CN109593175A - A kind of half aperture polyurethane hard bubble composite material of complete water type and preparation method thereof - Google Patents
A kind of half aperture polyurethane hard bubble composite material of complete water type and preparation method thereof Download PDFInfo
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- CN109593175A CN109593175A CN201811232893.7A CN201811232893A CN109593175A CN 109593175 A CN109593175 A CN 109593175A CN 201811232893 A CN201811232893 A CN 201811232893A CN 109593175 A CN109593175 A CN 109593175A
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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
- 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
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
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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
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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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 invention discloses a kind of half aperture polyurethane hard bubble composite materials of complete water type, a kind of half aperture hard polyurethane foam of complete water type and preparation method thereof.The polyurethane hard bubble composite material produces polyurethane interval plate for casting method, including component A isocyanates and B component, B component include polyhydric alcohol conjugate, foaming agent, catalyst, surfactant and thinner.The present invention also selects propene carbonate as thinner on the basis of using water as foaming agent, and using polyhydric alcohol conjugate, the polyurethane interval board size stability produced by casting method is good, and compressive strength is high, Density Distribution is uniform, and environmental protection.
Description
Technical field
The present invention relates to one kind for casting method production polyurethane interval plate polyurethane hard bubble composite material and a kind of full water
Half aperture hard polyurethane foam of type and preparation method thereof belongs to hard bubble heat preservation production field.
Background technique
Currently used as the combination material of casting method production polyurethane interval plate, foaming agent is mainly HCFC-141B, hydrochlorofluorocarbons
Destruction of the foaming agent to ozone layer, China will be forbidden to use HCFC-141b in 2026, can be used to substitute at present
HCFC-141b simultaneously has water, pentamethylene, HFC-245fa, HFC-365a, LBA etc. without the foaming agent of destruction to ozone layer.
Wherein, water is applied as chemical foaming agent in polyurethane field, to environment without destruction, and can directly continue to use it
Preceding foaming machine, without carrying out additional transformation.The producer that the country has begins to use pentamethylene as foaming agent, because its is inflammable
It is explosive, additional transformation need to be carried out to equipment；The prices such as HFC-245fa, HFC-365a, LBA are higher, and prolonged application value is low.
And water reacts the carbon dioxide generated with isocyanates and is easy evolution, foam size stability is poor；And generate
Polyureas causes foam bonding poor；It so water is larger as blowing agent formulations technological development difficulty, obtain it could not widely
Using.
Patent CN104877105A discloses a kind of polyurethane hard bubble composite material and preparation method thereof, and this method uses HFC-
365mfc/227ea is as foaming agent, higher cost, and not environmentally.
Patent CN1616512A discloses a kind of polyurethane rigid foam plastic, using HFC-245fa as foaming agent, but
It is to need 5-10 DEG C of low temperature use, hardly possible operation, complex process.
Patent CN101039979A discloses a kind of method that pentamethylene makes polyurethane pipeline for foaming agent, and this method reaches
To the purpose of substitution HCFC-141B, but pentamethylene is inflammable and explosive, more demanding to equipment and workshop, need to carry out huge transformation.
In conclusion being badly in need of a kind of higher environment-friendly foaming combination material of cost performance, it can solve the above-mentioned prior art and exist
Higher cost, problem not environmentally, not easy to operate, inflammable and explosive.Also, make the items of the polyurethane rigid foam material of preparation
It has excellent performance.
Summary of the invention
In view of the above-mentioned problems, can be used for casting method production polyurethane interval the object of the present invention is to provide a kind of environment-friendly type
The hard bubble composite material of plate.A kind of half aperture hard polyurethane foam of complete water type and preparation method thereof is also provided.
To achieve the above object, the present invention takes following technical scheme:
A kind of half aperture polyurethane hard bubble composite material of complete water type, preparing raw material includes component A and B component, wherein component A
For isocyanates, B component is mixture, is calculated with B component gross mass, the percentage of each component in B component are as follows:
84~95wt% of polyhydric alcohol conjugate, preferably 85~92wt%wt%；
Foaming agent 2.0~5.0wt%, 2.5~4.5wt%；
1.0~2.8wt% of catalyst, preferably 1.5~2.4wt%；
1.5~4.0wt% of surfactant, preferably 1.9~3.5wt%；
0.5~7wt% of thinner, preferably 1~5wt%.
Component A of the present invention is isocyanates, including polymeric MDI, liquefaction modified MDI etc., preferably Yantai Wanhua company
One of the M20S of 44V20, BASF company of 5005S, Bayer company of PM-200, Huntsman company or a variety of.
In half aperture polyurethane hard bubble composite material of the present invention, the mass ratio of the component A and B component is 0.8~
1.8:1, preferably 1~1.5:1.
In half aperture polyurethane hard bubble composite material of the present invention, the thinner is propene carbonate.
After propene carbonate is added in the present invention, viscosity is declined quickly；Because water reacts the dioxy generated with isocyanates
Change carbon and be easy evolution, foam size stability is poor, and carbon dioxide in foam finished product abscess obtained is added after propene carbonate
Evolution be eased, finished size stability is preferable, and can improve foam embrittlement phenomenon.
Polyhydric alcohol conjugate of the present invention includes following components:
30~55 mass parts of sorbierite and glycerol mixing starting polyether polyol, preferably 33~50 mass parts；
18~42 mass parts of sucrose and diethylene glycol (DEG) mixing starting polyether polyol, preferably 20~40 mass parts；
6~22 mass parts of propylene glycol polyether polyol, preferably 8~20 mass parts.
The hydroxyl value of sorbierite and glycerol mixing starting polyether polyol of the present invention is 400~600mgKOH/g, official
Energy degree is that 4.5~6,25 DEG C of viscosity are 4000~11000mPas；It is preferred that hydroxyl value is 450~550mgKOH/g, degree of functionality 5
~5.5,25 DEG C of viscosity are 5000~9500mPas.
The hydroxyl value of sucrose and diethylene glycol (DEG) mixing starting polyether polyol of the present invention is 350~500mgKOH/g, official
Energy degree is that 3~5,25 DEG C of viscosity are 2000~9000mPas；It is preferred that hydroxyl value is 420~460mgKOH/g, degree of functionality 3.8
~4.5,25 DEG C of viscosity are 2800~7500mPas.
The hydroxyl value of propylene glycol polyether polyol of the present invention is 80~300mgKOH/g, and 2,25 DEG C of degree of functionality viscous
Degree is 40~250mPas；It is preferred that hydroxyl value is 100~200mgKOH/g, 25 DEG C of viscosity are 100~120mPas.
The polyhydric alcohol conjugate that the present invention uses effectively avoids the problem that high functionality is too firm, low degree of functionality is too soft, so that
It full water formula intensity and flexible can well arrange in pairs or groups；Bonding is good, excellent in dimensional stability.
Surfactant of the present invention is selected from siloxane type surfactants, and the siloxane type surfactants are preferred
One of B8423, AK8805, H3636, DC193, B8404, AK8812, O-501, B8523, L5388 or a variety of；The table
Face activating agent is preferably B8423 and O-501.
Catalyst of the present invention is selected from amines catalyst and/or organic metal salt catalyst, the amines catalysis
The example of agent includes but is not limited to five methyl diethylentriamine, N, N- dimethyl cyclohexyl amine, triethylene diamine, triethylamine, 1,
4- lupetazin, N, one of N- dimethyl benzylamine and double dimethylamino ethyl ethers or a variety of, preferably pentamethyl diethyl
Alkene triamine, N, N- dimethyl benzylamine, N, one of N- dimethyl cyclohexyl amine or a variety of.
Foaming agent of the present invention is water.
The preparation method of B component in polyurethane hard bubble composite material of the present invention, comprising the following steps: by polyhydric alcohol conjugate
In each polyether polyol stirred tank is added, temperature control is to 75-80 DEG C while stirring, and surfactant, catalyst, drop is then added
Stick, foaming agent stir 40-50min.
Polyurethane hard bubble composite material of the present invention can be used for casting method production polyurethane interval plate.
A method of hard polyurethane foam is prepared, component A is mixed with B component, through high-pressure foam, the polyurethane is made
Hard bubble.
The condition of high-pressure foaming process of the present invention are as follows: 19~23 DEG C of material temperature, 100~150bar of pressure (gauge pressure), mould
38~45 DEG C of temperature of tool, demoulding time are 35~45min；It is preferred that 21 DEG C of material temperature, pressure 125bar (gauge pressure), mold temperature 40
℃；The high-pressure foaming process, the demoulding time of reaction mixture in a mold are 40min.
The hard polyurethane foam finished product that the present invention obtains absorbs water comparatively fast into the water, and surveyed percent opening is 40% or more.By this
Polyurethane interval plate foam density >=36kg/m made from the invention polyurethane hard bubble composite material3；Thermal coefficient≤
0.022W/(mK)；Compression strength >=150Kpa；Foam and panel adhesive strength >=0.1Mpa.
The positive effect of the present invention is to have used water as foaming agent, more environmentally-friendly, after addition propene carbonate,
Viscosity is declined quickly；It is easy evolution because water reacts the carbon dioxide generated with isocyanates, foam size stability is poor,
The evolution that carbon dioxide in foam finished product abscess obtained after propene carbonate is added is eased, finished size stability compared with
It is good, and foam toughness is preferable.
Specific embodiment
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
The raw material used in embodiment:
PM200 Wanhua Chemical Group Co., Ltd.；
Sorbierite and glycerol mixing starting polyether polyol: R2490 (25 DEG C of viscosity 9000mPas, degree of functionality 5, hydroxyl
Value 500mgKOH/g) Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.；NJ-6305C (25 DEG C of viscosity 5800mPas, official
Energy degree is 5.5, hydroxyl value 500mgKOH/g) Jurong Ningwu new material limited liability company；
Sucrose and diethylene glycol (DEG) mixing starting polyether polyol: R4110 (25 DEG C of viscosity 3000mPas, degree of functionality 4, hydroxyl
Value 440mgKOH/g), R420 (25 DEG C of viscosity 7000mPas, degree of functionality 4.5, hydroxyl value 430mgKOH/g) ten thousand Hua Huaxue it is (peaceful
Wave) Rong Wei polyurethane Co., Ltd；
Propylene glycol polyether polyol: C2010 (25 DEG C of viscosity 110mPas, degree of functionality 2, hydroxyl value 112mgKOH/g),
C2007 (25 DEG C of viscosity 100mPas, degree of functionality 2, hydroxyl value 170mgKOH/g), C2010B (25 DEG C of viscosity 160mPas,
Degree of functionality is 2, hydroxyl value 115mgKOH/g) Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd.；
O-501 Ying Chuan Specialty Chemical (Shanghai) Co., Ltd.；
B8423 Ying Chuan Specialty Chemical (Shanghai) Co., Ltd.；
Propene carbonate Linyi Li Xing Chemical Co., Ltd.；
Five methyl diethylentriamine Ying Chuan Specialty Chemical (Shanghai) Co., Ltd.；
N, N- dimethyl cyclohexyl amine Ying Chuan Specialty Chemical (Shanghai) Co., Ltd.；
N, N- dimethyl benzylamine Pin Hua chemical industry (Shanghai) Co., Ltd.；
Sucrose, diethylene glycol (DEG) and palm oil mixing starting polyether polyol: R8240 (25 DEG C of viscosity 5000mPas, hydroxyl value
400mgKOH/g, degree of functionality 4) Wanhua Chemical (Ningbo) Rongwei Polyurethane Co., Ltd..
Embodiment 1
(1) prepared by B component:
It is calculated with B component gross mass, each ingredient percent such as the following table 1 in B component.
1 B component of table composition
The preparation process of B component is: stirred tank is added in polyether polyol R2490, R4110, C2010 in B component, while stirring
Side temperature control is mixed to 80 DEG C of addition propene carbonates, O-501, B8423, five methyl diethylentriamine, N, N- dimethyl cyclohexyl amine,
N, N- dimethyl Bian amine, water, 80 turns/min of speed of agitator stir 40min.
(2) preparation of polyurethane interval plate:
Component A PM200 and B component are passed through high-pressure unit according to mass ratio 1:1 respectively to pour in being solidified into automatically in mold
Type, the condition of high-pressure foaming process are as follows: 21 DEG C of material temperature, pressure 125bar (gauge pressure), 40 DEG C of mold temperature；Reaction mixture is in mould
Demoulding time 40min in tool.Products obtained therefrom performance such as the following table 2.
2 properties of product of table
Embodiment 2
(1) prepared by B component:
It is calculated with B component gross mass, each ingredient percent such as the following table 3 in B component.
3 B component of table composition
The preparation process of B component is: stirred tank is added in polyether polyol NJ-6305C, R420, C2010B in B component,
Temperature control is to 80 DEG C of addition propene carbonates, O-501, B8423, five methyl diethylentriamine, N, N- diformazan basic ring while stirring
Hexylamine, N, N- dimethyl Bian amine, water, 80 turns/min of speed of agitator stir 40min.
(2) preparation of polyurethane interval plate:
Component A and B component are passed through high-pressure unit according to mass ratio 1.3:1 respectively to pour in curing molding automatic in mold,
The condition of high-pressure foaming process are as follows: 21 DEG C of material temperature, pressure 125bar (gauge pressure), 40 DEG C of mold temperature；Reaction mixture is in mold
In demoulding time 40min.Products obtained therefrom performance such as the following table 4.
4 properties of product of table
Embodiment 3
(1) prepared by B component:
It is calculated with B component gross mass, each ingredient percent such as the following table 5 in B component.
5 B component of table composition
The preparation process of B component is: stirred tank is added in polyether polyol R2490, R420, C2010 in B component, while stirring
Side temperature control is mixed to 80 DEG C of addition propene carbonates, O-501, B8423, five methyl diethylentriamine, N, N- dimethyl cyclohexyl amine,
N, N- dimethyl Bian amine, water, 80 turns/min of speed of agitator stir 40min.
(2) preparation of polyurethane interval plate:
Component A and B component are passed through high-pressure unit according to mass ratio 1.5:1 respectively to pour in curing molding automatic in mold,
The condition of high-pressure foaming process are as follows: 21 DEG C of material temperature, pressure 125bar (gauge pressure), 40 DEG C of mold temperature；Reaction mixture is in mold
In demoulding time 40min.Products obtained therefrom performance such as the following table 6.
6 properties of product of table
Comparative example 1
(1) prepared by B component:
It is calculated with B component gross mass, each ingredient percent such as the following table 7 in B component.
7 B component of table composition
The preparation process of B component is: stirred tank is added in polyether polyol R2490, R8240, C2010 in B component, while stirring
Side temperature control is mixed to 80 DEG C of addition propene carbonates, B8423, five methyl diethylentriamine, N, N- dimethyl cyclohexyl amine, N, N-
Dimethyl Bian amine, water, 80 turns/min of speed of agitator stir 40min.
(2) preparation of polyurethane interval plate:
Component A and B component are passed through high-pressure unit according to mass ratio 1.5:1 respectively to pour in curing molding automatic in mold,
The condition of high-pressure foaming process are as follows: 21 DEG C of material temperature, pressure 125bar (gauge pressure), 40 DEG C of mold temperature；Reaction mixture is in mold
In demoulding time 40min.Products obtained therefrom performance such as the following table 8.
8 properties of product of table
Claims (11)
1. a kind of half aperture polyurethane hard bubble composite material of complete water type, preparing raw material includes component A and B component, wherein component A is
Isocyanates, B component are mixture, are calculated with B component gross mass, the percentage of each component in B component are as follows:
84~95wt% of polyhydric alcohol conjugate, preferably 85~92wt%wt%；
Foaming agent 2.0~5.0wt%, 2.5~4.5wt%；
1.0~2.8wt% of catalyst, preferably 1.5~2.4wt%；
1.5~4.0wt% of surfactant, preferably 1.9~3.5wt%；
0.5~7wt% of thinner, preferably 1~5wt%；
The mass ratio of the component A and B component is 0.8~1.8:1, preferably 1~1.5:1.
2. combination material according to claim 1, which is characterized in that the component A is selected from polymeric MDI and liquefaction modified MDI
One of or a variety of, the preferably 44V20 of 5005S, Bayer company of PM-200, Huntsman company of Wan Hua chemical company
With one of the M20S of BASF AG or a variety of.
3. combination material according to claim 1 or 2, which is characterized in that the thinner is propene carbonate.
4. combination material according to claim 1-3, which is characterized in that the polyhydric alcohol conjugate includes with the following group
Point:
30~55 mass parts of sorbierite and glycerol mixing starting polyether polyol, preferably 33~50 mass parts；
18~42 mass parts of sucrose and diethylene glycol (DEG) mixing starting polyether polyol, preferably 20~40 mass parts；
6~22 mass parts of propylene glycol polyether polyol, preferably 8~20 mass parts.
5. combination material according to claim 1-4, which is characterized in that the sorbierite and glycerol mixing starting are poly-
The hydroxyl value of ethoxylated polyhydric alcohol is 400~600mgKOH/g, and degree of functionality is that 4.5~6,25 DEG C of viscosity are 4000~11000mPas；It is excellent
Selecting hydroxyl value is 450~550mgKOH/g, and degree of functionality is that 5~5.5,25 DEG C of viscosity are 5000~9500mPas.
6. combination material according to claim 1-5, which is characterized in that the sucrose and diethylene glycol (DEG) mixing starting are poly-
The hydroxyl value of ethoxylated polyhydric alcohol is 350~500mgKOH/g, and degree of functionality is that 3~5,25 DEG C of viscosity are 2000~9000mPas；It is preferred that
Hydroxyl value is 420~460mgKOH/g, and degree of functionality is that 3.8~4.5,25 DEG C of viscosity are 2800~7500mPas.
7. combination material according to claim 1-6, which is characterized in that the hydroxyl value of the propylene glycol polyether polyol
For 80~300mgKOH/g, 2,25 DEG C of viscosity of degree of functionality are 40~250mPas；It is preferred that hydroxyl value is 100~200mgKOH/g,
25 DEG C of viscosity are 100~120mPas.
8. combination material according to claim 1-7, which is characterized in that the foaming agent is water.
9. a kind of method that any one of -8 combination material prepare half aperture hard polyurethane foam of complete water type according to claim 1, packet
Include following steps:
(1) polyhydric alcohol conjugate, surfactant, catalyst, thinner and foaming agent are uniformly mixed, B component is made；
(2) B component obtained by step (1) is mixed with component A polyisocyanates, through high-pressure foam, the hard polyurethane foam is made.
10. according to the method described in claim 9, it is characterized in that, the condition of high-pressure foaming process described in step (2) are as follows:
19~23 DEG C of material temperature, 100~150bar of gauge pressure, 38~45 DEG C of mold temperature, demoulding time is 35~45min；It is preferred that material temperature 21
DEG C, gauge pressure 125bar, 40 DEG C of mold temperature；Demoulding time 40min.
11. a kind of half aperture hard polyurethane foam of complete water type prepared according to claim 9 or 10 the methods, which is characterized in that
The hard polyurethane foam percent opening is 40% or more；Foam density >=36kg/m3；Thermal coefficient≤0.022W/ (mK)；Pressure resistance
Degree >=150Kpa；Foam and panel adhesive strength >=0.1Mpa.
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| CN111320737A (en) * | 2020-04-13 | 2020-06-23 | 南京红宝丽聚氨酯有限公司 | Polyurethane raw material composition, preparation method and application of polyurethane rigid foam |
| CN111393600A (en) * | 2020-04-30 | 2020-07-10 | 明光市铭垚凹凸棒产业科技有限公司 | High-flame-retardant rigid polyurethane foam with expanded graphite and attapulgite and preparation method thereof |
| CN112280002A (en) * | 2020-10-31 | 2021-01-29 | 绍兴市华创聚氨酯有限公司 | All-water foaming system combined polyether for door body |
| CN113698569A (en) * | 2021-07-20 | 2021-11-26 | 佳化化学科技发展（上海）有限公司 | Combined polyether, polyurethane block foam for LNG pipe bracket and preparation method and application of polyurethane block foam |
| CN114437662A (en) * | 2021-12-29 | 2022-05-06 | 山东一诺威新材料有限公司 | Industrial environment-friendly polyurethane adhesive and preparation method and application thereof |
| CN114539504A (en) * | 2020-11-25 | 2022-05-27 | 万华化学集团股份有限公司 | High-fluidity pipeline thermal insulation material and preparation method thereof |
| JP2022103495A (en) * | 2020-12-28 | 2022-07-08 | 株式会社日本アクア | Urethane resin composition including renewable resources and curing agent for urethane resin composition |
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