CN103613733A - Novel method for preparing lignin waterborne polyurethane composite material - Google Patents
Novel method for preparing lignin waterborne polyurethane composite material Download PDFInfo
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- CN103613733A CN103613733A CN201310655816.3A CN201310655816A CN103613733A CN 103613733 A CN103613733 A CN 103613733A CN 201310655816 A CN201310655816 A CN 201310655816A CN 103613733 A CN103613733 A CN 103613733A
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- xylogen
- lignin
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a novel method for preparing a lignin waterborne polyurethane composite material. The method is characterized in that the lignin waterborne polyurethane is adopted as a system, epoxy chloropropane is mainly adopted to modify the lignin in order to improve the dispersibility of the lignin in the waterborne polyurethane and improve the activity of the surface functional group of the lignin, and the modified lignin and polyether polyol solution are processed in the reaction such as the formation of a prepolymer and chain extension to prepare a series of lignin waterborne polyurethane materials with different lignin contents. The method is simple, the scheme is feasible, and a novel method is provided for the development of the lignin in the macromolecule field such as the polyurethane.
Description
Technical field
The present invention relates to a kind of novel method of preparing xylogen type Waterborne PU Composite, be specifically related to adopt epoxychloropropane modified xylogen by pre-polymerization, the novel method of the aqueous polyurethane that a series of content of lignin of the reaction such as chain extension preparation are different.
Background technology
Urethane is because of its good physicals and mechanical property, be widely used in a lot of aspects such as communications and transportation, Products Industry, daily life, aqueous polyurethane is compared with urethane because of it, has the advantages such as pollution-free, environmental protection and is widely used in a plurality of fields such as industrial production and daily life.
Xylogen is the natural macromolecular compound that a class contains abundant alcoholic extract hydroxyl group and phenolic hydroxyl group, is the second largest integral part in plant.In recent years, in short supply along with environmental pollution and industrial chemicals, xylogen is because of the molecular structure of himself, and is reproducible, has pollution-free degradable feature, and xylogen is used in the high molecular fields such as urethane widely.Owing to containing oh group in lignin molecule, can be used as the main reaction thing isocyanic ester effect in a kind of alcohols and urethane, replace a part of polyether glycol, participate in reaction, so not only can improve the performance of urethane, and the consumption of saving polyether glycol, reducing costs, the effect of xylogen in urethane is mainly effect crosslinked and that fill.
Xylogen is because of in its water insoluble and organic solvent, so be seldom applied in the urethane of water-based.The technical problem of the most critical of the preparation of xylogen type aqueous polyurethane is dispersed in synthesis of polyurethane principal reaction thing of xylogen, and better and these two principal reaction phases appearances, therefore before reaction, first xylogen is carried out to modification, adopt epoxy chloropropane modified lignin resin under the catalysis of alkali, the surfactivity of xylogen is improved, can be dispersed in reaction solution better.
Summary of the invention
For realizing technical scheme provided by the present invention, be:
(1) modified lignin resin dissolves dispersion in polyether glycol
With the clean small beaker of 50mL, weigh that to account for polyether glycol quality be the ultrasonic dispersion of the acetone soln 20min that xylogen after 0.5%～2% modification adds 10mL, then put in the four-hole bottle with the 250mL of whipping appts, slowly add wherein again 20.0g polypropylene glycol to add in four neck flasks, 70 ℃ of stirring and dissolving 2h, the xylogen obtaining after modification is dispersed in the dispersion liquid in polyether glycol.
(2) preparation of xylogen type aqueous polyurethane
The temperature of the dispersion liquid of the polyether glycol of the xylogen of 1. waiting to contain the modification that has different mass is down to room temperature; pass into nitrogen protection; and uniform stirring; but want stirring velocity inviolent; at room temperature slowly drip the 2,4 toluene diisocyanate (TDI) of 8.7g, after TDI to be added; water-bath temperature is adjusted to 70 ℃, under mechanical stirring, reacts 2h.
2. after the first step reaction 2h, bath temperature is adjusted to 60 ℃, with dropper, slowly drip subsequently the DMPA of 1.87g, drip DMPA and with dropper, drip 1～2 dibutyl tin laurate more afterwards, from dripping catalyzer, start timing, reaction 2h, the viscosity of observe system in whole reaction process, adds appropriate acetone when viscosity is excessive, reduce the viscosity of system, in order to avoid system viscosity is excessive, cause reaction to carry out.After reaction 2h, bath temperature is adjusted to 40 ℃; When the temperature of water-bath is 40 ℃, after adding 1.39g TEA reaction 10min, add 150mL H
2o, then improves stirring velocity, continues to stir 1h, just obtains the water miscible liquid of xylogen type aqueous polyurethane.
3. then water miscible liquid 100mL is poured in mould, oven temperature is transferred to 60 ℃, dry 2 days, just obtain target product.
For better understanding the present invention, below in conjunction with embodiment, the present invention is done further and described in detail, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment:
(1) with the clean small beaker of 50mL, weigh that to account for polyether glycol quality be the ultrasonic dispersion of the acetone soln 20min that xylogen after 1% modification adds 10mL, then put in the four-hole bottle with the 250mL of whipping appts, slowly add wherein again 20.0g polypropylene glycol to add in four neck flasks, 70 ℃ of stirring and dissolving 2h, the xylogen obtaining after modification is dispersed in the dispersion liquid in polyether glycol.
(2) temperature of dispersion liquid of polyether glycol of waiting to contain the xylogen of the modification that has different mass is down to room temperature; pass into nitrogen protection; and uniform stirring; but want stirring velocity inviolent; at room temperature slowly drip the 2,4 toluene diisocyanate (TDI) of 8.7g, after TDI to be added; water-bath temperature is adjusted to 70 ℃, under mechanical stirring, reacts 2h.
(3) after the first step reaction 2h, bath temperature is adjusted to 60 ℃, with dropper, slowly drip subsequently the DMPA of 1.87g, drip DMPA and with dropper, drip 1～2 dibutyl tin laurate more afterwards, from dripping catalyzer, start timing, reaction 2h, the viscosity of observe system in whole reaction process, adds appropriate acetone when viscosity is excessive, reduce the viscosity of system, in order to avoid system viscosity is excessive, cause reaction to carry out.After reaction 2h, bath temperature is adjusted to 40 ℃; When the temperature of water-bath is 40 ℃, after adding 1.39gTEA reaction 10min, add 150mLH
2o, then improves stirring velocity, continues to stir 1h, just obtains the water miscible liquid of xylogen type aqueous polyurethane.
(4) then water miscible liquid 100mL is poured in mould, oven temperature is transferred to 60 ℃, dry 2 days, just obtain target product.Through mechanical test addition tensile strength in 1%, increase to some extent, reached 12.967Mpa.
Claims (3)
1. a novel method of preparing xylogen type Waterborne PU Composite, concrete steps are as follows:
(1) xylogen weighing after modification adds the ultrasonic dispersion of acetone soln, then put in the four-hole bottle with the 250mL of whipping appts, slowly add wherein again 20.0g polypropylene glycol to add in four neck flasks, 70 ℃ of stirring and dissolving 2h, the xylogen obtaining after modification is dispersed in the dispersion liquid in polyether glycol;
(2) dispersion liquid of step (1) is down to room temperature, passes into nitrogen protection, and uniform stirring; slowly drip the 2,4 toluene diisocyanate (TDI) of 8.7g, after TDI to be added; temperature is adjusted to 70 ℃; stir after lower reaction 2h, temperature is adjusted to 60 ℃, drips the DMPA of 1.87g; drip again afterwards 1～2 dibutyl tin laurate; after reaction 2h, temperature is adjusted to 40 ℃, adds 1.39gTEA reaction 10min, adds 150mL H
2o, continues to stir 1h, just obtains the water miscible liquid of xylogen type aqueous polyurethane;
(3) the water miscible liquid 100mL of step (2) is poured in mould, at 60 ℃, be dried 2 days, just obtain target product.
2. an a kind of novel method of preparing xylogen type Waterborne PU Composite as claimed in claim 1, is characterized in that: xylogen is originated in all agriculture and forestry organic waste materials that contain xylogen, comprises alkali lignin, sourwood quality, alcoholysis xylogen etc.
3. an a kind of novel method of preparing xylogen type Waterborne PU Composite as claimed in claim 1, it is characterized in that: the mass percent of the xylogen of modification is 0.5%～2%, its physical strength of xylogen type polyurethane that the content difference of xylogen obtains is also different.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310655816.3A CN103613733A (en) | 2013-12-05 | 2013-12-05 | Novel method for preparing lignin waterborne polyurethane composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310655816.3A CN103613733A (en) | 2013-12-05 | 2013-12-05 | Novel method for preparing lignin waterborne polyurethane composite material |
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| CN103613733A true CN103613733A (en) | 2014-03-05 |
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| CN201310655816.3A Pending CN103613733A (en) | 2013-12-05 | 2013-12-05 | Novel method for preparing lignin waterborne polyurethane composite material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628982A (en) * | 2015-02-13 | 2015-05-20 | 陕西科技大学 | Preparation method of alkali lignin-based waterborne polyurethane |
| CN104693406A (en) * | 2015-03-27 | 2015-06-10 | 陕西科技大学 | Preparing method of epoxy lignin modified waterborne polyurethane |
| CN105330810A (en) * | 2015-11-27 | 2016-02-17 | 南京林业大学 | Preparation method of attapulgite modified lignin type polyurethane material |
| CN105331321A (en) * | 2015-11-24 | 2016-02-17 | 苏州盖德精细材料有限公司 | Lignin modified waterborne polyurethane adhesive and preparation method thereof |
| CN109081900A (en) * | 2018-07-06 | 2018-12-25 | 山东圣泉新材料股份有限公司 | Modified polyalcohol and preparation method, modified polyurethane material and preparation method and application |
| CN110157439A (en) * | 2019-06-21 | 2019-08-23 | 成都新柯力化工科技有限公司 | A kind of modified polyurethane of weatherproof fixes the sand rehabilitating soil agent and preparation method |
| CN113201112A (en) * | 2021-04-06 | 2021-08-03 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
| CN113429543A (en) * | 2021-06-16 | 2021-09-24 | 中国制浆造纸研究院有限公司 | Method for preparing polyurethane rigid foam from epoxidized lignin polyol |
| CN113527611A (en) * | 2021-07-29 | 2021-10-22 | 华南理工大学 | Polyurethane dispersion liquid and preparation method and application thereof |
| CN114085517A (en) * | 2021-12-08 | 2022-02-25 | 齐鲁工业大学 | Lignin-modified waterborne polyurethane film and preparation method thereof |
| CN109575351B (en) * | 2017-09-28 | 2022-03-04 | 中国石油化工股份有限公司 | Lignin-based polyurethane foam and preparation method thereof |
-
2013
- 2013-12-05 CN CN201310655816.3A patent/CN103613733A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628982A (en) * | 2015-02-13 | 2015-05-20 | 陕西科技大学 | Preparation method of alkali lignin-based waterborne polyurethane |
| CN104628982B (en) * | 2015-02-13 | 2019-01-22 | 陕西科技大学 | A kind of preparation method of alkali lignin base water polyurethane |
| CN104693406A (en) * | 2015-03-27 | 2015-06-10 | 陕西科技大学 | Preparing method of epoxy lignin modified waterborne polyurethane |
| CN105331321A (en) * | 2015-11-24 | 2016-02-17 | 苏州盖德精细材料有限公司 | Lignin modified waterborne polyurethane adhesive and preparation method thereof |
| CN105330810A (en) * | 2015-11-27 | 2016-02-17 | 南京林业大学 | Preparation method of attapulgite modified lignin type polyurethane material |
| CN105330810B (en) * | 2015-11-27 | 2018-10-26 | 南京林业大学 | A kind of preparation method of attapulgite modified lignin type polyurethane material |
| CN109575351B (en) * | 2017-09-28 | 2022-03-04 | 中国石油化工股份有限公司 | Lignin-based polyurethane foam and preparation method thereof |
| CN109081900B (en) * | 2018-07-06 | 2021-01-26 | 山东圣泉新材料股份有限公司 | Modified polyol and preparation method thereof, modified polyurethane material and preparation method and application thereof |
| CN109081900A (en) * | 2018-07-06 | 2018-12-25 | 山东圣泉新材料股份有限公司 | Modified polyalcohol and preparation method, modified polyurethane material and preparation method and application |
| CN110157439A (en) * | 2019-06-21 | 2019-08-23 | 成都新柯力化工科技有限公司 | A kind of modified polyurethane of weatherproof fixes the sand rehabilitating soil agent and preparation method |
| CN110157439B (en) * | 2019-06-21 | 2021-06-15 | 湖南凯迪工程科技有限公司 | Wind erosion resistant modified polyurethane sand-fixation soil remediation agent and preparation method thereof |
| CN113201112A (en) * | 2021-04-06 | 2021-08-03 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
| CN113201112B (en) * | 2021-04-06 | 2022-06-14 | 华南理工大学 | Waterborne polyurethane with lignin as chain extender and preparation method and application thereof |
| CN113429543A (en) * | 2021-06-16 | 2021-09-24 | 中国制浆造纸研究院有限公司 | Method for preparing polyurethane rigid foam from epoxidized lignin polyol |
| CN113527611A (en) * | 2021-07-29 | 2021-10-22 | 华南理工大学 | Polyurethane dispersion liquid and preparation method and application thereof |
| CN114085517A (en) * | 2021-12-08 | 2022-02-25 | 齐鲁工业大学 | Lignin-modified waterborne polyurethane film and preparation method thereof |
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Application publication date: 20140305 |