CN106279614A - A kind of silicane-modified polyurethane fluid sealant performed polymer and preparation method thereof and fluid sealant - Google Patents
A kind of silicane-modified polyurethane fluid sealant performed polymer and preparation method thereof and fluid sealant Download PDFInfo
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- CN106279614A CN106279614A CN201610763703.9A CN201610763703A CN106279614A CN 106279614 A CN106279614 A CN 106279614A CN 201610763703 A CN201610763703 A CN 201610763703A CN 106279614 A CN106279614 A CN 106279614A
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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
- C08G18/65—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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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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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
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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
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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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
- C08G2190/00—Compositions for sealing or packing joints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
Abstract
The present invention relates to a kind of silicane-modified polyurethane fluid sealant performed polymer and preparation method thereof and fluid sealant, based on weight/mass percentage composition, the composition of raw materials of described performed polymer includes: polyether polyol 70% ~ 80%；Isocyanates 10% ~ 20%；Silane coupler 5% ~ 15%, wherein, the mixture that described polyether polyol is polyether polyol A and polyether polyol B is 0.2～0.3 in mass ratio, wherein, described polyether polyol A is polyether Glycols, and described polyether polyol B is polyether-tribasic alcohol.The performed polymer of the present invention uses Silante terminated so that it is in molecular structure, existing carbamate is the polyether segment of node, has again Silante terminated segment, combines the characteristic of silane and polyurethane, is used for making fluid sealant, and fluid sealant has the performance of low modulus height resilience.
Description
Technical field
The invention belongs to polyurethane sealant technical field, be applied to building trade, be specifically related to a kind of silane-modified poly-
Urethane fluid sealant, fluid sealant and preparation method.
Background technology
Polyurethane sealant is generally prepared from other materials by base polyurethane prepolymer for use as, its have high hot strength,
Excellent elasticity, wearability, oil resistivity and tolerance to cold, extensively application and building, square, highway are as inlay sealing material.
But at present, the polyurethane sealant performed polymer on market is most based on NCO end-blocking, occurs a large amount of after making fluid sealant
Bubble, easy expansion joint (E.J.), destroy and the interface of concrete binding, have a strong impact on sealing effectiveness.Also there is silicane-modified polyurethane close
The document report of sealing performed polymer, but be often high-modulus low resilience fluid sealant after making fluid sealant, be not suitable for concrete
Seam.
Summary of the invention
The technical problem to be solved is to overcome the deficiencies in the prior art, it is provided that a kind of silicane-modified polyurethane is close
Sealing performed polymer and preparation method thereof
The present invention also provides for a kind of single-component silane modified polyurethane sealant for building.
For solving above technical problem, the present invention adopts the following technical scheme that
A kind of silicane-modified polyurethane fluid sealant performed polymer, it is characterised in that: based on weight/mass percentage composition, described performed polymer
Composition of raw materials include:
Polyether polyol 70%～80%；
Isocyanates 10%～20%；
Silane coupler 5%～15%,
Wherein, the mixing that described polyether polyol is polyether polyol A and polyether polyol B is 0.2～0.3 in mass ratio
Thing, wherein, described polyether polyol A is polyether Glycols, and described polyether polyol B is polyether-tribasic alcohol.
Further, described polyether polyol A is the polypropylene oxide glycol of molecular weight 1000～2000；Described polyethers is many
Unit alcohol B is in the Polypropylene Oxide Triol of molecular weight 1500～3000 and the high activity polyether triol of molecular weight 5000～6000
The mixture of one or both.
Further, described isocyanates is toluene di-isocyanate(TDI) (TDI-80), methyl diphenylene diisocyanate
(MDI-100), the combination of one or more in isophorone diisocyanate (IPDI).
Further, described silane coupler is N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyl trimethoxy
The group of one or more in base silane, N-methyl-γ-aminopropyl dimethoxy silane, γ mercaptopropyitrimethoxy silane
Close.
The another kind of scheme that the present invention takes is: the preparation side of a kind of above-mentioned silicane-modified polyurethane fluid sealant performed polymer
Method, described preparation method comprises the following steps:
(1) make polyether polyol A and isocyanates react 1～3 hour at a temperature of 70 DEG C～90 DEG C, prepare end isocyanide
Acid esters performed polymer；
(2) make isocyanate terminated performed polymer that step (1) obtains and polyether polyol B anti-at a temperature of 70 DEG C～90 DEG C
Answer 3～4 hours, be subsequently adding silane coupler and react until NCO content runs out of at a temperature of 40 DEG C～60 DEG C, obtaining institute
State silicane-modified polyurethane fluid sealant performed polymer.
Further, described polyether polyol A first carries out pretreatment, then reacts with described isocyanates, wherein, described pre-
It is processed as being warming up to polyether polyol A 100 DEG C～120 DEG C, vacuum dehydration 1～3 hours.
Another technical scheme that the present invention takes is: a kind of single-component silane modified polyurethane sealant for building, presses
Weight/mass percentage composition meter, the composition of raw materials of described fluid sealant includes:
Wherein, described performed polymer is above-mentioned silicane-modified polyurethane fluid sealant performed polymer.
In the present invention, described adhesion promoter is N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyl trimethoxy
The combination of one or more in base silane, N-methyl-γ-aminopropyl dimethoxy silane.
In the present invention, described thixotropic agent is one or more in aerosil, polyamide wax, organobentonite
Combination.
In the present invention, described filler is the one in ground calcium carbonate, barium sulfate, titanium dioxide, Pulvis Talci, mica powder or many
The combination planted.
In the present invention, described plasticizer is the combination of one or more in DINP, DIDP, DBP, DOP.
In the present invention, described UV absorbent is one or more in UV-1, UV-320, UV-571, UV-1130
Combination.
In the present invention, described ultra-violet stabilizer is one or more in UV-P, UV-234, UV-1229, UV-1164
Combination.
In the present invention, described catalyst is dibutyl tin laurate (T-12), stannous octoate (T-9), zinc Isoocatanoate, different
The combination of one or more in Bismuth Octoate, butyl titanate, tetraisopropyl titanate.
In the present invention, the most described raw material all can prepare by being purchased and/or take known means, does not has
When being illustrated, it is satisfied by standardization chemical product requirement.
What the present invention taked another solution is that again a kind of above-mentioned single-component silane modified polyurethane sealant for building
Preparation method, described preparation method be by performed polymer, filler, plasticizer, thixotropic agent, adhesion promoter, UV absorbent,
Ultra-violet stabilizer, catalyst mix, extrusion, prepare described fluid sealant.
Due to the enforcement of technique scheme, the present invention compared with prior art has the advantage that
The performed polymer of the present invention uses Silante terminated so that it is in molecular structure, existing carbamate is the polyether chain of node
Section, has again Silante terminated segment, combines the characteristic of silane and polyurethane, be used for preparing fluid sealant, and fluid sealant has low mould
Measuring the performance of high resilience, fluid sealant is used for concrete joint, and the siloxanes of performed polymer generates silicon hydroxyl with the reaction of moisture in air
Base, carries out solidification crosslinking film forming under the effect of catalyst, and whole process does not produce carbon dioxide, and the colloid of solidification is closely knit,
Good with the caking property of concrete so that it is there is good sealing effectiveness.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following enforcement
Example.
Embodiment 1
The present embodiment provides a kind of silicane-modified polyurethane fluid sealant performed polymer, and this performed polymer is prepared by the following method:
200g polypropylene oxide glycol (molecular weight 1000, purchased from DOW Chemical, the trade mark is Voranol2110TB) is added
Reactor, is warming up to 110 DEG C after stirring, after vacuum dehydration 2 hours, be cooled to 80 DEG C, adds 220g MDI-100 stirring
Reacting 2 hours, (molecular weight 3000, purchased from the big chemical industry Limited Liability in Shandong blue star east to be subsequently adding 800g Polypropylene Oxide Triol
Company, the trade mark is DL-3000) react 3～4 hours at 80 DEG C, it is cooled to 50 DEG C, drips 114g γ-aminopropyl trimethoxy
Silane, until NCO content all runs out of, stirs 2 hours, obtains performed polymer.
Embodiment 2
The present embodiment provides a kind of silicane-modified polyurethane fluid sealant performed polymer, and this performed polymer is prepared by the following method:
200g polypropylene oxide glycol (molecular weight 2000, purchased from DOW Chemical, the trade mark is Voranol2120) is added anti-
Answer still, after stirring, be warming up to 110 DEG C, after vacuum dehydration 2 hours, be cooled to 80 DEG C, add 135g MDI-100 stirring anti-
Answer 2 hours, be subsequently adding 700g high activity polyether triol (molecular weight 6000, purchased from DOW Chemical, the trade mark is Voranol6055)
Reacting 3～4 hours at 80 DEG C, be cooled to 50 DEG C, dropping 108g γ-aminopropyltrimethoxysilane is until NCO content is whole
Run out of, stir 2 hours, obtain performed polymer.
The performed polymer of embodiment 1 and 2 is carried out performance test, and test result sees table 1.
Table 1 is the performance test results of the performed polymer of embodiment 1 and 2
| Performance | Embodiment 1 | Embodiment 2 |
| Outward appearance | Clear viscous liquids | Clear viscous liquids |
| Viscosity (25 DEG C) | 40,000cp | 55,000cp |
| Storage period | >=December | >=December |
| Hot strength | 0.8MPa | 1.0MPa |
| Elongation at break | 450% | 500% |
| 100% modulus | 0.3MPa | 0.34MPa |
Note: solidify 7 days at 25 DEG C by performed polymer+1% catalyst dibutyltin dilaurylate in 99% embodiment 1 and 2
After record data above.
Embodiment 3
The present embodiment provides a kind of single-component silane modified polyurethane sealant for building, and raw material used and consumption see
Table 1,
Wherein, performed polymer uses the performed polymer of embodiment 1；
Filler is ground calcium carbonate；
Plasticizer is DINP；
Adhesion promoter is γ-aminopropyltrimethoxysilane, and purchased from SHIN-ETSU HANTOTAI's organosilicon, the trade mark is KBM-903；
Thixotropic agent is aerosil, and purchased from moral mountain chemical industry, the trade mark is PM-20L；
UV absorbent is UV-1；
Ultra-violet stabilizer is UV-P；
Catalyst is dibutyl tin laurate.
The preparation method of this fluid sealant is: performed polymer, the filler of drying, plasticizer, thixotropic agent are added dual shaft planetary and divided
Dissipate in still, after low speed dispersion 15min, evacuation, inflated with nitrogen, after high speed dispersion 30min, it is sequentially added into adhesion promoter, ultraviolet
Light absorbers, ultra-violet stabilizer, catalyst, after continuing high speed dispersion 15min, extrude, fill, obtain fluid sealant.
Embodiment 4
The present embodiment provides a kind of single-component silane modified polyurethane sealant for building, and raw material used and consumption see
Table 1, in addition to performed polymer, plasticizer, remaining is with embodiment 3.
Performed polymer uses the performed polymer of embodiment 2；
Plasticizer be DINP, DIDP be the mixture of the composition of 3/2 in mass ratio.
Embodiment 5
The present embodiment provides a kind of single-component silane modified polyurethane sealant for building, and raw material used and consumption see
Table 1, in addition to filler, adhesion promoter, thixotropic agent, remaining is with embodiment 3.
Filler is titanium dioxide；
Adhesion promoter is N-phenyl-γ-aminopropyltrimethoxysilane, and purchased from SHIN-ETSU HANTOTAI's organosilicon, the trade mark is KBM-
573。
Thixotropic agent is polyamide wax, and purchased from Arkema of France, the trade mark is SLT.
Comparative example 1
This comparative example provides a kind of fluid sealant, and the performed polymer that this fluid sealant uses uses NCO end-blocking, and performed polymer can be from Cohan
Wound is buied.
Table 1 is embodiment 3～5 and the raw material composition of fluid sealant of comparative example 1
To embodiment 3～5 and the fluid sealant of comparative example 1 carry out performance test, performance test is according to " Q/
320584PBT014-2016 " the carrying out that specify detect, and result sees table 2.
Table 2 is embodiment 3～5 and the performance test results of fluid sealant of comparative example 1
The index of the fluid sealant of embodiment 3～5 is all higher than the respective model of the index " JC/T 482-2003 " of national standard
Requirement.
Above the present invention is described in detail, its object is to allow the personage being familiar with this art will appreciate that this
Invention content and be carried out, can not limit the scope of the invention with this, and the invention is not restricted to above-mentioned enforcement
Example, all equivalence changes made according to the spirit of the present invention or modification, all should contain within protection scope of the present invention.
Claims (10)
1. a silicane-modified polyurethane fluid sealant performed polymer, it is characterised in that: based on weight/mass percentage composition, described performed polymer
Composition of raw materials includes:
Polyether polyol 70% ~ 80%；
Isocyanates 10% ~ 20%；
Silane coupler 5% ~ 15%,
Wherein, the mixture that described polyether polyol is polyether polyol A and polyether polyol B is 0.2～0.3 in mass ratio,
Wherein, described polyether polyol A is polyether Glycols, and described polyether polyol B is polyether-tribasic alcohol.
Silicane-modified polyurethane fluid sealant performed polymer the most according to claim 1, it is characterised in that: described polyether polyol
A is the polypropylene oxide glycol of molecular weight 1000 ~ 2000；Described polyether polyol B is the polycyclic oxygen third of molecular weight 1500 ~ 3000
The mixture of the one or both in the high activity polyether triol of alkane triol and molecular weight 5000 ~ 6000.
Silicane-modified polyurethane fluid sealant performed polymer the most according to claim 1, it is characterised in that: described isocyanates is
The combination of one or more in toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone diisocyanate.
Silicane-modified polyurethane fluid sealant performed polymer the most according to claim 1, it is characterised in that: described silane coupler
For N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropyl dimethoxy
The combination of one or more in base silane, γ mercaptopropyitrimethoxy silane.
5. the preparation of the silicane-modified polyurethane fluid sealant performed polymer as described in a claim any one of claim 1 ~ 4
Method, it is characterised in that described preparation method comprises the following steps:
(1) make polyether polyol A and isocyanates react 1 ~ 3 hour at a temperature of 70 DEG C ~ 90 DEG C, prepare isocyanate terminated pre-
Aggressiveness；
(2) the isocyanate terminated performed polymer making step (1) obtain reacts 3 ~ 4 with polyether polyol B at a temperature of 70 DEG C ~ 90 DEG C
Hour, it is subsequently adding silane coupler and reacts until NCO content runs out of at a temperature of 40 DEG C ~ 60 DEG C, obtaining described silane
Modified polyurethane sealant performed polymer.
Preparation method the most according to claim 5, it is characterised in that: described polyether polyol A first carries out pretreatment, then with
Described isocyanates react, wherein, described pretreatment for polyether polyol A is warming up to 100 DEG C ~ 120 DEG C, vacuum dehydration 1 ~ 3
Hour.
7. a single-component silane modified polyurethane sealant for building, it is characterised in that based on weight/mass percentage composition, described close
The composition of raw materials of sealing includes:
Performed polymer 20% ~ 30%；
Filler 35% ~ 45%；
Plasticizer 10% ~ 20%；
Adhesion promoter 2% ~ 8%；
Thixotropic agent 3% ~ 8%；
UV absorbent 0.5% ~ 0.8%；
Ultra-violet stabilizer 0.2% ~ 0.5%；
Catalyst 0.01% ~ 0.2%；
Wherein, described performed polymer is that silicane-modified polyurethane fluid sealant described in claim any one of claim 1 ~ 4 is pre-
Aggressiveness.
Single-component silane modified polyurethane sealant for building the most according to claim 7, it is characterised in that: described adhesion
Accelerator is N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropyl
The combination of one or more in dimethoxysilane.
Single-component silane modified polyurethane sealant for building the most according to claim 7, it is characterised in that: described thixotroping
Agent is the combination of one or more in aerosil, polyamide wax, organobentonite.
Single-component silane modified polyurethane sealant for building the most according to claim 7, it is characterised in that fill out described in:
Material is the combination of one or more in ground calcium carbonate, barium sulfate, titanium dioxide, Pulvis Talci, mica powder.
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Cited By (16)
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|---|---|---|---|---|
| CN107245317A (en) * | 2017-06-14 | 2017-10-13 | 广州千顺工业材料有限公司 | Moisture-curable polyurethane hot-melt glue and preparation method thereof |
| CN107760249A (en) * | 2017-09-15 | 2018-03-06 | 广东普赛达密封粘胶有限公司 | A kind of not bubbling road gap-grouting glue used under hot and humid environment and preparation method thereof |
| CN107955571A (en) * | 2017-12-11 | 2018-04-24 | 浙江工业大学 | A kind of silane modified polyether base rubber of low viscosity and preparation method thereof |
| CN108048024A (en) * | 2017-12-15 | 2018-05-18 | 安徽省宣城市华纳新材料科技有限公司 | End-capping reagent and the heat-proof combustion-resistant silicane-modified polyurethane fluid sealant using its preparation |
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| CN109207111A (en) * | 2018-07-20 | 2019-01-15 | 安徽匠星联创新材料科技有限公司 | A kind of one-component polyurethane sealant and preparation method thereof |
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| CN110698629A (en) * | 2019-09-30 | 2020-01-17 | 嘉宝莉化工集团股份有限公司 | Polyether modified polyurethane curing agent and preparation method thereof |
| CN110845695A (en) * | 2019-11-27 | 2020-02-28 | 上海东大化学有限公司 | Water-swellable silane polyether type resin and preparation method thereof |
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| CN111704882A (en) * | 2020-05-20 | 2020-09-25 | 宿迁市同创化工科技股份有限公司 | Low-modulus MS glue and preparation method thereof |
| CN112029467A (en) * | 2020-09-16 | 2020-12-04 | 深圳市安伯斯科技有限公司 | High-transparency MS glue with pencil hardness reaching 3H and preparation method thereof |
| CN114989772A (en) * | 2021-07-05 | 2022-09-02 | 无锡博锦高分子研究发展有限公司 | Low-hardness textile polyurethane hot-melt adhesive and preparation method thereof |
| CN115403736A (en) * | 2022-09-09 | 2022-11-29 | 佳化化学科技发展（上海）有限公司 | Anti-aging and mildew-proof silane modified polyurethane sealant and preparation method thereof |
| CN115746243A (en) * | 2022-11-11 | 2023-03-07 | 安徽聚合辐化化工有限公司 | Waterborne polyurethane resin and preparation method thereof |
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