CN107522839A - A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature - Google Patents
A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature Download PDFInfo
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- CN107522839A CN107522839A CN201710762686.1A CN201710762686A CN107522839A CN 107522839 A CN107522839 A CN 107522839A CN 201710762686 A CN201710762686 A CN 201710762686A CN 107522839 A CN107522839 A CN 107522839A
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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
- C08G18/70—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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- 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
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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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- 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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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/28—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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C08G18/70—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
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of solvent-free preparation method for possessing anion and the waterborne polyurethane resin of nonionic nature, reacted using polyester diol or polyether Glycols with aliphatic isocyanates, it is re-introduced into T-shape nonionic dihydroxylic alcohols monomer, band carboxyl anion type two kinds of hydrophilic components of glycol monomer, group access adds water dispersion and emulsion after neutralizing, chain extending reaction is carried out with polyamine again, solvent need not be added by obtaining one kind, while have anionic property and the waterborne polyurethane resin of nonionic feature.Synthesis gained resin has the characteristic of anionic and non-ion aqueous polyurethane simultaneously, can improve sensitiveness shortcoming of the anion-type water-thinned polyurethane to low pH value and electrolyte.The solvent-free of the present invention possesses anion and the waterborne polyurethane resin of nonionic nature and has great application value in the leather and fur products treatment fluid of low pH value and high electrolyte content.
Description
Technical field
It is main the present invention relates to a kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature
It is used for leather and fur products process field.
Background technology
With the enhancing that people's Environmental Safety is realized, environmental regulation requirement is also increasingly strict, and many customer requirements are in leather
Industrially use low VOC even the aqueous chemical product of Diamond Search.In traditional aqueous polyurethane, employ such as DMF, NMP, third
Ketone equal solvent carries out performed polymer synthesis, and these solvents can be remained in partly on leather, form the source of slow release VOC in the future
Head.Therefore the development and application research to solvent-free aqueous polyurethane is more and more, and the market demand potential is huge.Meanwhile market
The style varied of upper leather, the chemicals used are also various in style.In the working solution of processing leather, commonly using to one
The working solution situation of a little low pH values or high electrolyte content, conventional anion type aqueous polyurethane can be demulsified in this working solution
Gel separates out.Therefore the aqueous polyurethane of resistance to low pH value and electrolyte-resistant is the important directions of everybody research.
Aqueous polyurethane is divided into anionic, cationic, nonionic.Contain in the molecule of anion-type water-thinned polyurethane
There is anionic hydrophilic segment, contain cationic hydrophilic segment, nonionic water in the molecule of cation-type water-thinned polyurethane
Property polyurethane stabilization mainly reached by containing non-ionic hydrophilic segment in molecule.
For anion-type water-thinned polyurethane, there is electric double layer structure in emulsion particle, have preferably machinery steady
Qualitative and preferable particle diameter fineness.
For non-ion aqueous polyurethane, in the absence of electric double layer structure, there is preferable acid resistance, alkali resistance
And salt tolerance.
Non-ion aqueous polyurethane brings certain parent to polyurethane using polyethylene glycols hydrophilic segment mostly at present
It is water-based.But such segment is synthesized on main chain, larger to the intensity effect of polyurethane, to the viscosity influence during synthesis
It is larger.
The content of the invention
The purpose of the present invention, which aims to provide, a kind of solvent-free possesses anion and the waterborne polyurethane resin of nonionic nature
Preparation method, to overcome weak point of the prior art.
To achieve the above object, technical scheme provided by the present invention is：One kind is solvent-free to possess anion and nonionic
The preparation method of the waterborne polyurethane resin of characteristic, it is characterised in that：Described solvent-free possess anion and nonionic nature
Waterborne polyurethane resin is reacted by polyester diol or the one of which of polyether Glycols with aliphatic isocyanates, is re-introduced into
T-shape nonionic dihydroxylic alcohols monomer, band carboxyl anion type two kinds of hydrophilic components of glycol monomer, group access add water after neutralizing
Dispersion and emulsion, then with polyamine carry out chain extending reaction, obtain one kind need not add solvent and meanwhile have anionic property and it is non-from
The waterborne polyurethane resin of sub- property feature.
The above-mentioned solvent-free preparation method for possessing anion and the waterborne polyurethane resin of nonionic nature, including it is following
Step：
（1）Polyester diol or polyether Glycols 50-100 parts, aliphatic diisocyanate 20-40 parts are added into reaction vessel,
Under lasting stirring and nitrogen atmosphere protection, 80-90 DEG C of reaction 2-3 hour is warming up to；
（2）Above-mentioned reaction system is cooled to 80-85 DEG C, adds T-shape nonionic dihydroxylic alcohols monomer 10-20 parts, band carboxyl the moon
Ionic glycol monomer 3-6 parts, 80-85 DEG C of reaction 4-6 hour of temperature is maintained, obtain the polyurethane prepolymer blocked with-NCO
Body；
（3）Triethylamine 2.5-5 parts are added in the base polyurethane prepolymer for use as blocked to above-mentioned-NCO, are stirred 30 minutes, then at a high speed
Add deionized water and ethylenediamine 1-5 parts under shearing condition, after stirring 60 minutes, the polyaminoester emulsion stablized, as institute
State solvent-free double ion waterborne polyurethane resin；
Above-mentioned raw materials used number is parts by weight.
The polyester diol is number-average molecular weight 1000-4000 polyneopentyl glycol adipate glycol, poly- hexanedioic acid
At least one of 2- methyl-1,3-propanediols esterdiol, PCDL.
The polyether Glycols are number-average molecular weight 400-4000 polyoxypropyleneglycol, in polytetrahydrofuran diol
It is at least one.
The aliphatic diisocyanate be IPDI IPDI, hexamethylene diisocyanate HDI, 4,
4 '-dicyclohexyl methyl hydride diisocyanate H12At least one of MDI.
The T-shape nonionic dihydroxylic alcohols monomer is a kind of polymer nonionic monomer, contains two primary hydroxyl functional groups
With a long side chain blocked by ethyoxyl.It can be embedded in along polymer backbone, and Nonionic stabilization is provided for water-base resin.Institute
It is Bai Situo companies nonionic dihydroxylic alcohols Ymer N120 to state T-shape nonionic dihydroxylic alcohols monomer.
The band carboxyl anion type glycol monomer is 2,2- dihydromethyl propionic acid DMPA, 2,2- dimethylolpropionic acids
At least one of DMBA.
The polyamine for participating in chain extending reaction is ethylenediamine, diethylenetriamine, triethylene tetramine, at least the one of polyethylene polyamine
Kind.
The beneficial effects of the invention are as follows：
（1）The present invention participates in polymerisation by introducing T-shape nonionic dihydroxylic alcohols monomer, utilizes T-shape nonionic dihydroxylic alcohols
The long side chain of ethyoxyl end-blocking on monomer so that long side chain is carried on performed polymer segment, is brought between larger strand
Steric hindrance, mitigate the winding between strand, the viscosity of performed polymer is reduced, so as to reach the purpose that need not add solvent.
（2）The present invention participates in polymerisation by introducing T-shape nonionic dihydroxylic alcohols monomer, utilizes T-shape nonionic dihydroxylic alcohols
The long side chain of ethyoxyl end-blocking on monomer so that with non-ionic hydrophilic group ethyoxyl on strand, so as to be carried for system
Good low pH value stability and freeze thaw stability are supplied.
（3）The present invention introduces carboxyl anion type glycol monomer simultaneously, utilizes the good hydrophilic brought after its neutralization
Ability, further increase the stability of emulsion ion.
Embodiment
Embodiments of the invention are described below in detail, following examples are only intended to that the present invention is further described,
It is not intended that limiting the scope of the invention, the person skilled in the art in the field can be according to the content of the invention described above
Some nonessential modifications and adaptations are made, still fall within protection scope of the present invention.
Embodiment one.
（1）By 100 parts of polyneopentyl glycol adipate glycol（Number-average molecular weight 2000）, 40 parts of isophorone diisocyanates
Ester adds reaction vessel, under lasting stirring and nitrogen atmosphere protection, is warming up to 80-90 DEG C and reacts 2 hours；
（2）Above-mentioned reaction system is cooled to 80-85 DEG C, 15 parts of Ymer N120 monomers, 5 parts of dihydromethyl propionic acid is added, maintains
80-85 DEG C of reaction 4-6 hour of temperature, obtain the base polyurethane prepolymer for use as blocked with-NCO；
（3）55-60 DEG C is cooled to, 3.7 parts of triethylamine is added in the base polyurethane prepolymer for use as blocked to above-mentioned-NCO, stirs 30 points
Clock, 4.5 parts of 370 parts of deionized water and ethylenediamine are then added under the conditions of high speed shear, after stirring 60 minutes, stablized
Polyaminoester emulsion, as described solvent-free double ion waterborne polyurethane resin.
Embodiment two.
（1）By 100 parts of polyoxypropyleneglycols（Number-average molecular weight 2000）, 50 parts of isocyanides of 4,4 '-dicyclohexyl methyl hydride two
Acid esters adds reaction vessel, under lasting stirring and nitrogen atmosphere protection, is warming up to 80-90 DEG C and reacts 2 hours；
（2）Above-mentioned reaction system is cooled to 80-85 DEG C, 20 parts of Ymer N120 monomers, 5 parts of dihydromethyl propionic acid is added, maintains
80-85 DEG C of reaction 4-6 hour of temperature, obtain the base polyurethane prepolymer for use as blocked with-NCO；
（3）55-60 DEG C is cooled to, 3.7 parts of triethylamine is added in the base polyurethane prepolymer for use as blocked to above-mentioned-NCO, stirs 30 points
Clock, 4 parts of 390 parts of deionized water and ethylenediamine are then added under the conditions of high speed shear, after stirring 60 minutes, that is stablized is poly-
Urethane emulsion, as described solvent-free double ion waterborne polyurethane resin.
Embodiment three.
（1）By 100 parts of polytetrahydrofuran diols（Number-average molecular weight 1000）, 40 parts of isocyanides of 4,4 '-dicyclohexyl methyl hydride two
Acid esters adds reaction vessel, under lasting stirring and nitrogen atmosphere protection, is warming up to 80-90 DEG C and reacts 2 hours；
（2）Above-mentioned reaction system is cooled to 80-85 DEG C, 18 parts of Ymer N120 monomers, 4 parts of dihydromethyl propionic acid is added, maintains
80-85 DEG C of reaction 4-6 hour of temperature, obtain the base polyurethane prepolymer for use as blocked with-NCO；
（3）55-60 DEG C is cooled to, 3 parts of triethylamine is added in the base polyurethane prepolymer for use as blocked to above-mentioned-NCO, stirs 30 minutes,
Then 3 parts of 360 parts of deionized water and ethylenediamine are added under the conditions of high speed shear, after stirring 60 minutes, the poly- ammonia stablized
Ester emulsion, as described solvent-free double ion waterborne polyurethane resin.
Although an embodiment of the present invention has been shown and described, it will be understood by those within the art that：Not
In the case of departing from the principle and objective of the present invention a variety of change, modification, replacement and modification can be carried out to these embodiments, this
The scope of invention is limited by claim and its equivalent substitution, without creative work improvements introduced etc., all should be included
Within protection scope of the present invention.
Claims (8)
- A kind of 1. solvent-free preparation method for possessing anion and the waterborne polyurethane resin of nonionic nature, it is characterised in that： The solvent-free waterborne polyurethane resin for possessing anion and nonionic nature is by its of polyester diol or polyether Glycols A kind of middle and aliphatic isocyanates react, and are re-introduced into T-shape nonionic dihydroxylic alcohols monomer, band carboxyl anion type dihydric alcohol list Two kinds of hydrophilic components of body, group access adds water dispersion and emulsion after neutralizing, then carries out chain extending reaction with polyamine, obtains one kind and is not required to Add solvent while there is anionic property and the waterborne polyurethane resin of nonionic feature.
- 2. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 1 Method, it is characterised in that comprise the following steps：（1）Polyester diol or polyether Glycols 50-100 parts, aliphatic diisocyanate 20-40 parts are added into reaction vessel, Under lasting stirring and nitrogen atmosphere protection, 80-90 DEG C of reaction 2-3 hour is warming up to；（2）Above-mentioned reaction system is cooled to 80-85 DEG C, adds T-shape nonionic dihydroxylic alcohols monomer 10-20 parts, band carboxyl the moon Ionic glycol monomer 3-6 parts, 80-85 DEG C of reaction 4-6 hour of temperature is maintained, obtain the polyurethane prepolymer blocked with-NCO Body；（3）Triethylamine 2.5-5 parts are added in the base polyurethane prepolymer for use as blocked to above-mentioned-NCO, are stirred 30 minutes, then at a high speed Add deionized water and ethylenediamine 1-5 parts under shearing condition, after stirring 60 minutes, the polyaminoester emulsion stablized, as institute State solvent-free double ion waterborne polyurethane resin；Above-mentioned raw materials used number is parts by weight.
- 3. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：It is polyneopentyl glycol adipate glycol that the polyester diol is number-average molecular weight 1000-4000, poly- At least one of hexanedioic acid 2- methyl-1,3-propanediols esterdiol, PCDL.
- 4. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：The polyether Glycols be number-average molecular weight 400-4000 polyoxypropyleneglycol, PolyTHF two At least one of alcohol.
- 5. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：The aliphatic diisocyanate is IPDI IPDI, hexamethylene diisocyanate At least one of HDI, 4,4 '-dicyclohexyl methyl hydride diisocyanate H12MDI.
- 6. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：The T-shape nonionic dihydroxylic alcohols monomer is a kind of polymer nonionic monomer, contains two primary hydroxyls Functional group and a long side chain blocked by ethyoxyl, it can be embedded in along polymer backbone, and it is steady to provide nonionic for water-base resin Fixedization.
- 7. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：The band carboxyl anion type glycol monomer is 2,2- dihydromethyl propionic acid DMPA, 2,2- dihydroxymethyls At least one of butyric acid DMBA.
- 8. the solvent-free preparation side for possessing anion and the waterborne polyurethane resin of nonionic nature according to claim 2 Method, it is characterised in that：The polyamine for participating in chain extending reaction is ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine It is at least one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710762686.1A CN107522839A (en) | 2017-08-30 | 2017-08-30 | A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710762686.1A CN107522839A (en) | 2017-08-30 | 2017-08-30 | A kind of solvent-free waterborne polyurethane resin preparation method for possessing anion and nonionic nature |
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| CN109096468A (en) * | 2018-09-11 | 2018-12-28 | 洛阳盛嘉新材料有限公司 | A kind of solvent-free waterborne polyurethane resin and preparation method thereof |
| CN109679062A (en) * | 2018-12-24 | 2019-04-26 | 清远市美佳乐环保新材股份有限公司 | One kind can film-forming high molecular emulsifier and preparation method thereof |
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| CN110862509A (en) * | 2019-11-29 | 2020-03-06 | 山东天庆科技发展有限公司 | Water-based solvent-free polyurethane resin and preparation method thereof |
| CN111138628A (en) * | 2020-01-14 | 2020-05-12 | 江苏钟山化工有限公司 | Preparation method of waterborne polyurethane for synthetic leather |
| WO2020199175A1 (en) * | 2019-04-04 | 2020-10-08 | Dow Global Technologies Llc | Solventless adhesive composition and method for preparing thereof |
| CN112409564A (en) * | 2020-12-24 | 2021-02-26 | 安徽安大华泰新材料有限公司 | Non-desolventizing water-based nonionic polyurethane and preparation method thereof |
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| CN109096468A (en) * | 2018-09-11 | 2018-12-28 | 洛阳盛嘉新材料有限公司 | A kind of solvent-free waterborne polyurethane resin and preparation method thereof |
| CN109679062A (en) * | 2018-12-24 | 2019-04-26 | 清远市美佳乐环保新材股份有限公司 | One kind can film-forming high molecular emulsifier and preparation method thereof |
| CN109897153A (en) * | 2019-03-25 | 2019-06-18 | 英德市国彩精细化工有限公司 | A kind of water-dispersion type nonionic isocyanate curing agent of high crosslink density and preparation method thereof |
| WO2020199175A1 (en) * | 2019-04-04 | 2020-10-08 | Dow Global Technologies Llc | Solventless adhesive composition and method for preparing thereof |
| CN113748182A (en) * | 2019-04-04 | 2021-12-03 | 陶氏环球技术有限责任公司 | Solvent-free adhesive composition and method for preparing same |
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| CN110862509A (en) * | 2019-11-29 | 2020-03-06 | 山东天庆科技发展有限公司 | Water-based solvent-free polyurethane resin and preparation method thereof |
| CN111138628A (en) * | 2020-01-14 | 2020-05-12 | 江苏钟山化工有限公司 | Preparation method of waterborne polyurethane for synthetic leather |
| CN111138628B (en) * | 2020-01-14 | 2021-03-05 | 江苏钟山化工有限公司 | Preparation method of waterborne polyurethane for synthetic leather |
| CN112409564A (en) * | 2020-12-24 | 2021-02-26 | 安徽安大华泰新材料有限公司 | Non-desolventizing water-based nonionic polyurethane and preparation method thereof |
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