CN107793549A - Aqueous polyurethane is from matting resin and preparation method thereof - Google Patents
Aqueous polyurethane is from matting resin and preparation method thereof Download PDFInfo
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- CN107793549A CN107793549A CN201711061225.8A CN201711061225A CN107793549A CN 107793549 A CN107793549 A CN 107793549A CN 201711061225 A CN201711061225 A CN 201711061225A CN 107793549 A CN107793549 A CN 107793549A
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- sulfonic acid
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- chain extender
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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
- C08G18/4854—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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of aqueous polyurethane from matting resin and preparation method thereof, including polytetramethylene ether diol, cycloalkyl aliphatic diisocyanate, diamino sulfonic acid salt, aqueous polyurethane association thickener；It is characterized in that：Also comprising 1 that at least one carbon number is more than 4,4 butanediols or 1,6 hexylene glycol aliphatic small molecule chain extenders, or two kinds of mixture, diamino sulfonic acid salt is 2 [(2 aminoethyl) amino] ethyl sulfonic acid sodium, at least two secondary amine class chain extenders are as chain extender before emulsification, and hydrazine hydrate is as emulsification rear chain extender；The amount of isocyanate species is n+3；The amount of aliphatic small molecule chain extender material is 1/n+3；The amount of 2 [(2 aminoethyl) amino] ethyl sulfonic acid sodium materials is 1.05 1.25/n+3；The amount of diamines material is 1.25 1.50/n+3.Have the advantages that from extinction effect is good, emulsion stability is good, product stability is good.
Description
Technical field
The invention belongs to polymeric material field, especially with respect to a kind of aqueous polyurethane from matting resin and its preparation side
Method.The present invention is applied to the finishing agent of leather and synthetic leather.
Background technology
At present, the domestic preparation method for waterborne polyurethane coating agent matting resin is broadly divided into two kinds：One is water
Water-based delustring filler, such as aerosil are added on the basis of property polyurethane finishing agent, by solid particle for light
Diffusing reflection caused by extinction effect reach final purpose；It is another then be a kind of special molecular structure of design or emulsion
Grain, in the drying process because water-soluble effect occurs during this for the change of particle shape, and different groups, is produced coarse
Surface reaches the extinction effect of film.If number of patent application is CN201110404622.7 " the water-based poly- ammonia of extinction type use for synthetic leather
Ester finishing agent ", by adding 1%-10% flatting silica, i.e. aerosil, to reach the effect of delustring.It is prepared by this mode
Matting resin, its major defect is stability deficiency, the requirement of emulsion particle diameter distribution uniformity is compared during the manufacturing
Height, precipitation is easily produced when storing for a long time.The a kind of of application number CN201510386759.2 is reacted from the water-based poly- ammonia of extinction type
Ester resin and preparation method and application, by tetrahydrofuran ether and isocyanate polymeric, by dihydroxymethyl into the base after salt
Group is emulsified, and using 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium and hydrazine hydrate as rear chain extender, preparing one kind has spherical junctions
The aqueous polyurethane emulsion of structure.The latex particle of this spherical structure can keep its spheroid form very well in the drying process,
Its extinction effect is determined by the dosage of hydrazine hydrate.Its shortcoming is that the rigidity of latex particle in itself is inadequate, emulsification, rear chain extension with
And dry during easily because acetone, moisture content volatilize etc. caused by microstress and cause the deformation of spheric granules, so as to cause to disappear
Light effect fails, or even ultimately forms the film of high glaze.Moreover, emulsification of this technology of preparing for performed polymer requires pole
Height, produce poor repeatability, industrialized quality stability deficiency.
The content of the invention
Present invention the shortcomings that existing for prior art, the structure of resin in itself is improved, prepare that " soft core is hard
The waterborne polyurethane resin particle of shell " structure, a kind of special hollow microsphere structure is formed, and ensure that this structure is done in emulsion
It is dry, there is good stability, and the technology to emulsification procedure is reduced in preparation process is produced especially during heated drying
It is required that make it have good industrialization reproducibility, and the good aqueous polyurethane of extinction effect is from matting resin and its preparation
Method.
Aqueous polyurethane of the present invention is from the synthetic of matting resin, including at least one molecular weight is 1000 or 2000
Polytetramethylene ether diol, or two kinds of mixture, its amount of substance are set as n unit, and n is the natural number more than 1；At least
One kind of cycloalkyl aliphatic diisocyanate, IPDI or 4,4'- dicyclohexyl methyl hydride diisocyanates
Or two kinds of mixture, at least one diamino sulfonic acid salt, aqueous polyurethane association thickener, catalyst, deionized water；Its
It is characterized in：Also comprising the BDO or 1,6- hexylene glycol aliphatic small molecule chain extension that at least one carbon number is more than 4
Agent, or two kinds of mixture, diamino sulfonic acid salt are 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium, at least two secondary amine class chain extensions
The mixture of agent, ethylenediamine or IPD or both expands after being used as emulsification as chain extender before emulsification, and hydrazine hydrate
Chain agent；The amount of isocyanate species is n+3；The amount of aliphatic small molecule chain extender material is 1/n+3；2- [(2- aminoethyls) ammonia
Base] amount of ethyl sulfonic acid sodium material is 1.05-1.25/n+3；The amount of diamines material is 1.25-1.50/n+3.
Aqueous polyurethane of the present invention from the preparation method of matting resin, it is characterized in that：
1) feed intake polytetramethylene ether diol, and 2000,800 parts of molecular weight enters 6000L reactors, is warming up to 1150C, take out true
Sky dehydration 0.5 hour, opens reflux condensation mode valve, is passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of diisocyanate, 0.6 part of catalyst enter the above
Reactor, react 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is
Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined
Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead
Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided
Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring
Value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few
Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
The present invention compared with prior art the advantages of be：Using Molecular Design and latex particle structure design, abandon
The way of flatting silica is added in aqueous polyurethane emulsion, reaches more more excellent from extinction effect than addition flatting silica, keeps away
Exempt from addition flatting silica and cause the negative effects such as emulsion unstability；With good emulsion stability, its performance mainly depends on
The rigid maintenance ability of molecular structure around Molecular Design, and hydrophilic radical, reduce aqueous polyurethane and disappear certainly
Photopolymer resin industrializes the difficulty requirement to emulsifying technology, improves the quality stability of the manufacturing.
Embodiment
Aqueous polyurethane of the present invention is from the synthetic of matting resin, including at least one molecular weight is 1000 or 2000
Polytetramethylene ether diol, or two kinds of mixture, its amount of substance are set as n unit, and n is the natural number more than 1, n list
Position is mol；Including at least cycloalkyl aliphatic diisocyanate, IPDI or 4,4'- dicyclohexyl methyl hydrides
One or two kinds of mixtures of diisocyanate, at least one diamino sulfonic acid salt is as hydrophilic chain extender, aqueous polyurethane
Association thickener, catalyst, deionized water；It is characterized in that：Also comprising Isosorbide-5-Nitrae-fourth two that at least one carbon number is more than 4
Alcohol or 1,6- hexylene glycol aliphatic small molecule chain extender, or two kinds of mixture, diamino sulfonic acid salt are 2- [(2- aminoethyls) ammonia
Base] ethyl sulfonic acid sodium, at least two secondary amine class chain extenders, before the mixture of ethylenediamine or IPD or both is as emulsification
Chain extender, and hydrazine hydrate is as emulsification rear chain extender；The amount of isocyanate species is n+3；Aliphatic small molecule chain extender thing
The amount of matter is 1/n+3；The amount of 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium material is 1.05-1.25/n+3；The amount of substance of diamines
For 1.25-1.50/n+3.
Aqueous polyurethane of the present invention from the preparation method of matting resin, it is characterized in that：
1) feed intake polytetramethylene ether diol, and 2000,800 parts of molecular weight enters 6000L reactors, is warming up to 1150C, take out true
Sky dehydration 0.5 hour, opens reflux condensation mode valve, is passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of diisocyanate, 0.6 part of catalyst enter the above
Reactor, react 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is
Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined
Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes, to keep viscosity when reacting；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead
Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided
Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to requiring
Value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few
Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
The present invention uses carbon number to carry out chain extension in the course of the polymerization process for more than 4 small molecule glycol, use not same amount
Chain extender control the purpose of different molecular weight to reach, and the design of different molecular weight will also influence latex particle inside points
Swelling action inside son amount size and latex particle with solvent or water, so as to influence latex particle size and in the drying process
Particle rigidly maintain ability；
In Molecular Design, a free cycloalkanes group diisocyanate is linked together with hydrophilic radical, with enhancing
The link strength and rigidity of latex particle hydrophilic radical annex, to reach the purpose for strengthening latex particle rigidity；
Using strand closed loop configuration, the part being connected with Diamines chain extender is the soft core part of long chain, with sulfonate
Connected part is duricrust part；After frozen water emulsifies, outwardly, soft core part inwardly, is formed soft latex particle hydrophilic segment
Core monocoque；
Controlled by the molecular weight of small molecule glycol, and the combination of different isocyanate groups and the control of amount, in chain extension process
The middle segment for forming different rigidity, to reach the purpose of Molecular Design；In moisture content volatilization process, soft core monocoque and
Between the polar molecule formed between sulfonate and other groups or intramolecular active force and hydrogen bond etc. can effectively ensure that latex
Grain maintains certain spherical state and indeformable, is finally reached the diffusing reflection effect of particle surface；
Closed loop is carried out using diamine chain stretching agent chain extension before emulsification, remaining remaining isocyanate group passes through hydrazine hydrate after emulsification
Short chain groups carry out chain conjunction, and the effect of hydrogen bond, and big latex particle effectively is carried out into microballoon, further forms rigidization
Particle, strengthen final extinction effect；
Sulfamic acid sodium salt is used as unique emulsifying agent（Hydrophilic chain extender）, effectively improve prior art and use carboxylate
As emulsifying agent, hydrophilic radical forms the problem of being swelled in organic solvent and water, ensures latex particle rigid structure and inside
Hydrophobic microscopic pattern is formed, spherical rigid structure is kept in the drying process and indeformable, there is good stability.
The present invention reaches the purpose of Molecular Design using stepwise reaction：
React the first step（By taking amount n=2 of polyol agent as an example）, be polyalcohol and isocyanates reaction, in catalyst action
Lower 2mol polyalcohol and 5moL isocyanates react, and generate 2mol end isocyano macromolecular, and remaining 1mol's is different
Cyanate.
Second step is reacted, is first time chain extending reaction.Add 1mol small molecule polyols, such as BDO, generation
Macromolecular after 1mol chain extension, and the end isocyano macromolecular of remaining 1mol reaction first step generations.
The 3rd step is reacted, is entered for 1mol reaction second step product of 2- [(2- aminoethyls) amino] the ethyl sulfonic acid sodium to 2mol
Row 1：2 chain extensions, molecular weight, which increases, to be twice.Meanwhile 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium is also hydrophilic chain extender, this step
All strand groups are all connected on hydrophilic radical.
The 4th step is reacted, the diamine chain stretching agent for being 1mol carries out 1 to the product for reacting the 3rd step：2 chain extensions, while by long point
Subchain carries out closed loop.After frozen water emulsification is added, hydrophilic radical is in the periphery of latex particle, because the relation of structure, sulfonate
The hydrophilic radical of formation is larger, and hydrophobic long chain is in the inside of latex particle, so as to form the breast of " soft core duricrust "
Plastic structure.The latex particle of this structure, there is the stability of good storage stability and different PH scope, and dry
During dry, because in the presence of molecular rigidity and intramolecule and outside hydrogen bond, with the volatilization of moisture content, latex particle maintains
Rigid structure it is very capable, it is not easy to because moisture content volatilization and cause particle deformation, it is right so as to form coarse film surface
Light forms good diffusing reflection effect.
The latex particle for the stabilization that the Molecular Design of the present invention is formed, and the rule of latex particle particle diameter distribution
Property, the manufacture for the aqueous polyurethane particle of hollow microsphere structure provides a kind of new thinking.
The injected volume " part " of each material is a mass unit in preparation method of the present invention, typically uses 1Kg as a matter
Unit is measured, the injected volume of each material can increase and decrease in proportion according to reactor capacity or batch size, each material in the present embodiment
Amount is than being relative preferred values with the reaction time.
Claims (2)
1. a kind of aqueous polyurethane is from matting resin, including the polytetramethylene ether two that at least one molecular weight is 1000 or 2000
Alcohol, or two kinds of mixture, its amount of substance are set as n unit, and n is the natural number more than 1；At least cycloalkyl aliphatic two
The mixing of one or both of isocyanates, IPDI or 4,4'- dicyclohexyl methyl hydride diisocyanates
Thing, at least one diamino sulfonic acid salt, aqueous polyurethane association thickener, catalyst, deionized water；It is characterized in that：Also wrap
Containing the BDO or 1,6- hexylene glycol aliphatic small molecule chain extender that at least one carbon number is more than 4, or two kinds
Mixture, diamino sulfonic acid salt are 2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium, at least two secondary amine class chain extenders, ethylenediamine or
The mixture of IPD or both is as chain extender before emulsification, and hydrazine hydrate is as emulsification rear chain extender；Isocyanic acid
The amount of ester material is n+3；The amount of aliphatic small molecule chain extender material is 1/n+3；2- [(2- aminoethyls) amino] ethyl sulfonic acid sodium
The amount of material is 1.05-1.25/n+3；The amount of diamines material is 1.25-1.50/n+3.
2. aqueous polyurethane according to claim 1 is from the preparation method of matting resin, it is characterized in that：1) poly- four are fed intake
Methylene ether glycol, 2000,800 parts of molecular weight enter 6000L reactors, are warming up to 1150C, dehydration 0.5 hour is vacuumized, is beaten
Reflux condensation mode valve is driven, is passed through nitrogen protection；
2）It is cooled to 800C, under moderate-speed mixer, the 100 parts of butanone that feed intake, 222.4 parts of diisocyanate, 0.6 part of catalyst enter the above
Reactor, react 1.5 hours；
3）Feed intake 18 parts 400 parts of butanone, small point of aliphatic of chain extender enters above reactor, and 800C continues reaction 2.0 hours；
4）It is cooled to 600C, feed intake under moderate-speed mixer 400 parts of acetone, adjustment temperature to 500C；At dispersion impeller edge, linear velocity is
Under more than 12m/s high speed shears, 2- [(2- aminoethyls) amino] 46.4 parts of ethyl sulfonic acid sodium hydrophilic chain extender, Ran Hougao are rapidly joined
Speed stirring 30 minutes；Continued that 600 parts of acetone are at the uniform velocity added dropwise in 30 minutes；
5）Prepare the mixture of 200 parts of 2.4 parts of secondary amine chain extenders and acetone in advance, put into reactor under high velocity agitation, and instead
Answer 5 minutes；
6）Rapidly join 2440 parts of frost deionized waters, high speed shearing emulsification 15 minutes；
7）Prepare 3 parts of hydrazine hydrate and the mixture of 27 parts of deionized water in advance, once put into above reactor, high speed shear 5 is divided
Clock；
8）Cooling water cooling is kept under moderate-speed mixer, is cured 2 hours；
9）45 are warming up to after curing at once0C removes most of acetone and butanone, then heats to 560C removes acetone to required value；
10）Solid content is adjusted using deionized water, and viscosity is adjusted with 20 parts of aqueous polyurethane association thickeners, can be added few
Substrate wetting agents or levelling agent 0.2-0.5 parts are measured, after qualified after testing, is packed by packaging instruction with 80 mesh filter screen filtrations.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711061225.8A CN107793549A (en) | 2017-11-02 | 2017-11-02 | Aqueous polyurethane is from matting resin and preparation method thereof |
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|---|---|---|---|
| CN201711061225.8A CN107793549A (en) | 2017-11-02 | 2017-11-02 | Aqueous polyurethane is from matting resin and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546323A (en) * | 2018-04-18 | 2018-09-18 | 万华化学集团股份有限公司 | Cation is from matting resin and its preparation method and application |
| CN108997559A (en) * | 2018-06-07 | 2018-12-14 | 安徽匠星联创新材料科技有限公司 | A kind of dumb light type water-base polyurethane material and preparation method thereof |
| CN109749042A (en) * | 2018-12-06 | 2019-05-14 | 杭州传化精细化工有限公司 | A kind of preparation method of sulfonic acid type water-based polyurethane dispersion |
| CN110423329A (en) * | 2019-08-29 | 2019-11-08 | 江苏宝泽高分子材料股份有限公司 | One kind is from extinction type waterborne polyurethane resin and preparation method thereof |
| CN111793188A (en) * | 2020-08-10 | 2020-10-20 | 上海思盛聚合物材料有限公司 | Hydroxyl-containing self-extinction waterborne polyurethane and high-performance self-extinction coating composed of same |
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| CN1425726A (en) * | 2002-12-30 | 2003-06-25 | 华南理工大学 | Polyurethane water dispersion and its preparing method |
| CN104974324A (en) * | 2015-06-30 | 2015-10-14 | 中科院广州化学有限公司南雄材料生产基地 | Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof |
| CN106349914A (en) * | 2016-08-25 | 2017-01-25 | 万华化学集团股份有限公司 | Aqueous matt surface finishing agent for PVC (Polyvinyl Chloride) leather and preparation method thereof |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1425726A (en) * | 2002-12-30 | 2003-06-25 | 华南理工大学 | Polyurethane water dispersion and its preparing method |
| CN104974324A (en) * | 2015-06-30 | 2015-10-14 | 中科院广州化学有限公司南雄材料生产基地 | Reactive self-delustering waterborne polyurethane resin, and preparation method and application thereof |
| CN106349914A (en) * | 2016-08-25 | 2017-01-25 | 万华化学集团股份有限公司 | Aqueous matt surface finishing agent for PVC (Polyvinyl Chloride) leather and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546323A (en) * | 2018-04-18 | 2018-09-18 | 万华化学集团股份有限公司 | Cation is from matting resin and its preparation method and application |
| CN108546323B (en) * | 2018-04-18 | 2020-08-28 | 万华化学集团股份有限公司 | Cation self-extinction resin and preparation method and application thereof |
| CN108997559A (en) * | 2018-06-07 | 2018-12-14 | 安徽匠星联创新材料科技有限公司 | A kind of dumb light type water-base polyurethane material and preparation method thereof |
| CN109749042A (en) * | 2018-12-06 | 2019-05-14 | 杭州传化精细化工有限公司 | A kind of preparation method of sulfonic acid type water-based polyurethane dispersion |
| CN109749042B (en) * | 2018-12-06 | 2021-03-30 | 杭州传化精细化工有限公司 | Preparation method of sulfonic acid type aqueous polyurethane dispersion |
| CN110423329A (en) * | 2019-08-29 | 2019-11-08 | 江苏宝泽高分子材料股份有限公司 | One kind is from extinction type waterborne polyurethane resin and preparation method thereof |
| CN111793188A (en) * | 2020-08-10 | 2020-10-20 | 上海思盛聚合物材料有限公司 | Hydroxyl-containing self-extinction waterborne polyurethane and high-performance self-extinction coating composed of same |
| CN111793188B (en) * | 2020-08-10 | 2021-03-12 | 上海思盛聚合物材料有限公司 | Hydroxyl-containing self-extinction waterborne polyurethane and self-extinction coating composed of same |
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