CN106957227A - A kind of method for producing tung oil polyalcohol and by-product glycerol - Google Patents
A kind of method for producing tung oil polyalcohol and by-product glycerol Download PDFInfo
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- CN106957227A CN106957227A CN201610012119.XA CN201610012119A CN106957227A CN 106957227 A CN106957227 A CN 106957227A CN 201610012119 A CN201610012119 A CN 201610012119A CN 106957227 A CN106957227 A CN 106957227A
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- Prior art keywords
- tung oil
- acid
- reaction
- methyl ester
- oil methyl
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- 239000002383 tung oil Substances 0.000 title claims abstract description 96
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000006227 byproduct Substances 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 150000004702 methyl esters Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011187 glycerol Nutrition 0.000 claims abstract description 22
- 230000000640 hydroxylating effect Effects 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 239000003921 oil Substances 0.000 claims abstract description 15
- 229960002163 hydrogen peroxide Drugs 0.000 claims abstract description 13
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 9
- 239000008346 aqueous phase Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000012071 phase Substances 0.000 claims abstract description 8
- 238000013517 stratification Methods 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003377 acid catalyst Substances 0.000 claims abstract description 6
- 239000002585 base Substances 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000012423 maintenance Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 66
- 229920005862 polyol Polymers 0.000 claims description 25
- 150000003077 polyols Chemical class 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 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 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043276 diisopropanolamine Drugs 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229960004365 benzoic acid Drugs 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003279 phenylacetic acid Substances 0.000 claims description 2
- 229960003424 phenylacetic acid Drugs 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 235000010447 xylitol Nutrition 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000006735 epoxidation reaction Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 5
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 20
- 239000008158 vegetable oil Substances 0.000 description 20
- 239000003549 soybean oil Substances 0.000 description 15
- 235000012424 soybean oil Nutrition 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 229920005830 Polyurethane Foam Polymers 0.000 description 8
- 239000011496 polyurethane foam Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002118 epoxides Chemical group 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003626 triacylglycerols Chemical class 0.000 description 2
- 150000005671 trienes Chemical class 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- IUARXXMHEFWVIW-UHFFFAOYSA-N 3-ethyl-3-methyldioxirane Chemical compound CCC1(C)OO1 IUARXXMHEFWVIW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 241001048891 Jatropha curcas Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- -1 small molecule polyol Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for producing tung oil polyalcohol and by-product glycerol,（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, lower floor's glycerine is isolated after reaction, tung oil methyl ester is obtained；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Stirring is lower to be added dropwise hydrogenperoxide steam generator, and control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyalcohol.The present invention can improve epoxide group reactivity feature using the conjugated double bond of tung oil, tung oil methyl ester is carried out first, isolate glycerine, tung oil polyalcohol is prepared by raw material of tung oil methyl ester again, hydroxylating agent is added in epoxidation simultaneously, crosslinking side reaction can be prevented effectively from, the economy of whole technique is greatly improved.
Description
Technical field
The invention belongs to polyurethane material field, and in particular to a kind of method for producing tung oil polyalcohol and by-product glycerol.
Background technology
With petering out for Global Oil fossil resource, the development and utilization of biomass resource receives much concern.Vegetable oil is the triglycerides of the Long carbon chain acid containing double bond, and it is widely distributed in nature, and species is various, wherein common includes tung oil, soybean oil, linseed oil, corn oil, rapeseed oil, peanut oil, olive oil, palm oil, castor oil etc..Special construction and degradability, polymer therefrom not only low cost, and environmentally friendly that vegetable oil has by it, are widely used in the multiple fields such as polyurethane, biodiesel, coating, bio-medical.
The characteristics of polyurethane material is due to good mechanical performance with shaping is easy to, has been widely used in industry and daily life.Main raw material(s) for producing polyurethane includes isocyanates, polyalcohol and other additives, and the ratio of wherein polyalcohol account for more than 50%.In industrial processes, polyalcohol is mainly used in polyurethane field, thus polyurethane industries among others influence factor be also polyalcohol market major influence factors.Polyalcohol can be divided into PPG and PEPA by molecular structure, wherein, PPG is occupied an leading position in the market, occupies more than the 70% of whole polyalcohol demand.
Generally, polyalcohol is to extract to prepare from oil.And oil is used as non-renewable resources, scarcity causes the continuous rise of its price, and cause the price continuous rise of the primary raw material of the polynary alcohol production such as downstream product expoxy propane, oxirane, and according to current depletion rate, petroleum resources are depleted eventually.Therefore, from sustainable development and the angle of enterprise competitiveness, the new material and new technology that can substitute petroleum base polyethers are found as strategic development task.
The U.S. is the major producing country of soybean oil in the world, and in addition to edible, the scientific research institution in the U.S. is also actively working to develop the various chemical products by raw material of soybean oil, to substitute petroleum-based chemicals.Concentrate on recently using the unsaturated bond in soybean oil strand, by the modification to double bond, vegetable oil is occurred epoxidation, hydroxylating, so as to prepare soybean oil polyol.The advantage of the method is that reaction temperature is relatively low（40-70℃）, product qualities, color and luster are good, so obtained extensive concern.
The Z.S. in kansas, U.S.A (Kansas) polymer research center
Petrovic etc. is reacted with peroxy acid with soybean oil, is prepared for epoxidized soybean oil, double bond is changed into epoxy radicals；Then under the catalytic action of effective catalyst tetrafluoro boric acid with water and alcohol ring-opening reaction occurs for epoxidized soybean oil, prepare the vegetable oil polyol containing hydroxyl, the hydroxyl value of polyalcohol is 110-213mgKOH/g, and viscosity is 1000-7000mPas, and conversion ratio is up to 85%-95%.
US20070123725 provides a kind of method for preparing soybean oil polyol, includes the epoxidation and hydroxylation procedures of polyunsaturated vegetable oil, forms vegetable oil-based polyether polyol.First, by the polyunsaturated vegetable oils such as soybean oil or rapeseed oil and organic acid and hydroperoxidation, epoxidized vegetable oil is formed, the mixed solution of epoxidized vegetable oil and first alcohol and water is then subjected to ring-opening reaction generation vegetable oil polyol.
US20060041157 describes the method for preparing soybean oil polyol, vegetable oil including making PART EPOXY reacts under catalysts conditions with Ring Opening Reagent, oligomeric vegetable oil polylol is formed, Ring Opening Reagent includes small molecule polyol, vegetable oil polyol or other polyols.The degree of functionality of oligomeric vegetable oil polyalcohol is 1-6, and hydroxyl value is 20-300mgKOH/g.
Tung oil is a kind of important raw material of industry and traditional exporting.At present, the annual production of China's tung oil accounts for 35% or so of world's tung oil yield up to more than 100,000 tons.Therefore, study tung oil and make more Product industrializations relevant with tung oil that there is special significance.But, high-quality vegetable oil polyol is prepared using tung oil, because tung oil degree of unsaturation is higher, and be unique polyunsaturated vegetable oil with conjugated double bond in nature, iodine number reaches more than 170, wherein more than 85% unsaturated bond is carbon carbon conjugated triene key, so tung oil prepare polyalcohol it is epoxidised during because the presence of conjugated double bond makes epoxide group reactivity higher, poor selectivity, easily occurs side reaction, so as to generate macromolecules cross-linking product, viscosity is caused to sharply increase, it is normally solid at room temperature, further synthesis of polyurethane material can not be used for.Research Literature（Such as Epoxidation of Natural
Triglycerides with Ethylmethyldioxirane,《Journal of the American Oil Chemists' Society》, 1996,73：461-464）Different vegetable oil are investigated, such as corn oil, soybean oil, sunflower oil, cottonseed oil, the epoxidation process of tung oil polyunsaturated vegetable oil, it is again seen that only the tung oil with conjugated double bond there occurs cross-linking reaction during epoxidised, viscosity is caused to increased dramatically, it is impossible to for preparing polyurethane material.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of method for producing tung oil polyalcohol and by-product glycerol.The characteristics of present invention can improve epoxide group reactivity using the conjugated double bond of tung oil, tung oil methyl ester is carried out first, isolate glycerine, then tung oil polyalcohol is prepared by raw material of tung oil methyl ester, epoxidised while adding hydroxylating agent, the generation of crosslinking side reaction can be effectively prevented from, and forms tung oil polyol product, the economy of whole production technology is significantly improved.
The method of present invention production tung oil polyalcohol and by-product glycerol, including following content：（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, product isolates lower floor's glycerine after reaction, then through washing, vacuum distillation, obtains tung oil methyl ester；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Lower dropwise addition hydrogenperoxide steam generator is stirred vigorously, control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyol product.
Step（1）Described methanol and the alcohol oil quality ratio of tung oil are 0.1:1-0.3:1.Described base catalyst is the one or more in potassium hydroxide, NaOH, lithium hydroxide, calcium hydroxide etc., preferably potassium hydroxide；The consumption of base catalyst is the 0.5%-1.5% of tung oil quality.
Step（1）Described tung oil methyl esterization reaction is 55-65 DEG C of progress under agitation, and the reaction time is 15-30min.
Step（1）Described washing temperature is 40-60 DEG C；Vacuum distillation is the residual methanol and moisture in removing system under the conditions of pressure 1000-3000Pa, 50-80 DEG C of temperature.
Step（2）Described acid catalyst is the one or more in sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid ion exchange resin etc., preferably sulfuric acid；Consumption is the 0.01%-1.0% of tung oil methyl ester quality.
Step（2）Described carboxylic acid can be the one or more in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid etc., preferably formic acid.Carboxylic acid can be with hydrogenperoxide steam generator reaction generation peroxycarboxylic acid, peroxycarboxylic acid makes the conjugated double bond in tung oil methyl ester be converted into epoxy bond, discharge carboxylic acid simultaneously, therefore while epoxy bond is generated, carboxylic acid is not consumed, but very few carboxylic acid content will cause system reaction rate slack-off, so it is 0.05 to control carboxylic acid and the mass ratio of tung oil methyl ester:1-0.5:1.
Step（2）Described hydroxylating agent can be alcohols or alcamines, and consumption is 0.5-2 times of tung oil methyl ester quality.One or more of the wherein described alcohols hydroxylating agent in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, BDO, pentaerythrite, xylitol, sorbierite etc., preferably butanol；One or more of the alcamines hydroxylating agent in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine etc., preferably triethanolamine.
Step（2）The consumption of the deionized water is 0.01-0.2 times of tung oil methyl ester quality, and the addition of deionized water can prevent the esterification of initial reaction stage carboxylic acid and hydroxylating agent, it is to avoid the consumption of carboxylic acid, increases double bond conversion rate.
Step（2）The hydrogenperoxide steam generator plays a part of oxidant, carboxylic acid is oxidized to peroxy acid.The concentration of hydrogen peroxide is higher, reacts more violent, system heat release is serious, easily occurs side reaction, so selection hydrogenperoxide steam generator concentration is 20wt%-60wt%, consumption is 0.6-1.2 times of tung oil methyl ester quality.
Step（3）The neutralization reaction can use ammoniacal liquor, sodium carbonate or sodium acid carbonate, preferably use the sodium bicarbonate aqueous solution that concentration is 5wt%-20wt% and neutralize.Described washing temperature is 50-80 DEG C, to prevent that emulsion from occurring in system.Described vacuum distillation is the hydroxylating agent and residual moisture in removing system under the conditions of pressure 1000-3000Pa, 60-120 DEG C of temperature, product moisture content is less than 0.1wt%.
What tung oil polyalcohol of the present invention was prepared by the invention described above method.Prepared tung oil polyol product hydroxyl value is 120-270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, available for preparing polyurethane material.
Tung oil is carbon carbon conjugated triene key due in molecule more than 85% unsaturated bond, makes epoxide group reactivity higher during polyalcohol is prepared, poor selectivity, easily occurs side reaction, so as to generate macromolecules cross-linking product, viscosity is caused to sharply increase, it is impossible to for further synthesis of polyurethane material.It is direct using vegetable oil as raw material compared in traditional plant oil polyalcohol preparation technology, the present invention carries out esterification first by raw material of tung oil, glycerine in tung oil is cemented out, isolate the glycerin by-products of high added value, then vegetable oil polyol is prepared by raw material of tung oil methyl ester, because the conjugated double bond of tung oil methyl ester still has the characteristics of improving epoxide group reactivity（The conjugated double bond structures that tung oil methyl esterization reaction will not be destroyed in tung oil）, the generation of crosslinking side reaction can be avoided, therefore epoxidised while addition hydroxylating agent, can be effectively prevented from the generation of crosslinking side reaction, formation meets desired tung oil polyol product, it is adaptable to the preparation of polyurethane material.In addition, in system add 1 ton of methanol about it is replaceable go out 0.4-0.5 tons of glycerol products, and excessive methanol can be recycled and reused by distillation technique, the market price of glycerine is 7500-8000 yuan/ton, and methanol is about 3000 yuan/ton, so present invention process can greatly improve the economy of whole technique.
Tung oil polyalcohol prepared by the present invention has the advantages that raw material is renewable, non-toxic and biological degradability is good, belongs to environment-friendly biopolyol compared with petroleum-based polyols.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of tung oil polyalcohol prepared by the present invention.
Embodiment
The inventive method is described further with reference to embodiment.In the present invention, wt% represents mass fraction.
The hydroxyl value of tung oil polyol product prepared by the present invention is determined according to the phthalic anhydride esterification method in GB/T12008.3-2009, and viscosity is determined according to the rotation viscometer method in GB/T 12008.7-2010.
Embodiment 1
800g tung oil, 160g methanol, 8g potassium hydroxide are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates rear stratification, isolates lower floor glycerol product 76.2g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 249mgKOH/g, viscosity 7700mPas, acid number 0.78mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.2%, available for preparing hard polyurethane foam product.
Embodiment 2
800g tung oil, 100g methanol, 4g NaOH are added in 2L autoclaves, it is stirred reaction, reaction temperature is 55 DEG C, reaction time is 30min, reaction terminates rear stratification, isolates lower floor glycerol product 70.8g, then with 40 DEG C of hot wash upper strata products 4 times, and the product after washing is distilled into 2h under the conditions of 3000Pa, 50 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 35 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 40 DEG C or so, after completion of dropping, and the constant temperature 5h at 40 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 162mgKOH/g, viscosity 2850mPas, acid number 0.63mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.9%, available for preparing polyurethane products.
Embodiment 3
800g tung oil, 220g methanol, 12g calcium hydroxides are added in 2L autoclaves, it is stirred reaction, reaction temperature is 65 DEG C, reaction time is 15min, reaction terminates rear stratification, isolates lower floor glycerol product 79.4g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 125g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 300g butanol, 50g deionized waters, be warming up to 45 DEG C and stir.Then 30wt% hydrogenperoxide steam generator 450g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 65 DEG C or so, after completion of dropping, and the constant temperature 3h at 65 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 232mgKOH/g, viscosity 9700mPas, acid number 0.88mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.0%, available for preparing hard polyurethane foam product.
Embodiment 4
800g tung oil, 120g methanol, 10g lithium hydroxides are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates rear stratification, isolates lower floor glycerol product 70.8g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 80g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 4g concentrated sulfuric acids, 250g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 40wt% hydrogenperoxide steam generator 350g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 187mgKOH/g, viscosity 14200mPas, acid number 0.91mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.3%, available for preparing hard polyurethane foam product.
Embodiment 5
800g tung oil, 180g methanol, 10g potassium hydroxide are added in 2L autoclaves, it is stirred reaction, reaction temperature is 60 DEG C, reaction time is 20min, reaction terminates stratification, isolates lower floor glycerol product 78.6g, then with 50 DEG C of hot wash upper strata products 3 times, and the product after washing is distilled into 2h under the conditions of 2000Pa, 60 DEG C, obtain tung oil methyl ester.
Tung oil methyl ester, the 150g formic acid of the above-mentioned preparations of 500g are added in 2000mL there-necked flasks（85wt% solution）, the 0.5g concentrated sulfuric acids, 500g butanol, 50g deionized waters, be warming up to 40 DEG C and stir.Then 20wt% hydrogenperoxide steam generator 500g are slowly added dropwise under intense agitation, control drop rate makes reaction temperature maintain 50 DEG C or so, after completion of dropping, and the constant temperature 4h at 50 DEG C, reaction terminates.After question response system layering, aqueous phase is removed, oil phase is washed with 10wt% sodium bicarbonate aqueous solutions to neutrality, then with 70 DEG C of hot wash products 3 times.Product after washing is distilled into 2h under the conditions of 2000Pa, 80 DEG C, tung oil polyol product is produced.After testing, hydroxyl value is 227mgKOH/g, viscosity 6840mPas, acid number 0.71mgKOH/g, and moisture is less than 0.1wt%, and yield is 93.0%, available for preparing hard polyurethane foam product.
Embodiment 6
With treatment process condition same as Example 1, difference is that the hydroxylating agent added in step 2 is 300g ethanol, and tung oil polyol product is made.After testing, hydroxyl value is 220mgKOH/g, viscosity 11800mPas, acid number 0.86mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.6%, available for preparing hard polyurethane foam product.
Embodiment 7
Using treatment process condition same as Example 1, difference is that the hydroxylating agent added is 300g triethanolamines, and tung oil polyol product is made.After testing, hydroxyl value is 223mgKOH/g, viscosity 12100mPas, acid number 0.87mgKOH/g, and moisture is less than 0.1wt%, and yield is 92.5%, available for preparing hard polyurethane foam product.
Embodiment 8
Using treatment process condition same as Example 1, difference is that carboxylic acid uses 125g glacial acetic acids in step 2.After testing, hydroxyl value is 132mgKOH/g, viscosity 2100mPas, and moisture is less than 0.1wt%, and yield is 92.1%, available for preparing polyurethane products.
Embodiment 9
Using treatment process condition same as Example 1, difference is that acid catalyst uses 0.5g phosphoric acid in step 2.After testing, hydroxyl value is 231mgKOH/g, viscosity 7340mPas, and moisture is less than 0.1wt%, and yield is 92.7%, available for preparing hard polyurethane foam product.
Comparative example 1
Using treatment process condition same as Example 1, difference is to be added without hydroxylating agent in step 2.The viscosity 415000mPas of product, because product viscosity is excessive and can not dissolve, it is impossible to further carry out hydroxylating, therefore product is not used to prepare hard polyurethane foam product.
Comparative example 2
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using soybean oil as raw material.After testing, hydroxyl value is 6.4mgKOH/g, and due to soybean oil methyl esters, not occur hydroxylating, hydroxyl value in step 2 too low, therefore product is not used to prepare polyurethane products.
Comparative example 3
Using treatment process condition same as Example 1, difference is to prepare polyalcohol using Jatropha curcas oil as raw material.After testing, hydroxyl value is 4.8mgKOH/g, and due to soybean oil methyl esters, not occur hydroxylating, hydroxyl value in step 2 too low, therefore product is not used to prepare polyurethane products.
Claims (12)
1. a kind of method for producing tung oil polyalcohol and by-product glycerol, it is characterised in that including following content：（1）It is added to after tung oil, methanol and base catalyst are mixed in proportion in autoclave, carries out tung oil methyl ester reaction, lower floor's glycerine is isolated after reaction, then through washing, vacuum distillation, obtains tung oil methyl ester；（2）Tung oil methyl ester and carboxylic acid, acid catalyst, hydroxylating agent, deionized water are mixed in proportion, 35-45 DEG C is warming up to；Lower dropwise addition hydrogenperoxide steam generator is stirred vigorously, control rate of addition makes reaction maintain after 40-65 DEG C, completion of dropping, maintenance reaction temperature 3-5h；（3）Reaction terminates rear stratification, isolates aqueous phase, oil phase is neutralized, washing, vacuum distillation, obtain tung oil polyol product.
2. according to the method described in claim 1, it is characterised in that：Step（1）Described methanol and the alcohol oil quality ratio of tung oil are 0.1:1-0.3:1.
3. according to the method described in claim 1, it is characterised in that：Step（1）Described base catalyst is the one or more in potassium hydroxide, NaOH, lithium hydroxide, calcium hydroxide, and consumption is the 0.5%-1.5% of tung oil quality.
4. according to the method described in claim 1, it is characterised in that：Step（1）Described tung oil methyl esterization reaction is 55-65 DEG C of progress under agitation, and the reaction time is 15-30min.
5. according to the method described in claim 1, it is characterised in that：Step（1）Described washing temperature is 40-60 DEG C；Vacuum distillation is the residual methanol and moisture in removing system under the conditions of pressure 1000-3000Pa, 50-80 DEG C of temperature.
6. according to the method described in claim 1, it is characterised in that：Step（2）Described acid catalyst is the one or more in sulfuric acid, phosphoric acid, hydrochloric acid, sulfonic acid ion exchange resin, and consumption is the 0.01%-1.0% of tung oil methyl ester quality.
7. according to the method described in claim 1, it is characterised in that：Step（2）Described carboxylic acid is the one or more in formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, phenylacetic acid etc., and it is 0.05 to control carboxylic acid and the mass ratio of tung oil methyl ester:1-0.5:1.
8. according to the method described in claim 1, it is characterised in that：Step（2）Described hydroxylating agent is alcohols or alcamines, and consumption is 0.5-2 times of tung oil methyl ester quality.
9. method according to claim 8, it is characterised in that：One or more of the described alcohols hydroxylating agent in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol, glycerine, butanol, 1,4- butanediols, pentaerythrite, xylitol, sorbierite；One or more of the alcamines hydroxylating agent in monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, monoethanolamine, diethanol amine, triethanolamine.
10. according to the method described in claim 1, it is characterised in that：Step（2）The consumption of the deionized water is 0.01-0.2 times of tung oil methyl ester quality；The hydrogenperoxide steam generator concentration is 20wt%-60wt%, and consumption is 0.6-1.2 times of tung oil methyl ester quality.
11. according to the method described in claim 1, it is characterised in that：Step（3）The neutralization reaction concentration neutralizes for 5wt%-20wt% sodium bicarbonate aqueous solution；The washing temperature is 50-80 DEG C；The vacuum distillation is the hydroxylating agent and residual moisture in removing system under the conditions of pressure 1000-3000Pa, 60-120 DEG C of temperature, product moisture content is less than 0.1wt%.
12. tung oil polyalcohol prepared by any methods describeds of claim 1-11, it is characterised in that：The product hydroxyl value of prepared tung oil polyalcohol is 120-270mgKOH/g, and acid number is less than 1.0mgKOH/g, and moisture is less than 0.1wt%, and yield is higher than 92%, available for preparing polyurethane material.
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