CN101260186A - Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material - Google Patents
Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material Download PDFInfo
- Publication number
- CN101260186A CN101260186A CNA2008100274519A CN200810027451A CN101260186A CN 101260186 A CN101260186 A CN 101260186A CN A2008100274519 A CNA2008100274519 A CN A2008100274519A CN 200810027451 A CN200810027451 A CN 200810027451A CN 101260186 A CN101260186 A CN 101260186A
- Authority
- CN
- China
- Prior art keywords
- bamboo powder
- weight part
- raw material
- polyester ether
- ether polylol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method which adopts bamboo powder as raw material to prepare polyether ester polyol through circulated liquefaction. The method comprises the following steps: firstly, solvent is mixed with catalyst, and then the bamboo powder is added and fully stirred, thereby carrying out degradation reaction for 10 to 30 minutes; then, circulated feeding is completed once again or more than one time; and the prepared polyether ester polyol has hydroxyl value with 200 to 550 mg KOH/g, solid content with 20 to 65 percent and viscosity with 200 to 4,500 MPa.S.
Description
Technical field
The present invention relates to the polyvalent alcohol field, particularly a kind of is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder.
Background technology
Polyether ester polyol compound is one of the important source material in urethane foam field.Industrial polyether ester polyol compound is to introduce olefinic compounds in the molecule of polyester polyols alkylol cpd, make two kinds of structure formations that have ester group and ehter bond in the molecule of polyester polyols alkylol cpd, the porous plastics that makes with it has the common trait of polyester, polyether-type, but because of its cost height, extensive application is restricted, therefore reduce the production cost of polyester ether polylol, just seem particularly important.The environmental problem of bringing along with the exhaustion day by day and the petrochemical complex of fossil energy becomes increasingly conspicuous, and is the concern that the feedstock production polyol compound is subjected to scientific circles day by day with the renewable resources, replaces petroleum polymer polyvalent alcohol product with this.The main component of biological material is Mierocrystalline cellulose, hemicellulose and xylogen, contains abundant hydroxyl, if can be used, just can replace industrial required industrial chemicals, and this will reduce the demand for petroleum resources.
[Mokuzai Gakkaishi such as Japan scholar Yao Yaoguang, 1993,39 (8): 930-938] timber has been carried out the liquefaction degraded, a spot of timber can be degraded in 60min fully, but when the timber solid content surpasses certain proportion, system viscosity can increase sharply, and polycondensation very easily takes place, and residue content also can constantly increase.Ge Jinjie, Wu Rui etc. [macromolecular material and engineering, 2003,19 (2) 194-197] liquefy bagasse under certain condition, under the situation of high solid-liquid ratio, also polycondensation can take place.Present liquefaction reaction, the weight ratio of plant biomass/liquefaction solvent is generally 1: 4～10, though plant biomass is cheap, the liquefaction solvent cost is higher.In order effectively to reduce the liquefied product cost, need to improve solid-to-liquid ratio in the liquefaction process, thereby make the utilization of plant biomass more abundant.In reaction process, want complete infiltration of plants biomass, need to consume a large amount of solvents, the solid content of biomass degradation product is less in the polyvalent alcohol product of gained, and utilising efficiency is lower, and product polyvalent alcohol viscosity is higher, the condensation drawback such as serious of reuniting between the liquefied product, cause production cost too high, influenced the performance index of product, become the bottleneck that its industry extension of restriction is produced.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of bamboo powder solid content height, cost are low, technology is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder simply.
Purpose of the present invention is achieved through the following technical solutions:
A kind of is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder, comprises the steps:
(1) at first with 100 parts by weight solvent and 1～6 weight part catalyst mix and stir, is preheating to 90～180 ℃; (2) add 10～50 weight part bamboo powder then, fully stir DeR 10～30 minutes; (3) feed intake with cocycle again or once, feed intake adds 50～150 parts by weight solvent, 1～6 weight part catalyzer and 30～200 weight part bamboo powder at every turn, fully stirs DeR 10～60 minutes; Prepare high solids content bamboo powder degraded product polyester ether polylol at last.The hydroxyl value of the polyester ether polylol for preparing is 200～550mg KOH/g, and solid content is 20～65%, and viscosity is 200～4500mPaS.
The particle diameter of described bamboo powder raw material is 20～100 orders.
Described solvent is polyvalent alcohol or its ester; Specifically can be one or more mixtures in NSC 11801, propylene carbonate, ethylene glycol, polyoxyethylene glycol or the glycerol.The molecular weight of described polyoxyethylene glycol is 100～1000, preferably poly(oxyethylene glycol) 400, Polyethylene Glycol-600 or cetomacrogol 1000.
Described catalyzer is acid or alkali, specifically can be hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid or sodium hydroxide; Preferably sulfuric acid.
The number of times that described circulation feeds intake is 1～6 time.
The present invention compared with prior art has following advantage and effect:
(1) the solid content height of the polyester ether polylol for preparing of the present invention, cost is low.
(2) raw material sources such as bamboo powder of the present invention are abundant, and are cheap and easy to get, and it is convenient, renewable to buy, and environmental protection.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
At first it is mixed 100 weight part poly(oxyethylene glycol) 400 and the stirring of 4 weight part hydrochloric acid, be warming up to 150 ℃, feeding intake for the first time under whipped state adds 20 weight part bamboo powder; Behind the reaction 10min, feeding intake for the second time adds the mixed solvent of 100 weight part polyoxyethylene glycol and 5 weight part hydrochloric acid earlier, adds 50 weight part bamboo powder again; Termination reaction behind the reaction 30min obtains solid content and is 23.6% bamboo powder polyester ether polylol, and viscosity is 550mPaS, and hydroxyl value is 470mg KOH/g.
Embodiment 2
At first it is mixed 100 weight part polyoxyethylene glycol and the stirring of 3 weight part sulfuric acid, be warming up to 160 ℃; Feeding intake for the first time under whipped state adds 30 weight part bamboo powder, and behind the reaction 10min, feeding intake for the second time adds 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier, adds 60 weight part bamboo powder again; Termination reaction behind the reaction 30min obtains solid content and is 31.1% bamboo powder polyester ether polylol, and viscosity is 1100mPaS, and hydroxyl value is 420mg KOH/g.
Embodiment 3
At first it is mixed 80 weight part polyoxyethylene glycol, 20 weight part glycerol and the stirring of 3 weight part sulfuric acid, be warming up to 150 ℃, feeding intake for the first time under whipped state adds 40 weight part bamboo powder; Behind the reaction 10min, feeding intake for the second time adds polyoxyethylene glycol and glycerol (mass ratio of polyoxyethylene glycol and glycerol is 4: the 1) mixed solvent and the 4 weight part vitriolic mixed solvents of 100 weight parts earlier, adds 80 weight part bamboo powder again; Termination reaction behind the reaction 30min obtains solid content and is 37.1% bamboo powder polyester ether polylol, and viscosity is 2100mPaS, and hydroxyl value is 410mg KOH/g.
Embodiment 4
At first it is mixed 100 weight part polyoxyethylene glycol and the stirring of 3 weight part sulfuric acid, be warming up to 150 ℃; Under whipped state, feed intake for the first time and add 30 weight part bamboo powder; Behind the reaction 10min, feeding intake for the second time adds 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier, adds 60 weight part bamboo powder again; Behind the reaction 20min, feeding intake for the third time adds 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier, adds 100 weight part bamboo powder again; Termination reaction behind the reaction 30min obtains solid content and is 38.8% bamboo powder polyester ether polylol, and viscosity is 2300mPaS, and hydroxyl value is 380mgKOH/g.
Embodiment 5
At first it is mixed 100 weight part polyoxyethylene glycol and the stirring of 3 weight part sulfuric acid, be warming up to 150 ℃; Under whipped state, feed intake for the first time and add 30 weight part bamboo powder; Behind the reaction 10min, feeding intake for the second time adds 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier, adds 70 weight part bamboo powder again; Behind the reaction 15min, feeding intake for the third time adds 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier, adds 100 weight part bamboo powder again; Behind the reaction 20min, the 4th feed intake adding 100 weight part polyoxyethylene glycol and 5 weight part vitriolic mixed solvents earlier add 150 weight part bamboo powder again; Termination reaction behind the reaction 40min obtains solid content and is 46.6% bamboo powder polyester ether polylol, and viscosity is 3700mPaS, and hydroxyl value is 350mg KOH/g.
Embodiment 6
At first it is mixed 80 weight part polyoxyethylene glycol, 20 weight part glycerol and the stirring of 3 weight parts, be warming up to 150 ℃, feeding intake for the first time under whipped state adds 50 weight part bamboo powder; Behind the reaction 15min, feeding intake for the second time adds polyoxyethylene glycol and glycerol (mass ratio 4: the 1) mixed solvent and the 4 weight part vitriolic mixed solvents of 100 weight parts earlier, adds 100 weight part bamboo powder again; Behind the reaction 20min, feeding intake for the third time adds polyoxyethylene glycol and glycerol (mass ratio 4: the 1) mixed solvent and the 6 weight part vitriolic mixed solvents of 100 weight parts earlier, adds 200 weight part bamboo powder again; Termination reaction behind the reaction 60min obtains solid content and is 53.8% bamboo powder polyester ether polylol, and viscosity is 4200mPaS, and hydroxyl value is 330mg KOH/g.
Embodiment 7
At first it is mixed 100 weight part polyoxyethylene glycol and the stirring of 3 weight part sulfuric acid, be warming up to 150 ℃; Under whipped state, feed intake for the first time and add 30 weight part bamboo powder; Behind the reaction 10min, feeding intake for the second time adds 50 weight part polyoxyethylene glycol and 3 weight part vitriolic mixed solvents earlier, adds 50 weight part bamboo powder again; Behind the reaction 10min, feeding intake for the third time adds 50 weight part ethylene glycol and 3 weight part vitriolic mixed solvents earlier, adds 100 weight part bamboo powder again; Behind the reaction 20min, the 4th feed intake adding 100 weight part polyoxyethylene glycol and 4 weight part vitriolic mixed solvents earlier add 150 weight part bamboo powder again; Behind the reaction 30min, the 5th feed intake adding 100 weight part polyoxyethylene glycol and 5 weight part vitriolic mixed solvents earlier add 150 weight part bamboo powder again; Behind the reaction 30min, the 6th feed intake adding 100 weight part ethylene glycol and 5 weight part vitriolic mixed solvents earlier add 200 weight part bamboo powder again; Termination reaction behind the reaction 40min obtains solid content and is 57.6% bamboo powder polyester ether polylol, and viscosity is 4350mPaS, and hydroxyl value is 310mg KOH/g.
Claims (4)
1, a kind of is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder, it is characterized in that comprising the steps: that (1) at first with 100 parts by weight solvent and 1～6 weight part catalyst mix and stir, is preheating to 90～180 ℃; (2) add 10～50 weight part bamboo powder then, fully stir DeR 10～30 minutes; (3) feed intake with cocycle again or once, feed intake adds 50～150 parts by weight solvent, 1～6 weight part catalyzer and 30～200 weight part bamboo powder at every turn, fully stirs DeR 10～60 minutes; Prepare high solids content bamboo powder degraded product polyester ether polylol at last.
2, according to claim 1 is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder, it is characterized in that: described solvent is one or more mixtures in NSC 11801, propylene carbonate, ethylene glycol, polyoxyethylene glycol or the glycerol.
3, according to claim 1 is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder, it is characterized in that: described catalyzer is hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid or sodium hydroxide.
4, according to claim 1 is the method that the raw material circulation liquefaction prepares polyester ether polylol with the bamboo powder, it is characterized in that: the number of times that described circulation feeds intake is 1～6 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100274519A CN101260186B (en) | 2008-04-15 | 2008-04-15 | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100274519A CN101260186B (en) | 2008-04-15 | 2008-04-15 | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101260186A true CN101260186A (en) | 2008-09-10 |
| CN101260186B CN101260186B (en) | 2011-06-08 |
Family
ID=39960899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100274519A Expired - Fee Related CN101260186B (en) | 2008-04-15 | 2008-04-15 | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101260186B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362818B (en) * | 2008-09-12 | 2012-01-11 | 南昌大学 | Method for preparing biodegradable polyurethane rigid foam from bamboo waste liquefaction products |
| CN103086844A (en) * | 2013-01-30 | 2013-05-08 | 中科院广州化学有限公司 | Method for preparing polyalcohol by ultrasonic wave assisting rapidly liquefied plant biomass |
| CN103601866B (en) * | 2013-11-26 | 2015-11-04 | 北京联合大学生物化学工程学院 | A kind of method utilizing plant polyatomic alcohol synthesis of polyurethane foam materials |
| CN106520171A (en) * | 2016-11-02 | 2017-03-22 | 中国林业科学研究院林产化学工业研究所 | Method for liquefaction of bamboo powder in water/n-butyl alcohol solvent system and separation of product thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528824A (en) * | 2003-09-26 | 2004-09-15 | 中国科学院广州化学研究所 | Vegetable fiber liquefied matter, and preparing method and use thereof |
| CN1255493C (en) * | 2004-11-23 | 2006-05-10 | 中国科学院广州化学研究所 | Epoxy resin adhesive containing non-wood fiber component and its preparation method |
-
2008
- 2008-04-15 CN CN2008100274519A patent/CN101260186B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362818B (en) * | 2008-09-12 | 2012-01-11 | 南昌大学 | Method for preparing biodegradable polyurethane rigid foam from bamboo waste liquefaction products |
| CN103086844A (en) * | 2013-01-30 | 2013-05-08 | 中科院广州化学有限公司 | Method for preparing polyalcohol by ultrasonic wave assisting rapidly liquefied plant biomass |
| CN103601866B (en) * | 2013-11-26 | 2015-11-04 | 北京联合大学生物化学工程学院 | A kind of method utilizing plant polyatomic alcohol synthesis of polyurethane foam materials |
| CN106520171A (en) * | 2016-11-02 | 2017-03-22 | 中国林业科学研究院林产化学工业研究所 | Method for liquefaction of bamboo powder in water/n-butyl alcohol solvent system and separation of product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101260186B (en) | 2011-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Loow et al. | Typical conversion of lignocellulosic biomass into reducing sugars using dilute acid hydrolysis and alkaline pretreatment | |
| Li et al. | The current and emerging sources of technical lignins and their applications | |
| Pan | Synthesis of polymers from organic solvent liquefied biomass: A review | |
| Li et al. | Lignin as a green and multifunctional alternative to phenol for resin synthesis | |
| CN102304213B (en) | Method for preparing polyurethane from straw fermentation residua through polyatomic alcohol liquefaction | |
| CN101362818B (en) | Method for preparing biodegradable polyurethane rigid foam from bamboo waste liquefaction products | |
| CN101260186B (en) | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material | |
| CN103013552B (en) | Method for preparing biological oil by liquefying biomass under atmospheric pressure by using solid acid catalyst | |
| EP3867325B1 (en) | An aqueous adhesive composition for lignocellulosic materials such as wood and a method of production | |
| CN105111997A (en) | Preparation method of double-component non-solvent polyurethane adhesive used for food-grade packaging | |
| CN101348553A (en) | Plant polyatomic alcohol polyurethane rigid foam material | |
| CN102492384A (en) | Method of preparing phenolic resin through liquefaction of lignin by using ionic liquid | |
| CN1850933A (en) | Lignin Environmental-protection type adhesive and its preparing method | |
| CN102070891A (en) | Polyester composite filled with lignin and preparation method thereof | |
| WO2018205020A1 (en) | Depolymerization of lignin for the production of bio-based polyols and phenols and lignin-based pf/pu/epoxy resins/foams | |
| CN111073325A (en) | Lignin/fiber thermoplastic composite material and preparation method thereof | |
| Xue et al. | Efficient dissolution of lignin in novel ternary deep eutectic solvents and its application in polyurethane | |
| CN114736507B (en) | Preparation method of biomass-based modified aldehyde-free environment-friendly artificial board adhesive | |
| CN105038262A (en) | Environment-friendly regenerable softener and preparation method thereof | |
| CN103554400A (en) | Liquefaction method of lignin for preparing thermoplastic phenolic resin | |
| CN109369886A (en) | A kind of method that eutectic solvent modified lignin resin is used for epoxy curing agent | |
| Yuan et al. | Fully bio-based adhesive designed through lignin-cellulose combination and interfacial bonding reinforcement | |
| JP2003277615A (en) | Resin composition | |
| CN101967363B (en) | Isocyanate/polyethylene terephthalate (PET) aqueous emulsion adhesive, preparation method thereof and use thereof | |
| CN102093574A (en) | Water dispersed lignin polyurethane material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee after: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Address before: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110608 Termination date: 20210415 |