CN104628982B - A kind of preparation method of alkali lignin base water polyurethane - Google Patents
A kind of preparation method of alkali lignin base water polyurethane Download PDFInfo
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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- 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
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- 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
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- 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
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/64—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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- 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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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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- 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
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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Abstract
The present invention is a kind of preparation method of alkali lignin base water polyurethane, it is to select diisocyanate, polyether polyol, alkali lignin, chain extender and neutralizer etc. for raw material that it, which is prepared, alkali lignin is added during using pre-polymer process synthesis aqueous polyurethane emulsion, and then prepares a series of alkali lignin base water polyurethane of different alkali lignin contents;This method is introduced into alkali lignin in aqueous polyurethane system, is one of to reduce polyalcohol dosage, improve water-base polyurethane material performance and assign the ideal method of product biological degradation property.
Description
Technical field
The invention belongs to natural macromolecular material fields, also belong to environmental-friendly ecomaterial field, are related to a kind of alkali wood
The preparation method of quality base water polyurethane.
Technical background
Lignin (lignin) abbreviation lignin is that the natural aromatic high score abundant of cellulose second is only second in plant kingdom
Son, industrial lignin derives from black liquid, thus has inexpensive, renewable, advantages of environment protection.Lignin structure is answered
The diversity of polygamy, the diversity in source and extraction process causes the difficulty and industrialized obstruction of development and utilization, thus studies
Huge opportunities and challenges are faced with exploitation lignin high molecular material.Currently, with the rapid development of society, petroleum resources
Increasingly exhausted, the various high polymer monomers from petroleum are restricted, and have seriously affected the raw material sources of polyurethane industrial, and when
Carve the development for affecting polyurethane industrial.Therefore yield is huge, reproducible environmentally friendly biological raw material increasingly obtains people
Attention and favor.Alkali lignin is exactly a kind of abundance, cheap renewable plant resources, so alkali lignin
Abundant reasonability utilize, to alleviating the energy that is faced of current mankind and environmental crisis is all of great practical significance
And strategic importance.
And aqueous polyurethane is since the introducing of main chain or pendant hydrophilic group is so that being formed by film often and having and is higher
Surface can, although polyurethane is dispersed in water phase by the method at salt, but just depositing due to these groups
Making the performances such as Water-resistance of Waterborne Polyurethane, solvent resistance, chemical-resistant and mechanical strength poor.To overcome above-mentioned lack
Point is modified the hot spot that research has become aqueous polyurethane research to aqueous polyurethane using distinct methods in recent years, domestic
Outer many researchers have carried out largely deeply comprehensive research.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of aqueous poly- ammonia of alkali lignin base
The mechanical strength of the preparation method of ester, products therefrom is higher, and preparation process is simple and low in cost.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of alkali lignin base water polyurethane, comprising the following steps:
Step 1: preparation purification alkali lignin;
Step 2: diisocyanate, the pure and mild purification alkali lignin of polyether polyols are added in three-necked flask, 60~90
It is stirred to react 1~5h at DEG C, is then cooled to 50~70 DEG C, adds DMPA hydrophilic chain extender and acetone, reacts 1~4h, drop
Temperature obtains Waterborne Polyurethane Prepolymer to 20~50 DEG C of dischargings;
Step 3: after gained Waterborne Polyurethane Prepolymer is neutralized with neutralizer, water is added to carry out high speed emulsification, vacuum distillation
It sloughs after solvent up to aqueous polyurethane emulsion.
It is described purification alkali lignin the preparation method comprises the following steps: by the aqueous solution of raw alkaline lignin mass concentration 5%~10%
NaOH solution adjust pH to 13~14, dissolve alkali lignin sufficiently, be filtered to remove insoluble matter, then use mass concentration 12%
Hydrochloric acid pH to 2~3 is adjusted at 60 DEG C, filter, be washed with distilled water repeatedly and be precipitated to neutrality, be dried in vacuo to obtain the final product.
In the step 2, the molar ratio of polyether polyol and diisocyanate is 1:(2~4), refine alkali lignin
Additional amount is to refine the additional amount of 0.5%~3.0%, the DMPA hydrophilic chain extender of alkali lignin and polyether polyol quality sum
It is the 2.0%~5.0% of the pure and mild purification alkali lignin gross mass of diisocyanate, polyether polyols, the additional amount of acetone is 10~
80mL。
In the step 2, refine alkali lignin to be mixed again with diisocyanate and polyether polyol after acetone solution,
The amount of dissolution acetone used is 20mL.
In the step 2, catalyst is added before being stirred to react, the additional amount of catalyst is diisocyanate, polyether polyols
The 0.05%~0.2% of pure and mild purification alkali lignin gross mass.
The catalyst is dibutyl tin dilaurate (being abbreviated as DBTDL).
The diisocyanate is isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) or diphenyl
- 4,4 ‵ of methane-diisocyanate (MDI).
The polyether polyol is polypropylene glycol (PPG), polytetrahydrofuran ether glycol (PTMG) or polyethylene glycol (PEG),
Number-average molecular weight is 2000.
The neutralizer is triethylamine, sodium hydroxide or potassium hydroxide, and the molar ratio of additional amount and DMPA are 1:1.
Compared with prior art, the present invention is in the synthesis process of aqueous polyurethane emulsion by adding alkali lignin,
The mechanical property for the membrane material that lotion is formed after solidifying significantly improves.Lignin in the present invention is alkali lignin, is paper maker
The byproduct of industry, low in cost, abundance.Aqueous polyurethane is a kind of ep-type material, and the present invention discards industrial
Object lignin had both obtained the material of performance improvement in conjunction with environment-friendly water-based polyurethane, and improved the application valence of lignin
Value, while its low production cost and having the characteristics that biodegradable, environmentally friendly, and present invention process is simple, with higher
Technology content.The mechanical strength of the obtained alkali lignin modified aqueous polyurethane of the invention is significantly improved, and can be used as
The materials such as film, coating.
Detailed description of the invention
Fig. 1 is the synthetic route chart of alkali lignin base water polyurethane by taking IPDI as an example.
Specific embodiment
The present invention is described in further details below with reference to embodiment.
Embodiment one
A kind of preparation method of alkali lignin base water polyurethane, the synthetic route chart of product is as shown in Figure 1, include following
Step:
Step 1: the NaOH solution of the aqueous solution of raw alkaline lignin mass concentration 6% is adjusted into pH to 13~14, makes alkali
Lignin sufficiently dissolves.It is filtered to remove insoluble matter, then with the hydrochloric acid of mass concentration 12% in 60 DEG C of downward pH to 2 or so, mistake
Filter, is washed with distilled water repeatedly and is precipitated to neutrality, and vacuum drying obtains purification alkali lignin.
Step 2: by 17.2g isophorone diisocyanate (IPDI), 50.0g polypropylene glycol (PPG2000), 0.26g essence
Alkaline lignin (with acetone solution) and 0.05g dibutyl tin dilaurate are added in three-necked flask, are stirred at 85 DEG C anti-
3h is answered, is then cooled to 65 DEG C, adds the acetone of 2.46g DMPA and 30mL, 3h is reacted, is cooled to 40 DEG C of dischargings, obtains aqueous
Base polyurethane prepolymer for use as.
Step 3: after the performed polymer that step 2 obtains is neutralized with the triethylamine (TEA) for being 1:1 with DMPA molar ratio, add
Water carries out high speed emulsification, is evaporated under reduced pressure after sloughing solvent up to modified aqueous polyurethane emulsion.
Performance verification: lotion is uniformly poured on polyfluortetraethylene plate, is placed a period of time at room temperature, is then placed in baking
In case, at 60 DEG C after dry 48h, standard dumbbell test piece is struck out.Using XWW-20B electronic universal tester, by GB/
The tensile strength and elongation at break of T1040-92 measurement glue film.The result shows that: its tensile strength is increased to by 27.6MPa
36.3MPa, elongation at break increase to 457.2% by 456.4%, and mechanical strength significantly improves.
Embodiment two
A kind of preparation method of alkali lignin base water polyurethane, comprising the following steps:
Step 1: the NaOH solution of the aqueous solution of raw alkaline lignin mass concentration 6% is adjusted into pH to 13~14, makes alkali
Lignin sufficiently dissolves.It is filtered to remove insoluble matter, then with the hydrochloric acid of mass concentration 12% in 60 DEG C of downward pH to 2 or so, mistake
Filter, is washed with distilled water repeatedly and is precipitated to neutrality, and vacuum drying obtains purification alkali lignin.
Step 2: by 12.5g toluene di-isocyanate(TDI) (TDI), 45.0g polytetrahydrofuran ether glycol (PTMG2000),
0.25g purification alkali lignin (with acetone solution) and 0.05g dibutyl tin dilaurate are added in three-necked flask, at 85 DEG C
It is stirred to react 4h, is then cooled to 60 DEG C, adds the acetone of 1.74g DMPA and 40mL, 2h is reacted, is cooled to 35 DEG C of dischargings,
Obtain Waterborne Polyurethane Prepolymer.
Step 3: the performed polymer that step 2 is obtained is added in NaOH aqueous solution, and high shear agitation is neutralized
Emulsification is evaporated under reduced pressure after sloughing solvent up to modified aqueous polyurethane emulsion.Wherein NaOH and DMPA molar ratio are 1:1.
Performance verification: lotion is uniformly poured on polyfluortetraethylene plate, is placed a period of time at room temperature, is then placed in baking
In case, at 60 DEG C after dry 48h, standard dumbbell test piece is struck out.Using XWW-20B electronic universal tester, by GB/
The tensile strength and elongation at break of T1040-92 measurement glue film.The result shows that: its tensile strength is increased to by 11.2MPa
12.7MPa, less, mechanical strength slightly improves for elongation at break variation.
Embodiment three
A kind of preparation method of alkali lignin base water polyurethane, comprising the following steps:
Step 1: the NaOH solution of the aqueous solution of raw alkaline lignin mass concentration 6% is adjusted into pH to 13~14, makes alkali
Lignin sufficiently dissolves.It is filtered to remove insoluble matter, then with the hydrochloric acid of mass concentration 12% in 60 DEG C of downward pH to 2 or so, mistake
Filter, is washed with distilled water repeatedly and is precipitated to neutrality, and vacuum drying obtains purification alkali lignin.
Step 2: by -4,4 ‵ of 13.75g diphenyl methane-diisocyanate (MDI), 47.6g polyethylene glycol
(PEG2000), 0.28g refines alkali lignin (with acetone solution) and 0.05g dibutyl tin dilaurate is added to three-necked flask
In, it is stirred to react 5h at 85 DEG C, is then cooled to 65 DEG C, adds the acetone of 2.24g DMPA and 35mL, reacts 1.5h,
30 DEG C of dischargings are cooled to, Waterborne Polyurethane Prepolymer is obtained.
Step 3: the performed polymer that step 2 is obtained is added in KOH aqueous solution, and high shear agitation is neutralized
Emulsification is evaporated under reduced pressure after sloughing solvent up to modified aqueous polyurethane emulsion.Wherein KOH and DMPA molar ratio are 1:1.
Performance verification: lotion is uniformly poured on polyfluortetraethylene plate, is placed a period of time at room temperature, is then placed in baking
In case, at 60 DEG C after dry 48h, standard dumbbell test piece is struck out.Using XWW-20B electronic universal tester, by GB/
The tensile strength and elongation at break of T1040-92 measurement glue film.The result shows that: its tensile strength is increased to by 30.8MPa
38.6MPa, elongation at break increase to 443.5% by 433.6%, and mechanical strength significantly improves.
Claims (8)
1. a kind of preparation method of alkali lignin base water polyurethane, which comprises the following steps:
Step 1: preparation purification alkali lignin: by the aqueous solution of the raw alkaline lignin NaOH solution of mass concentration 5%~10%
PH to 13~14 is adjusted, alkali lignin is dissolved sufficiently, is filtered to remove insoluble matter, then with the hydrochloric acid of mass concentration 12% in 60
PH to 2~3 is adjusted at DEG C, filtering is washed with distilled water repeatedly and is precipitated to neutrality, is dried in vacuo to obtain the final product;
Step 2: diisocyanate, the pure and mild purification alkali lignin of polyether polyols are added in three-necked flask, polyether polyol with
The molar ratio of diisocyanate is 1:(2~4), it is stirred to react 1~5h at 60~90 DEG C, is then cooled to 50~70 DEG C, with
On the basis of the pure and mild purification alkali lignin gross mass of diisocyanate, polyether polyols, add DMPA hydrophilic chain extender 2.0%~
5.0% and 10~80mL acetone reacts 1~4h, is cooled to 20~50 DEG C of dischargings, obtains Waterborne Polyurethane Prepolymer;
Step 3: after gained Waterborne Polyurethane Prepolymer is neutralized with neutralizer, water is added to carry out high speed emulsification, vacuum distillation is sloughed
Up to aqueous polyurethane emulsion after solvent.
2. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: the step
In rapid two, the additional amount for refining alkali lignin is refine alkali lignin and polyether polyol quality sum 0.5%~3.0%.
3. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: the step
In rapid two, alkali lignin is refined to mix again with diisocyanate and polyether polyol after acetone solution, dissolves acetone used
Amount be 20mL.
4. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: the step
In rapid two, catalyst is added before being stirred to react, the additional amount of catalyst is diisocyanate, the pure and mild purification alkali of polyether polyols is wooden
The 0.05%~0.2% of plain gross mass.
5. a kind of preparation method of alkali lignin base water polyurethane according to claim 4, it is characterised in that: described to urge
Agent is dibutyl tin dilaurate (DBTDL).
6. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: described two
Isocyanates is that isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) or -4,4 ‵-two of diphenyl methane are different
Cyanate.
7. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: described poly-
Ethoxylated polyhydric alcohol is that polypropylene glycol (PPG), polytetrahydrofuran ether glycol (PTMG) or polyethylene glycol (PEG), number-average molecular weight are
2000。
8. a kind of preparation method of alkali lignin base water polyurethane according to claim 1, it is characterised in that: in described
It is triethylamine, sodium hydroxide or potassium hydroxide with agent, the molar ratio of additional amount and DMPA are 1:1.
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