CN101597367B - Preparation method of polyurethane based on vegetable oil and lactic acid - Google Patents
Preparation method of polyurethane based on vegetable oil and lactic acid Download PDFInfo
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- CN101597367B CN101597367B CN2008101170343A CN200810117034A CN101597367B CN 101597367 B CN101597367 B CN 101597367B CN 2008101170343 A CN2008101170343 A CN 2008101170343A CN 200810117034 A CN200810117034 A CN 200810117034A CN 101597367 B CN101597367 B CN 101597367B
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 27
- 239000004310 lactic acid Substances 0.000 title claims abstract description 27
- 235000015112 vegetable and seed oil Nutrition 0.000 title claims abstract description 22
- 239000008158 vegetable oil Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004814 polyurethane Substances 0.000 title abstract description 9
- 229920002635 polyurethane Polymers 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003921 oil Substances 0.000 claims description 27
- 235000019198 oils Nutrition 0.000 claims description 27
- 235000012424 soybean oil Nutrition 0.000 claims description 23
- 239000003549 soybean oil Substances 0.000 claims description 23
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 22
- 235000013311 vegetables Nutrition 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- -1 diisocyanate compound Chemical class 0.000 claims description 12
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 210000000582 semen Anatomy 0.000 claims description 4
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000004593 Epoxy Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 102000004882 Lipase Human genes 0.000 abstract 1
- 108090001060 Lipase Proteins 0.000 abstract 1
- 239000004367 Lipase Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 235000019421 lipase Nutrition 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 12
- 238000010792 warming Methods 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- GRELGUDMSKNQIE-UHFFFAOYSA-N C(C(O)C)(=O)NC(=O)OCC Chemical compound C(C(O)C)(=O)NC(=O)OCC GRELGUDMSKNQIE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- 108010084311 Novozyme 435 Proteins 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of polyurethane based on vegetable oil and lactic acid, characterized by being prepared by the following steps: (1) oxidizing the vegetable oil to be epoxy vegetable oil by oxyful under the catalysis of lipase; (2) enabling the epoxy vegetable oil to react with the lactic acid to generate biopolyol; and (3) mixing the biopolyol with vulcabond compound and heating and solidifying the mixture to generate the polyurethane. The polyurethane takes vegetable oil and lactic acid which are renewable resources as the main raw material, has novel and simple process route and higher glass transition temperature and belongs to the technical field of chemical materials and production technologies thereof.
Description
Technical field
The present invention relates to a kind of urethane based on vegetables oil and lactic acid and preparation method thereof, belong to chemical materials and production technical field thereof.
Background technology
At present the starting material of polyurethane production substantially all come from petroleum resources, but petroleum resources gradually the serious environmental pollution that brings of shortage and petroleum-based products become the severe problem that the mankind face.Caused various countries scientific workers' very big interest in recent years for feedstock production urethane with the vegetables oil.Vegetables oil output is big, low price, annual renewable, is one of important renewable resources.Utilize the vegetables oil method for producing polyurethanes to mainly contain at present:
1) vegetables oil and polyvalent alcohol are carried out alcoholysis, generate polyol, generate urethane with the diisocyanate compound reaction then.The polyvalent alcohol that is adopted is generally glycerine, and the gained polyol is generally diglyceride or monoesters acyl glyceryl ester, and alcoholysis reaction is carried out in the presence of catalyzer usually.(Pro.Polym.Sci.，2006，31：633-670；CN1844183A)。
2) utilize unsaturated double-bond in the ozone oxidation vegetables oil, generate the polyol that has end position hydroxyl, generate urethane with the diisocyanate compound reaction then.Utilize in the polyol per molecule of this method gained and contain three oh groups at most.(J.Amer.Oil.Chem.Soc.，2007，84：55-63；Biomacromolecules，2005，6：713-719)
3) vegetables oil is oxidized to epoxidized vegetable oil, handles generating polyol then by hydrolysis, hydrogenation, esterification or halogenation etc., generate urethane with the diisocyanate compound reaction then.(Int.J.Bio.Macromol.，2007，40：407-422；US2006041156-A1；Biomacromolecules，2005，6：713-719；J.Polym.Sci.A：Polym.Chem.，2000，38：3900-3910)
In the above-mentioned method for preparing vegetable oil-based polyols, method 1) described alcoholysis reaction is at high temperature carried out usually; Method 2) ozone industrialization use cost is higher in.In addition, utilize method 1) and 2) hydroxyl value of gained polyol is generally lower, average per molecule is lower than three oh groups usually.Method 3) reaction in usually needs a large amount of catalyzer, post catalyst reaction remove complicated operation, the hydroxyl value of gained polyol is relevant with the degree of unsaturation of vegetables oil, each unsaturated double-bond only can derive an oh group usually.In addition, adopt the vitreous state temperature of above-mentioned three kinds of method gained urethane generally all below 40 ℃.
Present method has overcome above-mentioned defective, adopts lactic acid to make epoxidized vegetable oil generation ring-opening reaction, prepares biopolyol and and then is used for the synthetic of urethane thereby introduce hydroxyl.Utilize average in the ideal case each unsaturated double-bond of this method can derive two oh groups, can realize higher degree of crosslinking when reacting with diisocyanate compound.Simultaneously, because the whole process of preparation of vegetables oil and lactyl urethane does not relate to the use of any organic solvent and poisonous catalyzer, reaction conditions gentleness, reactions steps is simple, processing condition are easy to control, and raw material has recyclability, therefore have wide industrialized developing and application prospect.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the urethane based on vegetables oil and lactic acid, it is characterized in that following steps:
1) under lipase-catalyzed effect, utilize hydrogen peroxide that vegetables oil is oxidized to epoxidized vegetable oil;
2) with gained epoxidized vegetable oil and lactic acid reaction, generate biopolyol;
3) with gained biopolyol and diisocyanate compound reaction, generate urethane.
Among the above-mentioned preparation method, used vegetables oil can be a kind of in soybean oil, plam oil, Semen Maydis oil, rapeseed oil, Oleum Gossypii semen, Viscotrol C, OK a karaoke club oil, the sunflower seeds wet goods crude vegetal, or the mixture of above-mentioned two kinds or above vegetables oil.
Described method steps 2) in, the proportioning of lactic acid and epoxidized vegetable oil is: epoxidized vegetable oil 50～91%, lactic acid 9～50%; Optimum ratio is: epoxidized vegetable oil 55～75%, lactic acid 25～45%.Temperature of reaction is 60～120 ℃, and the reaction times is 4～24 hours; Preferable reaction temperature is 75～90 ℃, and the preferred reaction time is 5～9 hours.The mechanism of lactic acid and epoxidized vegetable oil reaction is as follows, the carboxyl of lactic acid and the reaction of the epoxide group of epoxidized vegetable oil, generate an ester bond and produce a hydroxyl groups, because originally contain an oh group in the lactic acid molecules, so each epoxide group on average can derive two oh groups (Fig. 1).
Described method steps 3) in, utilize the biopolyol method for producing polyurethanes to be: earlier biopolyol is mixed with diisocyanate compound, the proportioning of reactant is: biopolyol 30～95%, diisocyanate cpd 5～70%; Optimum ratio is: biopolyol 60～75%, diisocyanate cpd 25～40%.Be warming up to 60～150 ℃ and mix then, be incubated 10-48 hour and be cured processing; Preferable reaction temperature is 75～95 ℃, and the preferred reaction time is 12～24 hours.
The diisocyanate compound that is adopted is one or more in hexamethylene diisocyanate, tolylene diisocyanate, lysinediisocyanate and the diphenyl diisocyanate.The vitreous state temperature of gained urethane can prepare the urethane with particular glass attitude temperature by selecting suitable vegetables oil and diisocyanate compound between-30～150 ℃.
Description of drawings
The synthetic route of Fig. 1 vegetables oil and lactyl urethane
Fig. 2 soybean oil, epoxy soybean oil and LA-ESO's
1The HNMR spectrogram
Annotate: SOY, soybean oil; ESO, epoxy soybean oil; ESO-standard, the epoxy soybean oil standard substance; LA-ESO, the biopolyol that lactic acid and epoxy soybean oil reaction generate
Infrared (IR) of the soybean oil based polyurethane preparation process of Fig. 3 analyzes
Annotate: SOY, soybean oil; ESO, epoxy soybean oil; LA-ESO, the biopolyol that lactic acid and epoxy soybean oil reaction generate; PU, the urethane that utilizes LA-ESO and diphenyl diisocyanate (MDI) to prepare.
From figure as can be known, peak 821cm
-1Appearance show that soybean oil oxidizing reaction has taken place generated epoxide group; Peak 1217cm
-1And 1201cm
-1, and peak 1103cm
-1And 1160cm
-1Occur showing that the formation reaction of urethane has all taken place two class oh groups in the biopolyol (being the hydroxyl groups that originally contains of lactic acid and the oh group by the reaction generation).
Fig. 4 is based on the vitreous state temperature of the urethane of soybean oil and lactic acid
Annotate: LA-ESO, the biopolyol that lactic acid and epoxy soybean oil reaction generate; MDI, diphenyl diisocyanate
Embodiment
In the 20ml reactor, add soybean oil 1000mg, toluene 5ml, oleic acid 50mg, lipase Novozym 435 100mg, reactor is warming up to 40 ℃, and said mixture stirred, add hydrogen peroxide (30%, the aqueous solution) 700 μ l, continue to stir, 24h is carried out in reaction.Then with high purity water washing reaction system removing unnecessary hydrogen peroxide, take out organic phase, utilize Rotary Evaporators to remove toluene 40 ℃ of vacuum-evaporation, the higher liquid substance of gained viscosity is epoxy soybean oil.Epoxy soybean oil
1H NMR spectrogram and IR analytical results are respectively as shown in Figures 2 and 3.
In the 20ml reactor, add rapeseed oil 1000mg, toluene 5ml, oleic acid 50mg, lipase Novozym 435 100mg, reactor is warming up to 40 ℃, and said mixture stirred, add hydrogen peroxide (30%, the aqueous solution) 700 μ l, continue to stir, 24h is carried out in reaction.Then with high purity water washing reaction system removing unnecessary hydrogen peroxide, take out organic phase, utilize Rotary Evaporators to remove toluene 40 ℃ of vacuum-evaporation, the higher liquid substance of gained viscosity is epoxy rapeseed oil.
In the 20ml reactor, add epoxidised soybean oil 1000mg, lactic acid 300mg, magnetic agitation mixes, and reactor is warming up to 90 ℃, insulation 6h.With the reaction mixture evaporate to dryness, the light yellow material of gained thickness is soybean oil base polyol,
1H NMR spectrogram and IR analytical results are respectively as shown in Figures 2 and 3.
Embodiment 4
In the 20ml reactor, add epoxidation rapeseed oil 1000mg, lactic acid 300mg, magnetic agitation mixes, and reactor is warming up to 100 ℃, insulation 8h.With the reaction mixture evaporate to dryness, the light yellow material of gained thickness is the rapeseed oil polylol.
In reactor, add soybean oil base polyol 1000mg, diphenyl diisocyanate 300mg, be warming up to 100 ℃ then gradually, mix, curing reaction carries out 10h.Open reactor, take out solidified urethane, the finished product 1300mg that weighs, color is displaing yellow slightly, and translucent, the vitreous state temperature is 30.79 ℃ (Fig. 4).
In reactor, add soybean oil base polyol 1000mg, diphenyl diisocyanate 400mg, be warming up to 100 ℃ then gradually, mix, curing reaction carries out 10h.Open reactor, take out solidified urethane, the finished product 1400mg that weighs, color is displaing yellow slightly, and translucent, the vitreous state temperature is 64.31 ℃ (Fig. 4).
In reactor, add soybean oil base polyol 1000mg, diphenyl diisocyanate 500mg, be warming up to 100 ℃ then gradually, mix, curing reaction carries out 10h.Open reactor, take out solidified urethane, the finished product 1500mg that weighs, color is displaing yellow slightly, and translucent, the vitreous state temperature is 95.75 ℃ (Fig. 4).
Embodiment 8
In reactor, add rapeseed oil polylol 1000mg, diphenyl diisocyanate 400mg, be warming up to 120 ℃ then gradually, curing reaction carries out 12h.Open reactor, take out solidified urethane, the finished product 1400mg that weighs.
Claims (5)
1. preparation method based on the urethane of vegetables oil and lactic acid is characterized in that:
1) under lipase-catalyzed effect, utilize hydrogen peroxide that vegetables oil is oxidized to epoxidized vegetable oil;
2) with gained epoxidized vegetable oil and lactic acid reaction, generate biopolyol, the proportioning of each reactive component is when lactic acid and epoxidized vegetable oil reaction: epoxidized vegetable oil 50～91%, lactic acid 9～50%;
3) with gained biopolyol and diisocyanate compound reaction, generate urethane, the proportioning of each reactive component is when biopolyol and diisocyanate compound reaction: biopolyol 30～95%, diisocyanate cpd 5～70%.
2. preparation method according to claim 1, it is characterized in that the vegetables oil described in the step 1) comprises soybean oil, plam oil, Semen Maydis oil, rapeseed oil, Oleum Gossypii semen, Viscotrol C, sunflower seed oil, can be an above-mentioned wherein vegetable oil during preparation, also can be the mixture of above-mentioned two or more vegetables oil.
3. preparation method according to claim 1 is characterized in that step 2) in lactic acid and the epoxidized vegetable oil temperature when reacting be 60～120 ℃, the reaction times is 4～24 hours.
4. preparation method according to claim 1, the temperature of reaction when it is characterized in that preparing urethane in the step 3) is 60～150 ℃, 10～48 hours reaction times.
5. preparation method according to claim 1, it is characterized in that the diisocyanate compound that is adopted comprises 1, hexamethylene-diisocyanate, tolylene diisocyanate, lysinediisocyanate and MDI, can be above-mentioned wherein a kind of diisocyanate compound during preparation, also can be the mixture of above-mentioned two or more diisocyanate compounds.
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| CN106753811B (en) * | 2016-11-24 | 2020-06-26 | 常州大学 | Preparation method of derivative synthesized by esterification and coupling of epoxy vegetable oil, citric acid ester and dicarboxylic anhydride |
| CN109610202A (en) * | 2018-10-29 | 2019-04-12 | 薛向东 | A kind of environment-protection coating printing adhesive and preparation method thereof |
| CN109880039A (en) * | 2019-01-08 | 2019-06-14 | 湖北大学 | A kind of preparation method of palm oil-base aqueous polyurethane |
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| CN101016225A (en) * | 2007-02-07 | 2007-08-15 | 上海中科合臣股份有限公司 | Preparing method for high hydroxyl value plant oil polyhydric alcohol |
| CN101186694A (en) * | 2007-12-27 | 2008-05-28 | 北京市丰信德科技发展有限公司 | Method for preparing polyether polyol from plant oil |
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| CN101016225A (en) * | 2007-02-07 | 2007-08-15 | 上海中科合臣股份有限公司 | Preparing method for high hydroxyl value plant oil polyhydric alcohol |
| CN101186694A (en) * | 2007-12-27 | 2008-05-28 | 北京市丰信德科技发展有限公司 | Method for preparing polyether polyol from plant oil |
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