CN102718962A - Segmented polyether compound modified lignin and preparation method thereof - Google Patents
Segmented polyether compound modified lignin and preparation method thereof Download PDFInfo
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- CN102718962A CN102718962A CN2012102155154A CN201210215515A CN102718962A CN 102718962 A CN102718962 A CN 102718962A CN 2012102155154 A CN2012102155154 A CN 2012102155154A CN 201210215515 A CN201210215515 A CN 201210215515A CN 102718962 A CN102718962 A CN 102718962A
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Abstract
The invention belongs to the field of chemical synthesis, concretely relates to a segmented polyether compound modified lignin and a preparation method thereof and is characterized in that the segmented polyether compound modified lignin is prepared from the following raw materials in parts by weight: 100 parts of purified lignin, 0.1-1 part of base catalyst, 20-100 parts of solvent, 70 parts of propylene oxide and 30 parts of epoxy ethane. The invention has the advantages that (1) because the epoxy ethane is added into the segmented polyether compound modified lignin prepared by applying the method disclosed by the invention, the flexibility of molecules is further improved; (2) the pollution of the lignin as a main pollutant in paper-manufacturing industry to environments is reduced, and wastes are changed into valuables, so that the utilization ratio of lignin resources is increased; and (3) the lignin is used as a raw material for manufacturing polyurethane materials, so that the consumption of petroleum resources is reduced, and energy sources are saved.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of block polyether compound modified lignin and preparation method thereof.
Background technology
Xylogen extensively is present in the spermatophyte, and is very huge in the quantity that occurring in nature exists, and the xylogen of China only about 6% obtains utilizing.Xylogen owing to be not fully utilized, has become one of primary pollution source in the paper industry as the by product of wood saccharification industry and paper industry, not only causes serious environmental to pollute, and also causes the significant waste of resource.Xylogen is mainly elementary composition by carbon, hydrogen, three kinds of oxygen, It is generally accepted that xylogen is the natural phenolic macromolecular compound of the crosslinking net that is formed by connecting through C-0 key or C-C key hydrocinnamyl (C9) unit.Owing to contain a large amount of phenolic hydroxyl groups and alcoholic extract hydroxyl group, general formula often is designated as R-OH.Pulp industry is through methods such as alkali or acid catalysiss; Make the ehter bond in the lignin molecule take place to rupture and separate with semicellulose with Mierocrystalline cellulose; And be dissolved in the water with the form of salt; Form so-called black liquor or red liquid, industrial lignin is actually the fragment by the natural lignin that extracts in the black liquor, its relative molecular mass at hundreds of between millions of.Molecular weight ranges accounts for 50% 20000～50000, accounts for 45% between the 1000-20000.
At present; Xylogen is in Industrial Application: add people's xylogen in (1) rubber stiffener tree elastomer; Phenolic group in its molecule and carboxyl, amine and aldehydes reaction with as anti-aging agent are woven into more tough and tensile network; Make soft and limber tree elastomer is in the network structure, thereby improve the physical and mechanical properties of tree elastomer.(2) application of xylogen aspect plastics: utilize the functional group of lignin molecule to cause the caprolactam monomer mass polymerization, having made with the lignin molecule is core, is the L-CL radial copolymer of arm with the caprolactone segment.(3) application in tackiness agent: xylogen is a kind of natural high moleculer eompound, itself cohesiveness is just arranged, and passes through phenol, aldehyde or other method modification again, and its cohesiveness can be better.
International and domestic correlative study for xylogen at present is also a lot.The patent No. of Guangzhou Chemistry Inst., Chinese Academy of Sciences is ZL96119137.6; The applying date is in 1996.8.30's " preparation method of xylogen graft copolymer " patent of invention, discloses to use electrochemical method graft copolymerization to obtain having the polymer monomer of alkene or substituted olefine.The lignin polymers monomer that this invention obtains is to have alkene or substituted olefine, also has very big difficulty as being applied to macromolecular material.
Summary of the invention
The purpose of this invention is to provide a kind of block polyether compound modified lignin and preparation method thereof, the block polyether compound modified lignin for preparing has good mutual solubility, reactivity, can be used for hard polyurethane foam material.
A kind of block polyether compound modified lignin of the present invention according to the parts by weight meter, is processed by following raw material: 30 parts in 100 parts in purifying xylogen, 0.1～1 part of alkaline catalysts, 20～100 parts of solvents, 70 parts of propylene oxide and oxyethane.
Wherein, alkaline catalysts is preferably n n dimetylaniline.
Solvent is preferably N.
The preparation method of block polyether compound modified lignin of the present invention may further comprise the steps:
(1) voltage-resistant reactor is evacuated to vacuum tightness-0.09KPa, mends nitrogen to normal pressure, 4～5 times repeatedly, oxygen determination content≤150ppm;
(2) get purifying xylogen, alkaline catalysts and solvent to voltage-resistant reactor; Reinforced back feeds nitrogen protection, and airtight voltage-resistant reactor also stirs, heat temperature raising to 90～140 ℃; When reaction pressure is 0.2～0.6MPa, feed the propylene oxide and the oxyethane that mix;
(3) oxyethane and propylene oxide reaction be fully to normal pressure, stops heating, stops to stir after being cooled to room temperature; Feeding nitrogen makes voltage-resistant reactor to normal pressure; Underpressure distillation is then removed the lower boiling fraction for 120 ℃, obtains the product block polyether compound modified lignin.
The block polyether compound modified lignin that the present invention makes can be used in makes rigid poly urethanes insulating foam material.
The invention has the advantages that: the block polyether compound modified lignin that method of the present invention makes is used in (1), owing to added the kindliness that oxyethane has more increased molecule; (2) reduce xylogen as the principal pollutant in the paper industry and pollution on the environment is turned waste into wealth, improved the utilization ratio of xylogen resource; (3) make polyurethane material with xylogen as raw material, reduced, practiced thrift the energy consumption of petroleum resources.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1:
Employed purifying xylogen all obtains according to following preparation method:
According to the parts by weight meter, get 100 parts of thick alkali lignins, be made into the aqueous solution of massfraction 10%, using the NaOH regulator solution pH value of massfraction 10% is 12; All dissolve to xylogen, after 6000r/rain spinning 5min removed not dissolved impurity, liquid was heated to 60 ℃; Using the sulphur acid for adjusting pH value of massfraction 20% is 3, leaves standstill, and removes supernatant liquid; The throw out washing, through 6000r/rain spinning 10min, throw out is washed till neutrality; At 105 ℃ of dry back grind into powders, weighing obtains 70 parts of purifying xylogen, and sealing is preserved subsequent use.The chemical constitution of the purifying xylogen that obtains is: the xylogen massfraction is 95%, and the total reducing sugar massfraction is 2.70%, and the ash content massfraction is 1.70%, and the phenolic hydroxyl group molality is 2.6mol/kg.
Prepare block polyether compound modified lignin according to following steps:
(1) voltage-resistant reactor is evacuated to vacuum tightness-0.09KPa, mends nitrogen to normal pressure, 5 times repeatedly, oxygen determination content≤150ppm;
(2) according to the parts by weight meter, get 100 parts in purifying xylogen, 0.1 part of catalyzer n n dimetylaniline, 100 parts of solvent Ns are to voltage-resistant reactor; Reinforced back feeds nitrogen protection; Airtight voltage-resistant reactor also stirs, and stirring velocity is 200r/min, heat temperature raising to 90 ℃; When reaction pressure is 0.3MPa, feed 70 parts of propylene oxide and 30 parts of oxyethane of mixing;
(3) oxyethane and propylene oxide reaction are fully to normal pressure; Stop heating; Be cooled to and stop after the room temperature stirring, feed nitrogen and make voltage-resistant reactor, then underpressure distillation under 80 ℃, the condition of 1.33KPa to normal pressure; Remove lower boiling fraction below 120 ℃, obtain the product block polyether compound modified lignin.
Claims (4)
1. block polyether compound modified lignin is characterized in that being processed by following raw material according to the parts by weight meter: 30 parts in 100 parts in purifying xylogen, 0.1～1 part of alkaline catalysts, 20～100 parts of solvents, 70 parts of propylene oxide and oxyethane.
2. block polyether compound modified lignin according to claim 1 is characterized in that alkaline catalysts is a n n dimetylaniline.
3. block polyether compound modified lignin according to claim 1 is characterized in that solvent is a N.
4. the preparation method of the described block polyether compound modified lignin of claim 1 is characterized in that may further comprise the steps:
(1) voltage-resistant reactor is evacuated to vacuum tightness-0.09KPa, mends nitrogen to normal pressure, 4～5 times repeatedly, oxygen determination content≤150ppm;
(2) get purifying xylogen, alkaline catalysts and solvent to voltage-resistant reactor; Reinforced back feeds nitrogen protection, and airtight voltage-resistant reactor also stirs, heat temperature raising to 90～140 ℃; When reaction pressure is 0.2～0.6MPa, feed the propylene oxide and the oxyethane that mix;
(3) oxyethane and propylene oxide reaction be fully to normal pressure, stops heating, stops to stir after being cooled to room temperature; Feeding nitrogen makes voltage-resistant reactor to normal pressure; Underpressure distillation is then removed the lower boiling fraction for 120 ℃, obtains the product block polyether compound modified lignin.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131020A (en) * | 2013-01-22 | 2013-06-05 | 华南理工大学 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
| CN110982057A (en) * | 2019-12-17 | 2020-04-10 | 上海东大聚氨酯有限公司 | Polyether polyol derived from solvent-free liquefied lignin and preparation method thereof |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
| CN114133508A (en) * | 2022-01-14 | 2022-03-04 | 南京先进生物材料与过程装备研究院有限公司 | High-performance lignin-based polyurethane and preparation method thereof |
| CN114230750A (en) * | 2021-12-17 | 2022-03-25 | 南京先进生物材料与过程装备研究院有限公司 | Lignin-based polyurethane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297475A (en) * | 2006-04-28 | 2007-11-15 | Asahi Glass Co Ltd | Method for producing polyether, polyurethane, prepolymer having isocyanate terminal and polyurethane foam |
| CN101157708A (en) * | 2007-08-31 | 2008-04-09 | 中国林业科学研究院林产化学工业研究所 | Block polyether compound modified lignin and preparation method and uses thereof |
-
2012
- 2012-06-27 CN CN2012102155154A patent/CN102718962A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007297475A (en) * | 2006-04-28 | 2007-11-15 | Asahi Glass Co Ltd | Method for producing polyether, polyurethane, prepolymer having isocyanate terminal and polyurethane foam |
| CN101157708A (en) * | 2007-08-31 | 2008-04-09 | 中国林业科学研究院林产化学工业研究所 | Block polyether compound modified lignin and preparation method and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 慕朝师等: "聚醚多元醇的研究进展", 《化工技术与开发》, vol. 38, no. 12, 31 December 2009 (2009-12-31), pages 13 - 14 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131020A (en) * | 2013-01-22 | 2013-06-05 | 华南理工大学 | Carboxylic sulfonic-acid-group lignin dye dispersing agent and preparation method thereof |
| CN110982057A (en) * | 2019-12-17 | 2020-04-10 | 上海东大聚氨酯有限公司 | Polyether polyol derived from solvent-free liquefied lignin and preparation method thereof |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
| CN114230750A (en) * | 2021-12-17 | 2022-03-25 | 南京先进生物材料与过程装备研究院有限公司 | Lignin-based polyurethane and preparation method thereof |
| CN114230750B (en) * | 2021-12-17 | 2023-10-31 | 南京先进生物材料与过程装备研究院有限公司 | Lignin-based polyurethane and preparation method thereof |
| CN114133508A (en) * | 2022-01-14 | 2022-03-04 | 南京先进生物材料与过程装备研究院有限公司 | High-performance lignin-based polyurethane and preparation method thereof |
| CN114133508B (en) * | 2022-01-14 | 2023-10-31 | 南京先进生物材料与过程装备研究院有限公司 | High-performance lignin-based polyurethane and preparation method thereof |
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Application publication date: 20121010 |