CN103755948A - Bio-based polyalkylene glycol and preparation method thereof - Google Patents
Bio-based polyalkylene glycol and preparation method thereof Download PDFInfo
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- CN103755948A CN103755948A CN201410021808.8A CN201410021808A CN103755948A CN 103755948 A CN103755948 A CN 103755948A CN 201410021808 A CN201410021808 A CN 201410021808A CN 103755948 A CN103755948 A CN 103755948A
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- aklylene glycol
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- tetrahydrofuran
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
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Abstract
The invention relates to bio-based polyalkylene glycol and a preparation method thereof. The product is a segmented copolymer which is prepared by using furfural derivative tetrahydrofuran and 2-methyltetrahydrofuran produced from wood fiber biomass as raw materials by a polymerization process, and has the structure shown in the specification. The preparation method comprises the following steps: adding tetrahydrofuran and an initiator in a mass ratio of 1:(2-10) into a reaction kettle in an inert gas atmosphere, and reacting at a temperature of 80-150 DEG C and a pressure of 0.2-0.5MPa for 4-15 hours to prepare a polytetramethylene glycol homopolymer; cooling the reaction kettle to normal temperature and normal pressure, adding 2-methyltetrahydrofuran into the reaction kettle, reacting at a temperature of 100-120 DEG C and a pressure of 0.4-1MPa for 2-8 hours to prepare the bio-based polyalkylene glycol, wherein the molar ratio of 2-methyltetrahydrofuran to tetrahydrofuran is 1:(1-10). The bio-based polyalkylene glycol has the advantages that the product by a process flow for producing bio-based PAG (polyalkylene glycol) from wood fiber biomass can achieve the performance index of fossil based PAG, and can completely replace an existing fossil based product.
Description
Technical field
The invention belongs to field of renewable energy resource utilization, particularly a kind of biological poly aklylene glycol and preparation method thereof.
Background technology
Polyalkylene glycol (PAG) is unique synthetic lubricant, be the high molecular polymer that contains diether linkage structure in the main chain being formed by epoxy compounds and derivative copolymerization thereof or homopolymerization, its primary structure unit is comprised of oxyethane (EO), propylene oxide (PO), butylene oxide ring (BO) or tetrahydrofuran (THF) (THF).PAG multipolymer can be divided into unregulated polymer and block polymer according to the distribution of sequence monomer.Because it has high oxygen level, it also has the occasion of carbon deposit and greasy filth except clean for petroleum products, and variable structure becomes water-soluble or water-insoluble product, and it is only soluble oil.
For the synthetic of polyethers, it is the focus that people study always.As far back as 1859, the people such as Lourenco, by tube sealing technology, to 115-120 ℃, obtained the low-molecular weight polymer with diether linkage structure by the mixture direct heating of ethylene glycol and glycol dibromide first.At same year, people's separation such as Wurtz have obtained the polymerisate polyoxyethylene glycol of oxyethane and water.1863, people's reported first such as Wurtz the ring-opening polymerization that under room temperature, a small amount of alkali or zinc chloride can intensifier ring oxidative ethanes.Until 1927, talent's reported first such as Levene and Walti are by being heated to 165 ℃ of polymerizations that can realize propylene oxide.Nineteen twenty-nine, Staudinger and Schweitzer have reported that potassium, tin tetrachloride, Trimethylamine 99 etc. can promote the ring-opening polymerization of oxyethane under gentle condition, and the speed to reaction is studied, point out that tin tetrachloride also can realize the ring-opening polymerization of propylene oxide simultaneously, in addition Staudinger, by cooperating with Svedberg, has obtained the polymerisate of different molecular weight first.And then the Indigo of Farbenindustrie laboratory study personnel, find that the compound of metallic iron or iron content can efficiently promote the ring-opening polymerization of oxyethane.In the development of decades subsequently, various catalyzer continue to bring out, and have obtained that molecular weight is high, narrowly distributing and the low polyethers product of degree of unsaturation.Mainly there is at present the method for three kinds of catalysis epoxy alkane ring opening polymerizations, respectively: acid catalyzed polymerisation, base catalyzed polymerization and coordination catalysis polymerization.Wherein base catalyzed polymerization be industrialization the most ripe, apply maximum methods, but polycoordination is current state-of-the-art method, is also the method that people pay close attention to.Acid catalyzed polymerisation is eliminated gradually because cost is high, aftertreatment is complicated at present.
At present, the raw material of producing PAG all derives from fossil resource, from the angle of environment protection and Resources Strategy, answers active development to utilize reproducible resource to produce PAG.
Summary of the invention
The object of this invention is to provide a kind of a kind of biological poly aklylene glycol that utilizes reproducible wood fiber biomass production bio-based PAG and preparation method thereof, this product not only has viscosity index that fossil base PAG is high, low pour point, lower generation carbon deposit and greasy filth trend, excellent solvability and rubber compatibility, low flammability, also has renewable, high temperature resistant, the more excellent oxidation of raw material and thermostability, automatically cleaning, shear thickening, degradability.
Biological poly aklylene glycol of the present invention is that to take furfural derivatives tetrahydrofuran (THF) and the 2-methyltetrahydrofuran that wood fiber biomass produces be raw material, the segmented copolymer with following structure of producing through polymerization technique:
9≤m≤40；1≤n≤20。
The molecular weight of described biological poly aklylene glycol is between 800-3500.
Described wood fiber biomass is preferably rich in the biomass of half fiber, as corn cob, bagasse, rice husk, cotton seed hulls; Furfural is to be made through acid hydrolysis process by lignocellulose; Tetrahydrofuran (THF) be by furfural on palladium catalyst through decarbonylation technique, make through hydrogenation technique on nickel catalyzator again; 2-methyltetrahydrofuran is through two step hydrogenation techniques, to be made on copper zinc-aluminium and nickel catalyzator by furfural.
Biological poly aklylene glycol of the present invention has unique contrary dissolubility, gets between m:n=1-9, can obtain the contrary molten point of 50 ~ 80 ℃.That is: biological poly aklylene glycol has contrary dissolubility, and contrary molten o'clock between 50 ~ 80 ℃.Biological poly aklylene glycol of the present invention is the complete water-soluble limpid uniform solution that is at room temperature, separates out as not dissolving phase under being raised to certain high temperature from water, and when solution cools down, polymkeric substance is soluble in water again.The function that the contrary solubility temperature of PAG is m/n: m/n is larger, the temperature that polymkeric substance is separated out from water is higher, and hardening liquid stability is better, and drag-out is less.
This product can be used as metal working fluid, fire resistant hydraulic oil, braking fluid, compressor lubricant, refrigeration lubricant, two stroke engine oil, crankcase oils.
Biological poly aklylene glycol of the present invention (PAG) makes by the following method:
Tetrahydrofuran (THF) and initiator are joined in reactor under inert atmosphere (as logical nitrogen), the mass ratio of tetrahydrofuran (THF) and initiator is 1:2-10, temperature of reaction is 80-150 ℃, and pressure 0.2-0.5MPa makes polytetrahydrofuran diol homopolymer after reaction 4-15h; Subsequently reactor is cooled under normal temperature and pressure, again 2-methyltetrahydrofuran is joined in reactor, the mol ratio of 2-methyltetrahydrofuran and tetrahydrofuran (THF) is 1:1-10, temperature of reaction is 100-120 ℃, pressure 0.4-1MPa, after reaction 2-8h, make biological poly aklylene glycol, molecular weight control is between 800-3500.
Described initiator is comprised of the first initiator and the second initiator, and both mole proportionings are 1:2-10;
Described the first initiator is an alkali metal salt, and an alkali metal salt can be a kind of in sodium hydroxide, sodium carbonate, sodium methylate, potassium methylate, potassium hydroxide;
Described the second initiator is a kind of in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, propylene glycol.
Tool of the present invention has the following advantages:
Along with the continuous exhaustion of fossil resource in recent years, people are also more positive and deep to the exploration of new forms of energy and novel material, the present invention develops the operational path with wood fiber biomass production bio-based PAG, product has reached fossil base PAG performance index, can substitute existing fossil base product completely.
Embodiment
embodiment 1
Sodium methylate and methyl alcohol initiator that configuration 50g mol ratio is 1:4, then join in reactor under nitrogen atmosphere with 10g tetrahydrofuran (THF), be warming up to 100 ℃, pressure 0.4MPa, after reaction 6h, reactor is cooled under normal temperature and pressure, add 3g 2-methyltetrahydrofuran, the mol ratio of 2-methyltetrahydrofuran and tetrahydrofuran (THF) is 1:4 again, and temperature of reaction is 100 ℃, pressure 0.8MPa, makes bio-based PAG after reaction 4h.
embodiment 2
Sodium hydroxide and ethanol initiator that configuration 50g mol ratio is 1:4, then join in reactor under nitrogen atmosphere with 10g tetrahydrofuran (THF), be warming up to 80 ℃, pressure 0.4MPa, after reaction 6h, reactor is cooled under normal temperature and pressure, add 1.2g 2-methyltetrahydrofuran, the mol ratio of 2-methyltetrahydrofuran and tetrahydrofuran (THF) is 1:10 again, and temperature of reaction is 120 ℃, pressure 0.4MPa, makes bio-based PAG after reaction 4h.
embodiment 3
Potassium hydroxide and ethylene glycol initiator that configuration 50g mol ratio is 1:2, then join in reactor under nitrogen atmosphere with 10g tetrahydrofuran (THF), be warming up to 150 ℃, pressure 0.2MPa, after reaction 4h, reactor is cooled under normal temperature and pressure, add 2.4g 2-methyltetrahydrofuran, the mol ratio of 2-methyltetrahydrofuran and tetrahydrofuran (THF) is 1:5 again, and temperature of reaction is 100 ℃, pressure 0.8MPa, makes bio-based PAG after reaction 4h.
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Relative molecular weight | 970 | 1590 | 3380 |
| 40 ℃ of viscosity (mm 2/s） | 53 | 130 | 700 |
| Viscosity index | 212 | 230 | 269 |
| Pour point/℃ | -40 | -34 | -29 |
| Relative density (20/20 ℃) | 1.036 | 1.046 | 1.058 |
| Close flash point/℃ | 194 | 202 | 172 |
| Contrary fusing point/℃ | 52 | 70 | 78 |
Claims (6)
1. a biological poly aklylene glycol, it is characterized in that: biological poly aklylene glycol is that to take furfural derivatives tetrahydrofuran (THF) and the 2-methyltetrahydrofuran that wood fiber biomass produces be raw material, the segmented copolymer with following structure of producing through polymerization technique:
9≤m≤40；1≤n≤20。
2. biological poly aklylene glycol according to claim 1, is characterized in that: the molecular weight of described biological poly aklylene glycol is between 800-3500.
3. biological poly aklylene glycol according to claim 1, is characterized in that: biological poly aklylene glycol has contrary dissolubility, and contrary molten o'clock between 50 ~ 80 ℃.
4. the preparation method of a biological poly aklylene glycol according to claim 1, it is characterized in that: tetrahydrofuran (THF) and initiator are joined in reactor under inert atmosphere, the mass ratio of tetrahydrofuran (THF) and initiator is 1:2-10, temperature of reaction is 80-150 ℃, pressure 0.2-0.5MPa, makes polytetrahydrofuran diol homopolymer after reaction 4-15h; Subsequently reactor is cooled under normal temperature and pressure, again 2-methyltetrahydrofuran is joined in reactor, the mol ratio of 2-methyltetrahydrofuran and tetrahydrofuran (THF) is 1:1-10, temperature of reaction is 100-120 ℃, pressure 0.4-1MPa, after reaction 2-8h, make biological poly aklylene glycol, molecular weight control is between 800-3500.
5. the preparation method of biological poly aklylene glycol according to claim 4, is characterized in that: described initiator is comprised of the first initiator and the second initiator, and both mole proportionings are 1:2-10; Described the first initiator is an alkali metal salt; Described the second initiator is a kind of in methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, propylene glycol, propylene glycol.
6. the preparation method of biological poly aklylene glycol according to claim 5, is characterized in that: described an alkali metal salt is a kind of in sodium hydroxide, sodium carbonate, sodium methylate, potassium methylate, potassium hydroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622922A (en) * | 2016-04-06 | 2016-06-01 | 苏州博纳化学科技有限公司 | Preparation method of hydrophilic dihydroxyl compounds |
| WO2018220983A1 (en) * | 2017-05-30 | 2018-12-06 | 保土谷化学工業株式会社 | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| CN112194786A (en) * | 2020-09-18 | 2021-01-08 | 上海凯众材料科技股份有限公司 | Novel modified PTMEG and preparation method of polyurethane microporous elastomer thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081463A (en) * | 1963-07-25 | 1967-08-31 | Monsanto Co | Preparation of polyoxytetramethylene glycol |
| US3359332A (en) * | 1963-07-25 | 1967-12-19 | Monsanto Co | Preparation of polyoxytetra-methylene glycol |
| EP0051499A1 (en) * | 1980-11-04 | 1982-05-12 | Japan Synthetic Rubber Co., Ltd. | A process for the preparation of polyether glycols |
| CN1037891A (en) * | 1988-04-05 | 1989-12-13 | 三井东圧化学株式会社 | The manufacture method of bisphenol A with high purity |
| US4990679A (en) * | 1988-11-23 | 1991-02-05 | Ciba-Geigy Corporation | Poly(tetrahydrofuran) |
| CN1200740A (en) * | 1996-07-10 | 1998-12-02 | 巴斯福公司 | Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having low degree of unsaturation |
| US6559278B1 (en) * | 1997-04-08 | 2003-05-06 | Mueller Herbert | Method for producing tetrahydrofuran polymers |
| CN102395619A (en) * | 2009-04-15 | 2012-03-28 | 因温斯特技术公司 | Improving miscibility of otherwise immiscible compounds |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
| WO2012177415A1 (en) * | 2011-06-21 | 2012-12-27 | Dow Global Technologies Llc | Energy efficient polyalkylene glycols and lubricant composition containing same |
-
2014
- 2014-01-17 CN CN201410021808.8A patent/CN103755948A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1081463A (en) * | 1963-07-25 | 1967-08-31 | Monsanto Co | Preparation of polyoxytetramethylene glycol |
| US3359332A (en) * | 1963-07-25 | 1967-12-19 | Monsanto Co | Preparation of polyoxytetra-methylene glycol |
| EP0051499A1 (en) * | 1980-11-04 | 1982-05-12 | Japan Synthetic Rubber Co., Ltd. | A process for the preparation of polyether glycols |
| US4371713A (en) * | 1980-11-04 | 1983-02-01 | Japan Synthetic Rubber Co., Ltd. | Process for the preparation of polyether glycol |
| CN1037891A (en) * | 1988-04-05 | 1989-12-13 | 三井东圧化学株式会社 | The manufacture method of bisphenol A with high purity |
| US4990679A (en) * | 1988-11-23 | 1991-02-05 | Ciba-Geigy Corporation | Poly(tetrahydrofuran) |
| CN1200740A (en) * | 1996-07-10 | 1998-12-02 | 巴斯福公司 | Compositions of polytetramethylene ether glycols and polyoxy alkylene polyether polyols having low degree of unsaturation |
| US6559278B1 (en) * | 1997-04-08 | 2003-05-06 | Mueller Herbert | Method for producing tetrahydrofuran polymers |
| CN102395619A (en) * | 2009-04-15 | 2012-03-28 | 因温斯特技术公司 | Improving miscibility of otherwise immiscible compounds |
| WO2012177415A1 (en) * | 2011-06-21 | 2012-12-27 | Dow Global Technologies Llc | Energy efficient polyalkylene glycols and lubricant composition containing same |
| CN102558106A (en) * | 2011-12-15 | 2012-07-11 | 北京金骄生物质化工有限公司 | Method for preparing 2-methyltetrahydrofuran from waste biomass |
Non-Patent Citations (1)
| Title |
|---|
| 中国机械工程学会热处理学会: "《热处理手册》", 31 August 2013 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622922A (en) * | 2016-04-06 | 2016-06-01 | 苏州博纳化学科技有限公司 | Preparation method of hydrophilic dihydroxyl compounds |
| CN105622922B (en) * | 2016-04-06 | 2018-04-20 | 苏州博纳化学科技有限公司 | A kind of preparation method of hydrophily dihydroxyl compound |
| WO2018220983A1 (en) * | 2017-05-30 | 2018-12-06 | 保土谷化学工業株式会社 | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| CN110603281A (en) * | 2017-05-30 | 2019-12-20 | 保土谷化学工业株式会社 | Preparation method of biological polyether polyol, biological polyether polyol and biological polyurethane resin |
| JPWO2018220983A1 (en) * | 2017-05-30 | 2020-04-16 | 保土谷化学工業株式会社 | Biopolyether polyol production method, biopolyether polyol and biopolyurethane resin |
| EP3632958A4 (en) * | 2017-05-30 | 2020-12-30 | Hodogaya Chemical Co., Ltd. | Method for producing biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| US11279792B2 (en) | 2017-05-30 | 2022-03-22 | Hodogaya Chemical Co., Ltd. | Method for producing a biopolyether polyol, biopolyether polyol, and biopolyurethane resin |
| JP2022079647A (en) * | 2017-05-30 | 2022-05-26 | 保土谷化学工業株式会社 | Method for producing bio-polyether polyol, bio-polyether polyol and bio-polyurethane resin |
| JP7083825B2 (en) | 2017-05-30 | 2022-06-13 | 保土谷化学工業株式会社 | Method for Producing Biopolyester Polyol, Biopolyester Polyol and Biopolyurethane Resin |
| TWI768017B (en) * | 2017-05-30 | 2022-06-21 | 日商保土谷化學工業股份有限公司 | Process for producing bio-based polyether polyol, bio-based polyether polyol and bio-based polyurethane resin |
| CN110603281B (en) * | 2017-05-30 | 2022-12-13 | 保土谷化学工业株式会社 | Preparation method of biological polyether polyol, biological polyether polyol and biological polyurethane resin |
| CN112194786A (en) * | 2020-09-18 | 2021-01-08 | 上海凯众材料科技股份有限公司 | Novel modified PTMEG and preparation method of polyurethane microporous elastomer thereof |
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