG C with Haake extruding machine, then again with Haake injection molding machine (Haake MiniJet II,
Karlsruhe, Germany) at 155 DEG C, under conditions of 600bars, need to prepare 5 parallel PLA/DOTP according to test
(20%) sample.
1. Performance Properties Evaluation of table
In table,aGlass transition temperature (Tg) obtained by dynamic mechanical analysis (DMA) curve；bVolatility experiment is root
According to standard " HG/T 4455-2012 " at 70 DEG C, for 24 hours under conditions of measure；cStorage modulus is by dynamic mechanical analysis
(DMA) it measures.
As shown in Table 1, the plasticizer prepared by the present invention, can significantly improve the ductility of polylactic acid (PLA).With
Traditional petroleum base DOTP is compared, and plasticising performance is more preferable, and thermal stability is more excellent.Of particular note is that even if addition 5%
WFOPA-3, plasticizing efficiency is also higher than the DOTP of addition 20%, and mechanics (storage modulus) and thermostabilization are higher.
Furthermore as shown in Figure 5, the additive amount of plasticizer WFOPA-3 and glass transition temperature (Tg, measured by DSC) experiment
Data point can be evenly scattered in around Fox equation curve, this illustrates that WFOPA-3 and polylactic acid have good compatibility.
Embodiment 12
By PVC powder (100 parts) and WFOPA-1 (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5
Part) premixed；Then the above-mentioned material mixed is kneaded at 175 DEG C 5 min with Haake extruding machine, is then infused again with Haake
Molding machine (Haake MiniJet II, Karlsruhe, Germany) is under conditions of 165 DEG C, 600 bars, according to test needs
Prepare 5 parallel PVC/WFOPA-1 samples.
By PVC powder (100 parts) and WFOPA-2 (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5
Part) premixed；Then the above-mentioned material mixed is kneaded at 175 DEG C 5 min with Haake extruding machine, is then infused again with Haake
Molding machine (Haake MiniJet II, Karlsruhe, Germany) is under conditions of 165 DEG C, 600 bars, according to test needs
Prepare 5 parallel PVC/WFOPA-2 samples.
By PVC powder (100 parts) and WFOPA-3 (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5
Part) premixed；Then the above-mentioned material mixed is kneaded at 175 DEG C 5 min with Haake extruding machine, is then infused again with Haake
Molding machine (Haake MiniJet II, Karlsruhe, Germany) is under conditions of 165 DEG C, 600 bars, according to test needs
Prepare 5 parallel PVC/WFOPA-3 samples.
By PVC powder (100 parts) and DOTP (40 parts), heat stabilizer: calcium stearate (1.5 parts), zinc stearate (0.5 part)
It is premixed；Then the above-mentioned material mixed is kneaded 5min at 175 DEG C with Haake extruding machine, is then molded again with Haake
Machine (Haake MiniJet II, Karlsruhe, Germany) under conditions of 600bars, needs to make at 165 DEG C according to test
Standby 5 parallel PVC/DOTP samples out.
2. Performance Properties Evaluation of table
In table,aGlass transition temperature (Tg) obtained by dynamic mechanical analysis (DMA) curve；bT5%, T10%Table respectively
Sample product are measured in the temperature of weightlessness 5% and 10% by thermogravimetric (TGA)；cMobility: the PVC sample after plasticising is immersed just
In hexane, at 23 ± 2 DEG C, under conditions of relative humidity is 50 ± 10%, calculated after impregnating for 24 hours according to Mass lost percentage
It obtains.
As shown in Table 2, the plasticizer prepared by the present invention, can significantly improve the ductility of PVC, and with polymerization
The increase of n is spent, elongation at break energy and thermal stability are better, even better than traditional petroleum base DOTP, illustrate discarded food
There is excellent plasticising performance and thermal stability with vegetable oil chitin alcohol ether-ester plasticizers.The discarded food for needing to particularly point out
It is better than DOTP with the resistance to migration of vegetable oil chitin alcohol ether-ether, illustrates that it is safer.
By the PVC sample after above-mentioned plasticising, on UV-vis spectrometer (Perkin-Elmer, Model Lambda 25)
Test analysis is carried out, as a result as shown in Figure 6.Furthermore it will be appreciated from fig. 6 that WFOPA-1, WFOPA-2, WFOPA-3, WFOPAM etc. all
Transmitance within the scope of UV wavelength 200-400nm is almost nil, and it is excellent to illustrate that the PVC prepared using waste cooking oils is had
Different uvioresistant performance.
Claims (10)
1. a kind of method for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil, which is characterized in that with discarded food
It is raw material with vegetable oil, first passes through hydrolysis, isomerization reaction, then carry out Diels-Alder addition reaction acquisition with maleic anhydride
Vegetable oil chitin, vegetable oil chitin is reacted with the esterification of dihydric alcohol monoalky lether synthesizes vegetable oil chitin alcohol ether-ether；Its
In, the molar ratio of vegetable oil chitin and dihydric alcohol monoalky lether are as follows: 1: 1~5；The structure of the dihydric alcohol monoalky lether is logical
Formula are as follows:
In formula, n are as follows: 1~5, R1For H or CH3, R2For C1-6Alkyl.
2. the method according to claim 1 for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil, special
Sign is that steps are as follows:
1) sodium hydroxide, ethanol-water solution are taken, reactor is added, stirs and is heated to 60-70 DEG C, is then added dropwise discarded edible
Vegetable oil is into reaction system, after reacting 2-5h, regulation system pH to 2~3, and the reaction was continued 1-5h is to terminating；Extracted with solvent
Mixture is taken, obtains organic phase, and be washed with deionized；Solvent and water are removed finally by the mode of vacuum distillation, is obtained
Sticky adopting dark liquid；
2) sticky adopting dark liquid, potassium hydroxide, ethylene glycol are taken, 165-190 DEG C of temperature control, is stirred to react 10-12h；Then it is added and goes
Ionized water, 90-110 DEG C of temperature control the reaction was continued 0.5-1h, is down to room temperature for reaction temperature；Adjust pH to 2~3；Extracted again with solvent
It takes organic phase and is washed with deionized；Solvent and water, the vegetable oil acid being conjugated are removed finally by vacuum distillation；
3) plant oil base acid, maleic anhydride, hydroquinone and the acetic acid of conjugation are taken, 105-130 DEG C of temperature control, nitrogen protection react 5-
7h；Then deionized water the reaction was continued under reflux conditions 0.5-1h is added, system temperature is down to room temperature；Organic phase solvent
Extraction, and spend ion-cleaning；Solvent and water finally are removed with the mode of vacuum distillation, obtains vegetable oil chitin；
4) vegetable oil chitin is taken, dihydric alcohol monoalky lether, catalyst, dehydrating agent reacts 5-8h at 120-150 DEG C；Pass through
Refinement treatment removes excessive dihydric alcohol monoalky lether and dehydrating agent, is washed out remaining liq to system pH to neutrality；Finally
By vacuum distillation dehydration, vegetable oil chitin alcohol ether-ether is obtained；Wherein, catalyst is p-methyl benzenesulfonic acid, sulfuric acid, four fourth of metatitanic acid
One of ester, stannous chloride, cation exchange resin, dosage are 0.5~5wt%；Dehydrating agent is in toluene or hexamethylene
One kind, dosage are 40~70wt%.
3. the method according to claim 2 for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil, special
Sign is, in step 1), first stirs and is heated to 60-70 DEG C, then discarded edible vegetable oil is added drop-wise in reaction system, instead
After answering 2h, with 0.5-1mol/L hydrochloric acid regulation system pH to 2~3, and after the reaction was continued 1h, reaction was completed.
4. the method according to claim 2 for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil, special
Sign is, in step 2), first reacts 10h under 180-190 DEG C of stirring, and deionized water is then added in 90-100 DEG C of reaction 0.5h
Afterwards, reaction temperature is down to room temperature.
5. the method according to claim 2 for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil, special
Sign is, in step 3), 5-6h is reacted under 105-120 DEG C, nitrogen protection, then be added deionized water under reflux conditions after
After continuous reaction 0.5h, system temperature is down to room temperature.
6. the described in any item method institutes for preparing vegetable oil chitin alcohol ether-ether using discarded edible vegetable oil of claim 1-5
The vegetable oil polyacid base alcohol ether-ether of acquisition.
7. vegetable oil polyacid base alcohol ether-ether according to claim 6, which is characterized in that its component includes:
Wherein, R1=H or CH3, R2=C1-C6Alkyl, n=1~5.
8. application of the vegetable oil chitin alcohol ether-ether as plasticizer described in claim 6 or 7.
9. application according to claim 8, it is characterised in that: by polylactic acid and vegetable oil chitin alcohol ether-ether in extruding machine
In carry out mixing extrusion molding；Then the polylactic acid sample for being mixed with vegetable oil chitin alcohol ether-ether is prepared on injection molding machine as needed
The product needed；Wherein, the mass ratio of plant oil base alcohol ether ester and polylactic acid are as follows: 5~20: 100.
10. application according to claim 9, it is characterised in that: using vegetable oil polyacid alcohol ether-ether as plasticizer, PVC is added
Powder and heat stabilizer first carry out mechanical premix, mixture are then carried out mixing extrusion molding, is prepared with uvioresistant performance
PVC material.
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| CN114805076A (en) * | 2022-03-03 | 2022-07-29 | 广州米奇化工有限公司 | Ester compound and preparation method, processing liquid and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126121A (en) * | 2020-09-03 | 2020-12-25 | 合肥飞木生物科技有限公司 | Method for preparing cold-resistant and extraction-resistant rubber plasticizer by using unsaturated fatty acid methyl ester |
| CN114805076A (en) * | 2022-03-03 | 2022-07-29 | 广州米奇化工有限公司 | Ester compound and preparation method, processing liquid and application thereof |
| CN114805076B (en) * | 2022-03-03 | 2024-01-23 | 广州米奇化工有限公司 | Ester compound and preparation method, processing liquid and application thereof |
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| CN109970556B (en) | 2022-02-22 |
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