TWI665185B - 一種使用環氧脂肪酸烷基酯類製備生質多元醇之方法 - Google Patents
一種使用環氧脂肪酸烷基酯類製備生質多元醇之方法 Download PDFInfo
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- TWI665185B TWI665185B TW107140293A TW107140293A TWI665185B TW I665185 B TWI665185 B TW I665185B TW 107140293 A TW107140293 A TW 107140293A TW 107140293 A TW107140293 A TW 107140293A TW I665185 B TWI665185 B TW I665185B
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- Prior art keywords
- fatty acid
- acid alkyl
- alkyl ester
- epoxy fatty
- preparing
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 59
- 239000000194 fatty acid Substances 0.000 title claims abstract description 59
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 59
- 229920005862 polyol Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 46
- -1 fatty acid esters Chemical class 0.000 title claims description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 69
- 150000003077 polyols Chemical class 0.000 claims abstract description 55
- 239000002028 Biomass Substances 0.000 claims abstract description 40
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 31
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 24
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002608 ionic liquid Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 229940049964 oleate Drugs 0.000 claims description 12
- 239000003225 biodiesel Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 9
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
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- 150000002148 esters Chemical class 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
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- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 3
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
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- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- 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
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- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
- C07C27/26—Purification; Separation; Stabilisation
- C07C27/34—Purification; Separation; Stabilisation by extraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
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- B01J2531/002—Materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
本發明係一種利用環氧脂肪酸烷基酯類製備生質多元醇之方法，使用
酸性離子液體為催化劑，催化環氧脂肪酸烷基酯與開環試劑合成生質多元醇，所合成的生質多元醇可用於製備生質聚氨酯及生質聚氨酯發泡材等。本製程中所使用的酸性離子液體可有效催化酯化、環氧化及開環羥基化反應等以合成生質多元醇，且具有容易分離、可回收再使用、減廢的優點。
Description
本發明係關於製備生質多元醇之方法，特別是指一種利用布倫斯特酸性離子液體催化環氧脂肪酸烷基酯進行羥基化反應之方法。
多元醇可應用於製作聚氨酯材料、聚氨酯發泡材、人造皮革、塗料、接著劑等，一般常用來合成聚氨酯的多元醇有聚酯多元醇、聚醚多元醇等，聚酯多元醇常以己二酸及二元醇經縮合聚合而得，其具耐高溫性、耐候性及耐磨性佳等優點，但耐水解性較差。聚醚多元醇可由環氧乙烷、環氧丙烷或四氫呋喃等開環聚合而得，依照不同用途可合成阻燃型聚醚多元醇、接枝型聚醚多元醇等，聚醚多元醇因柔軟性、延伸性及耐水解性佳，為廣泛使用之多元醇。然而製備多元醇之原料大多為石化來源，石化燃料與石化產品的合成及使用過程會造成大量溫室氣體的排放，石化產品的廢棄物處理方式也成為一大隱憂，基於節能減碳及環保兩大議題，生質材料的發展已成為當今全球的趨勢。
植物油來源廣且價格便宜，是廣為使用的生質原料，利用油脂鏈上的不飽和雙鍵可將其改質為生質多元醇，該油脂基生質多元醇可完全
分解，其通常具高官能基數，所製備之生質聚氨酯材料耐水解性、耐熱性佳，可取代石化來源之聚醚、聚酯多元醇，現已實際應用於汽車座墊、座椅靠背、鞋底等。
緣此，目前生質多元醇常以植物油為原料，利用其不飽和雙鍵進行環氧化及羥基化反應，環氧基的開環羥基化反應通常使用強酸如硫酸(如美國專利號US9216940)、三氟化硼(BF3)、氟硼酸(如美國專利號US6433121)、磷酸(如中國專利公告號CN104672113)等作為催化劑，其腐蝕性強、可能造成原料或產物碳化、無法回收再利用、反應後需使用大量強鹼水溶液中和，增加後處理成本且產生大量廢水，其中三氟化硼於潮濕空氣中會發煙、具有劇毒，於反應操作上更加危險。為避免前述問題，有學者使用固體酸觸媒(如中國專利公開號CN104725210)以沸石、高嶺土、蒙脫石等負載過酸金屬鹽催化羥基化反應合成油脂基生質多元醇。
此外，除使用強酸作為催化劑外，亦可選用無機鹼催化劑，如鹼金屬氫氧化物或鹼金屬烷氧化物，或使用有機鹼如有機胺化合物等催化開環羥基化反應(如中國專利公告號CN100465152、CN100390128、CN101125912)，使用有機鹼催化劑可避免反應槽及管線腐蝕問題，但反應後需使用酸性物質中和再加入吸附劑吸附，不但增加成本且觸媒不易回收再使用。
近年來，離子液體因蒸氣壓低、可調整酸鹼性、毒性低等優點，逐漸備受矚目。酸性離子液體可用於催化酯化反應、轉酯化反應、環氧化反應(如中國專利公告號CN101735175、CN10287007)、開環羥基化反應(如中國專利公告號CN104341297)等，於反應結束後可進行回收再使用，成功
克服強酸、鹼催化製程之缺點。
本發明的目的在於使用生質原料以綠色製程製備生質多元醇，並克服習知使用強酸或鹼催化製程之缺點。為達以上目的，本發明之方法係利用酸性離子液體為觸媒，催化環氧脂肪酸烷基酯與醇類進行羥基化反應合成生質多元醇，生質多元醇可取代石化來源多元醇做為聚氨酯材料、聚氨酯發泡材、人造皮革、塗料、接著劑等之原料。羥基化反應製程為綠色製程，不需使用溶劑，反應後僅需使用去離子水及弱鹼水溶液萃取，觸媒分離容易、可重複使用，並可有效減廢及減少管線腐蝕。
本發明中所使用的環氧脂肪酸烷基酯類可為脂肪酸烷基酯類之環氧化物，如環氧油酸烷基酯類、環氧亞油酸烷基酯類、環氧亞麻酸烷基酯類或其混合物，其中脂肪酸烷基酯類可由植物油、動物油或廢食用油經轉酯化製得，油酸烷基酯類、亞油酸烷基酯類、亞麻酸烷基酯類可由油酸、亞油酸、亞麻酸與醇類酯化而得。
本發明中羥基化反應所使用的醇類可為單元醇或多元醇或其混合物，單元醇如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇及其異構物，多元醇如乙二醇、丙二醇、丁二醇及其異構物、丙三醇(甘油)…等。
本發明中做為催化劑的酸性離子液體為布倫斯特酸性離子液體(BRØNSTED ACID IL)，主要是由烷基磺酸取代吡啶兩性化合物與布倫斯特酸結合而得。布倫斯特酸性離子液體製備方式簡單，且利用酸性離子液體進行環氧脂肪酸烷基酯類的羥基化反應可成功克服傳統強酸、鹼催化製程
之缺點。傳統強酸、鹼催化製程較難將開環試劑與觸媒有效分離再利用，除了需使用大量水清洗，亦需要額外添加強鹼或酸將產物、廢水中和，酸性離子液體具高選擇性、耐水性佳、後處理容易、可重複使用等優點。反應結束後將反應溶液以去離子水萃取分層，將水層濃縮乾燥後即可回收酸性離子液體，離子液體可重複使用，反應中過量的開環試劑可有效與離子液體分離並迴流至反應器中再使用，可有效降低製程成本
本發明提供一種使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其包含步驟如下：以烷基磺酸取代吡啶兩性化合物與布倫斯特強酸合成為布倫斯特酸性離子液體，其中烷基磺酸取代吡啶兩性化合物與布倫斯特強酸之莫耳比，係介於1.0至1.5之間；環氧脂肪酸烷基酯類與布倫斯特酸性離子液體依比例混合，並加入醇類作為開環試劑形成反應溶液，將反應溶液升溫至攝氏30℃至100℃之間並維持1至24小時進行開環羥基化反應，其中醇類與環氧脂肪酸烷基酯類之莫耳比係介於4至20之間，布倫斯特酸性離子液體與環氧脂肪酸烷基酯類之莫耳比係介於0.01至0.15之間；以及將反應溶液以去離子水萃取後靜置分層成為上層溶液與下層溶液，將下層溶液濃縮乾燥後得可回收再使用之離子液體，將上層溶液以弱鹼水溶液及去離子水洗滌後除水得生質多元醇。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中，烷基磺酸取代吡啶兩性化合物中，烷基係為CnH2n，其中n係為3至6之正整數。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中布倫斯特強酸係為磷酸、硫酸、甲基磺酸、苯磺酸或對甲苯磺酸其中之一。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中布倫斯特酸性離子液體中之烷基磺酸取代吡啶兩性化合物與布倫斯特強酸之莫耳比，更進一步介於1.0至1.2之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中環氧脂肪酸烷基酯類係為脂肪酸烷基酯之環氧化物，脂肪酸烷基酯係為生質柴油、或不飽和脂肪酸烷基酯類、或生質柴油及不飽和脂肪酸烷基酯類之混合物，其中生質柴油係為植物油、動物油或廢食用油經轉酯化製得之脂肪酸甲酯，其中不飽和脂肪酸酯類係為油酸烷基酯類、亞油酸烷基酯類、亞麻酸烷基酯類其中之一或二者以上之混合物。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該醇類為單元醇、或多元醇、或單元醇及多元醇之混合物，單元醇係為甲醇、乙醇、丙醇、丁醇、及其異構物其中之一，多元醇係為乙二醇、丙二醇、丁二醇及其異構物、丙三醇(甘油)其中之一。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中生質柴油之環氧化物之開環羥基化反應時間係介於1至20小時之間，不飽和脂肪酸烷基酯類之環氧化物之開環羥基化反應時間係介於4至24小時之間，以及生質柴油及不飽和脂肪酸烷基酯類之環氧化物之開環羥基化反應時間係介於1至20小時之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中醇類與環氧脂肪酸烷基酯類之莫耳比更進一步係介於4至12之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中布倫斯特酸性離子液體與環氧脂肪酸烷基酯類之莫耳比更進一步係介於
0.05至0.12之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中布倫斯特酸性離子液體與環氧脂肪酸烷基酯類之莫耳比更進一步係介於0.05至0.10之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中開環羥基化反應溫度進一步係介於攝氏40℃至80℃之間。
所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中開環羥基化反應溫度進一步係介於40℃至60℃之間。
由於本發明係揭露一種使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中，所使用之化學計量原理及方法等相關基礎已為相關技術領域具有通常知識者所能明瞭，故以下文中之說明，不再作完整描述，盍先敘明。
首先，先將醇類與環氧脂肪酸烷基酯的進料莫耳比控制在範圍介於4至12之間，催化劑布倫斯特酸性離子液體與環氧脂肪酸烷基酯的莫耳比控制在範圍介於0.01至0.15之間，反應溫度控制在攝氏40℃至80℃之間，於常壓環境下反應1至24小時。當反應結束後，以去離子水萃取後靜置分層，得到上層及下層，下層為離子液體及未反應醇類，經濃縮乾燥後得可
回收再使用之離子液體；上層以去離子水及鹼水萃取後除水得生質多元醇，生質多元醇的產率由1H NMR(核磁共振氫譜)分析約為60%至70%以上。
以下為驗證本發明所述技術之相關實施例，但本發明不限於下列實施例。
實施例一係將環氧脂肪酸甲酯與單元醇加入反應器中，單元醇與環氧脂肪酸甲酯的莫耳比範圍介於4至10之間，並加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧脂肪酸甲酯的莫耳比範圍介於0.05至0.10之間，於範圍介於攝氏40℃至60℃之間的溫度持續反應4至20小時，於反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，羥值為179mgKOH/g。
實施例二係將環氧脂肪酸甲酯與多元醇加入反應器中，多元醇與環氧脂肪酸甲酯的莫耳比範圍介於4至8之間，加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧脂肪酸甲酯的莫耳比範圍介於0.05至0.10之間，在範圍介於攝氏40℃至80℃之間的溫度持續反應1至20小時，當反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，羥值範圍介於309至322mgKOH/g之間。
實施例三係將環氧油酸甲酯與甲醇加入反應器中，甲醇與環氧油酸甲酯的莫耳比範圍介於4至10之間，並加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧油酸甲酯的莫耳比範圍介於0.05至0.10之間，在40℃的溫度下持續反應16至24小時，當反應停止後以去離子水萃取靜置分層，
得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，羥值為170mgKOH/g。
實施例四係將環氧油酸甲酯與多元醇加入反應器中，多元醇與環氧油酸甲酯的莫耳比範圍介於4至10之間，並加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧油酸甲酯的莫耳比範圍介於0.05至0.10之間，在溫度介於40℃至80℃之間持續反應4至20小時，反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，羥值範圍介於319至408mgKOH/g之間。
實施例五係將環氧脂肪酸丁酯與單元醇加入反應器中，單元醇與環氧脂肪酸丁酯的莫耳比範圍介於6至12之間，並加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧油酸丁酯的莫耳比範圍介於0.05至0.15之間，並在溫度介於攝氏40℃至60℃之間持續反應16至24小時，當反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，羥值範圍介於263至293mgKOH/g之間。
實施例六係將環氧脂肪酸丁酯與多元醇加入反應器中，多元醇與環氧脂肪酸丁酯的莫耳比範圍介於6至12之間，並加入布倫斯特酸性離子液體做為催化劑，催化劑與環氧油酸丁酯的莫耳比範圍介於0.05至0.15之間，並在攝氏溫度介於40℃至80℃範圍下持續反應4至20小時，當反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，
羥值範圍介於204至269mgKOH/g之間。
實施例七係將環氧脂肪酸甲酯及回收離子液體加入反應器中並預熱至攝氏40℃，再加入多元醇持續反應20至24小時，當反應停止後以去離子水萃取靜置分層，得到上層與下層，下層濃縮乾燥後得可回收再使用之離子液體，上層以去離子水及弱鹼水溶液萃取後除水得生質多元醇，重複上述步驟至產物羥值明顯下降為止。本實施例中，離子液體回收使用3次，產物羥值分別為286、266、286mgKOH/g。
實施例八係將100份實施例二中之生質多元醇加入1至10份發泡劑、0.1至0.5份錫催化劑、0.1至1份胺催化劑、1份界面活性劑，並以機械攪拌混合均勻，再加入50份硬化劑混合均勻後倒入模具，於室溫下持續反應，得到聚氨酯發泡材料。
從以上實施例的陳述，本發明的目的在於使用生質原料以綠色製程製備生質多元醇，並克服習知使用強酸或鹼催化製程之缺點。為達以上目的，本發明之方法係利用酸性離子液體為觸媒，催化環氧脂肪酸烷基酯與醇類進行羥基化反應合成生質多元醇，生質多元醇可取代石化來源多元醇做為聚氨酯材料、聚氨酯發泡材、人造皮革、塗料、接著劑等之原料。羥基化反應製程為綠色製程，不需使用溶劑，反應後僅需使用去離子水及弱鹼水溶液萃取，觸媒分離容易、可重複使用，並可有效減廢及減少管線腐蝕。
Claims (12)
- 一種使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其包含步驟如下：以一烷基磺酸取代一吡啶兩性化合物與一布倫斯特強酸合成為一布倫斯特酸性離子液體，其中該烷基磺酸取代該吡啶兩性化合物與該布倫斯特強酸之莫耳比，係介於1.0至1.5之間；一環氧脂肪酸烷基酯類與該布倫斯特酸性離子液體依比例混合，並加入一醇類作為開環試劑形成一反應溶液，將該反應溶液升溫至攝氏30℃至100℃之間並維持1至24小時進行開環羥基化反應，其中該醇類與該環氧脂肪酸烷基酯類之莫耳比係介於4至20之間，該布倫斯特酸性離子液體與該環氧脂肪酸烷基酯類之莫耳比係介於0.01至0.15之間；以及將該反應溶液以一去離子水萃取後靜置分層成為一上層溶液與一下層溶液，將該下層溶液濃縮乾燥後得可回收再使用之一離子液體，將該上層溶液以一弱鹼水溶液及該去離子水洗滌後除水得一生質多元醇。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該烷基磺酸取代該吡啶兩性化合物中，烷基係為CnH2n，其中n係為3至6之正整數。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該布倫斯特強酸係為磷酸、硫酸、甲基磺酸、苯磺酸或對甲苯磺酸其中之一。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該布倫斯特酸性離子液體中之該烷基磺酸取代該吡啶兩性化合物與該布倫斯特強酸之莫耳比，更進一步介於1.0至1.2之間。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該環氧脂肪酸烷基酯類係為一脂肪酸烷基酯之環氧化物，該脂肪酸烷基酯係為一生質柴油、或一不飽和脂肪酸烷基酯類、或該生質柴油及該不飽和脂肪酸烷基酯類之混合物，其中該生質柴油係為植物油、動物油或廢食用油經轉酯化製得之一脂肪酸甲酯，其中該不飽和脂肪酸酯類係為油酸烷基酯類、亞油酸烷基酯類、亞麻酸烷基酯類其中之一或二者以上之混合物。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該醇類為一單元醇、或一多元醇、或該單元醇及該多元醇之混合物，該單元醇係為甲醇、乙醇、丙醇、丁醇、及其異構物其中之一，該多元醇係為乙二醇、丙二醇、丁二醇及其異構物、丙三醇其中之一。
- 如申請專利範圍第5項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該生質柴油之環氧化物之開環羥基化反應時間係介於1至20小時之間，該不飽和脂肪酸烷基酯類之環氧化物之開環羥基化反應時間係介於4至24小時之間，以及該生質柴油及該不飽和脂肪酸烷基酯類之環氧化物之開環羥基化反應時間係介於1至20小時之間。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該醇類與該環氧脂肪酸烷基酯類之莫耳比更進一步係介於4至12之間。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該布倫斯特酸性離子液體與該環氧脂肪酸烷基酯類之莫耳比更進一步係介於0.05至0.12之間。
- 如申請專利範圍第9項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中該布倫斯特酸性離子液體與該環氧脂肪酸烷基酯類之莫耳比更進一步係介於0.05至0.10之間。
- 如申請專利範圍第1項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中開環羥基化反應溫度進一步係介於攝氏40℃至80℃之間。
- 如申請專利範圍第11項所述之使用環氧脂肪酸烷基酯類製備生質多元醇之方法，其中開環羥基化反應溫度進一步係介於40℃至60℃之間。
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