CN102167809B - Method for preparing biobased polyether polylol from vegetable oil - Google Patents
Method for preparing biobased polyether polylol from vegetable oil Download PDFInfo
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- CN102167809B CN102167809B CN201110054557XA CN201110054557A CN102167809B CN 102167809 B CN102167809 B CN 102167809B CN 201110054557X A CN201110054557X A CN 201110054557XA CN 201110054557 A CN201110054557 A CN 201110054557A CN 102167809 B CN102167809 B CN 102167809B
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- polyhydric alcohol
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- ethoxylated polyhydric
- polyether polylol
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Abstract
The invention discloses a method for preparing biobased polyether polylol from vegetable oil, which comprises the following steps: adding micromolecule alcohol or an amine type compound and a catalyst A into the vegetable oil for heating reaction, and preparing modified vegetable oil; taking the obtained modified vegetable oil and epoxypropane as raw materials, and preparing a biobased polyether polylol crude product under the action of a catalyst B; and neutralizing the obtained biobased polyether polylol crude product with acid, performing dehydration treatment and obtaining a biobased polyether polylol product. The vegetable oil is adopted as the raw material for obtaining the biobased polyether polylol through modification. Compared with the polyether polylol in the past, the biobased polyether polylol has the characteristics of being convenient to purchase the raw materials, being renewable, reducing the using amount of the epoxypropane and reducing the cost, and can better meet the requirement of environment protection. The biobased polyether polylol is mainly used for plastic racetracks, polyurethane glue and polyurethane elastomers.
Description
Technical field
The present invention relates to a kind of preparation method of biological poly ethoxylated polyhydric alcohol.
Background technology
At present elastomeric polyethers all be with glycerine, glycol ether, Ucar 35 as initiator, propylene oxide and oxyethane is as chain propagation agent, the inside 98% above petroleum derivative, petroleum resources are Nonrenewable resources, along with expanding economy drains off.The used initiator of the present invention is a modified vegetable oil, is 20-35% in the occupancy volume of elastomeric polyethers, has significantly reduced the use of petroleum derivative, is renewable resources, can reduce the dependence to petroleum resources.
The main molecules of vegetables oil consists of the triacyl glycerol ester, also has phosphatide, Viteolin and the vitamin E of small-amount free lipid acid and partial glycerol ester, 0.1-0.5%.In general, the oleic acid content in the vegetables oil is high more, and linoleic acid plus linolenic acid content is low more, and its oxidative stability is good more.Contain a large amount of carbon-carbon double bonds in the vegetables oil molecule, the oxidation mechanism of vegetables oil mainly shows as active allyl reaction, and this confirms the major cause of its oxidative stability difference.The vegetables oil major part obtains by stablizing raw material, is a kind of worthwhile urethane raw therefore, and shortcoming is that it lacks and the necessary reactive hydrogen of isocyanate reaction.In this connection, mainly exception is Viscotrol C, and it has part of hydroxyl, can be used as urethane raw, and use certain fields at present, but the plantation of Viscotrol C area and planting number are limited, and the planting area of other vegetables oil is restriction too much not.
Therefore, must introduce in the above plant through the chemical means process reactive hydrogen that polyurethane industrial is required.According to the prior art level, the method that realizes this point is to adopt epoxidation and hydroxylation modification basically.Several kinds of method and technologies that prepare vegetable oil-based polyether polyol are arranged at present: (1) feeds propylene oxide after with ydrogen peroxide 50 hydroxyl value vegetables oil, the synthetic vegetables oil rigid-foam polyether polyol that contains; (2) in synthetic plant oil polyether glycol, directly add the synthetic vegetables oil rigid-foam polyether of plam oil; (3) directly with vegetables oil and the synthetic vegetables oil rigid-foam polyether of small molecular alcohol; (4) with hydroxyl value vegetables oil and epoxidized vegetable oil reaction, the synthetic plant oil polyether glycol that contains.
Summary of the invention
The object of the present invention is to provide a kind of renewable, environmental protection, cost low prepare the method for biological poly ethoxylated polyhydric alcohol by vegetables oil.
Technical solution of the present invention is:
A kind ofly prepare the method for biological poly ethoxylated polyhydric alcohol, it is characterized in that: comprise the following steps: by vegetables oil
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the vegetables oil, make modified vegetable oil; Catalyst A is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, earth alkali metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with resulting modified vegetable oil of step (1) and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol bullion under the catalyst B effect; Catalyst B is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, earth alkali metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol bullion that step (2) is obtained neutralizes with acid, carries out processed again, obtains biological poly ethoxylated polyhydric alcohol product.
Small molecular alcohol is terepthaloyl moietie, Ucar 35, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethylolamine, trolamine or alkyl ethanol amine.
The mol ratio of small molecular alcohol or aminated compounds and vegetables oil is in the step (1): 1:1.0-4.0, temperature of reaction is 100-200 ℃.
The consumption of catalyst A is the 0.2-2.0% of reactant weight in the step (1); The consumption of catalyst B is the 0.1-1.0% of reactant weight in the step (2).
Said vegetables oil is wherein one or more of VT 18, plam oil, Semen Maydis oil, peanut oil, Oleum Gossypii semen, Uni Ace R, olive wet goods.
In carrying out with acid in the step (3) and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5 ~ 7.5; The processed temperature is 90-120 ℃, and dewatering time is 60-150 minute.
It is that raw material obtains the biological poly ethoxylated polyhydric alcohol through modification that the present invention adopts vegetables oil; This biological poly ethoxylated polyhydric alcohol and polyether glycol ratio in the past, have raw material buy convenient, renewable; Reduce the consumption of propylene oxide; The characteristics that reduce cost can satisfy environmental requirement better, and main application is plastic cement race track, polyurethane glue and polyurethane elastomer.
Embodiment
Embodiment 1:
In the glass still of 2L, add VT 18 1000g, 180 glycol ethers, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modified soybean oil A hydroxyl value: 112mgKOH/g.
A:520g adds in the autoclave with modified soybean oil, the catalyzer sodium hydroxide of 2.5g, and vacuum is to the highest; Nitrogen replacement twice, PO/EO (9.4/0.6) mixture (be the mixture of propylene oxide and oxyethane, the weight ratio of propylene oxide and oxyethane is 9.4:0.6) of feeding 1000g; Reaction times 2-4 hour, make with extra care (with acid neutralization and dehydration, during acid is carried out and the time; Used acid is phosphoric acid or tetra-sodium, is neutralized to pH=7; The processed temperature is 100 ℃, and dewatering time is 100 minutes), obtaining hydroxyl value is the biological poly ethoxylated polyhydric alcohol of 36.4mgKOH/g.
Embodiment 2:
In the glass still of 2L, add plam oil 1000g, 140 tetramethylolmethanes, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modified soybean oil B hydroxyl value: 180mgKOH/g.
Modification plam oil B:200g is added in the autoclave, the catalyzer sodium hydroxide of 2.5g, vacuum is to the highest; Nitrogen replacement twice, PO/EO (9.4/0.6) mixture of feeding 1000g, reaction times 2-4 hour; Make with extra care (with acid neutralization and dehydration; During acid is carried out and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=6; The processed temperature is 90 ℃, and dewatering time is 140 minutes), obtaining hydroxyl value is the biological poly ethoxylated polyhydric alcohol of 41.2mgKOH/g.
Embodiment 3
In the glass still of 2L, add peanut oil 1000g, 160 trolamines, 4g sodium hydroxide stirs and is warming up to 170 degree, reacts 3 hours, detects hydroxyl value, and blowing records modification peanut oil C hydroxyl value: 201mgKOH/g.
Modification peanut oil C:210g is added in the autoclave, the catalyzer sodium hydroxide of 2.5g, vacuum is to the highest; Nitrogen replacement twice, PO/EO (9.4/0.6) mixture of feeding 800g, reaction times 2-4 hour; Make with extra care (with acid neutralization and dehydration; During acid is carried out and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5; The processed temperature is 120 ℃, and dewatering time is 60 minutes), obtaining hydroxyl value is 58.7mgKOH/g, viscosity 590mPas/25 ℃ biological poly ethoxylated polyhydric alcohol.
Embodiment 4:
A kind ofly prepare the method for biological poly ethoxylated polyhydric alcohol, comprise the following steps: by vegetables oil
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the vegetables oil, make modified vegetable oil; Catalyst A is basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxide compound, basic metal (lithium, sodium, potassium, rubidium, caesium, francium) oxyhydroxide, earth alkali metal (beryllium, magnesium, calcium, strontium, barium, radium) oxide compound, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with resulting modified vegetable oil of step (1) and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol bullion under the catalyst B effect; Catalyst B is alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol bullion that step (2) is obtained neutralizes with acid, is carrying out processed, obtains biological poly ethoxylated polyhydric alcohol product;
Small molecular alcohol is terepthaloyl moietie, Ucar 35, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethylolamine, trolamine or alkyl ethanol amine.
The mol ratio of small molecular alcohol or aminated compounds and vegetables oil is in the step (1): 1:1.0-4.0, temperature of reaction is 100-200 ℃.
The consumption of catalyst A is the 0.2-2.0% of reactant weight in the step (1); The consumption of catalyst B is the 0.1-1.0% of reactant weight in the step (2).
Said vegetables oil is wherein one or more of VT 18, plam oil, Semen Maydis oil, peanut oil, Oleum Gossypii semen, Uni Ace R, olive wet goods.All the other are with embodiment 1.
Claims (3)
1. one kind prepares the method for biological poly ethoxylated polyhydric alcohol by vegetables oil, it is characterized in that: comprise the following steps:
(1) small molecular alcohol or aminated compounds and catalyst A are joined reacting by heating in the vegetables oil, make modified vegetable oil; Catalyst A is alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxides, metal halide or aluminum oxide;
(2) be raw material with resulting modified vegetable oil of step (1) and propylene oxide, reaction makes biological poly ethoxylated polyhydric alcohol bullion under the catalyst B effect; Catalyst B is alkalimetal oxide, alkaline earth metal oxide, metal halide or aluminum oxide;
(3) the biological poly ethoxylated polyhydric alcohol bullion that step (2) is obtained neutralizes with acid, carries out processed again, obtains biological poly ethoxylated polyhydric alcohol product;
The mol ratio of small molecular alcohol or aminated compounds and vegetables oil is in the step (1): 1: 1.0-4.0, temperature of reaction is 100-200 ℃.
2. according to claim 1ly prepare the method for biological poly ethoxylated polyhydric alcohol by vegetables oil, it is characterized in that: small molecular alcohol is terepthaloyl moietie, Ucar 35, glycol ether, glycerine, tetramethylolmethane, a Virahol, diisopropanol or three Virahols; Aminated compounds is thanomin, diethylolamine, trolamine or alkyl ethanol amine.
3. according to claim 1 and 2ly prepare the method for biological poly ethoxylated polyhydric alcohol, it is characterized in that by vegetables oil: in carrying out with acid in the step (3) and the time, used acid is phosphoric acid or tetra-sodium, is neutralized to pH=5.5～7.5; The processed temperature is 90-120 ℃, and dewatering time is 60-150 minute.
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| CN104448292A (en) * | 2014-12-09 | 2015-03-25 | 淄博德信联邦化学工业有限公司 | Polyether polyol for high-efficiency strengthening material as well as preparation method of polyether polyol |
| CN107722258A (en) * | 2017-09-30 | 2018-02-23 | 山东隆华新材料股份有限公司 | A kind of continuous producing method of bio-based polymers PPG |
| CN110387033A (en) * | 2018-04-17 | 2019-10-29 | 高春青 | It is a kind of for synthesizing the bio-based resin and preparation method thereof of sustained and controlled release chemical fertilizer polymer capsule |
| CN112457480B (en) * | 2020-11-26 | 2023-09-26 | 山东尚正新材料科技股份有限公司 | Preparation method of bio-based modified high-activity polyether polyol |
| CN113698587A (en) * | 2021-09-08 | 2021-11-26 | 航锦科技股份有限公司 | Preparation method of hard foam polyether polyol |
| CN115322361A (en) * | 2022-09-16 | 2022-11-11 | 句容宁武新材料股份有限公司 | Synthetic method of plant oil-based polyether polyol |
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| CN101353422A (en) * | 2008-09-05 | 2009-01-28 | 绍兴市恒丰聚氨酯实业有限公司 | Synthetic method of polyether polyatomic alcohol |
| CN101805258B (en) * | 2010-03-18 | 2013-03-27 | 宁波万华容威聚氨酯有限公司 | Preparation method of novel vegetable oil polyol for polyurethane rigid foam |
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