CN1807479A - Modified polyurethane hard bubble and its uses - Google Patents
Modified polyurethane hard bubble and its uses Download PDFInfo
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- CN1807479A CN1807479A CN 200510045368 CN200510045368A CN1807479A CN 1807479 A CN1807479 A CN 1807479A CN 200510045368 CN200510045368 CN 200510045368 CN 200510045368 A CN200510045368 A CN 200510045368A CN 1807479 A CN1807479 A CN 1807479A
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Abstract
The invention relates to a modified polyurethane hard bubble and the application in water resistance, heat preservation of exterior wall, containing component (A) and component (B), the characteristic is that the component (A) is polyhydroxy compound combined material which is made by adding modifier and other multifarious auxiliary agent in polyether or polyester polyol, the modifier is made by polyhexamethylene adipate and tolylenediisocyanate; The component (B) is isocyanate. The modified polyurethane hard bubble of this invention is applied to heat preservation of exterior wall, having the advantage of low density, high specific tenacity, small thermal conductivity factor, simple and convenient construction work. It is a perfect heat-insulating material of exterior wall.
Description
Technical field
The invention belongs to the polyurethanes technology field, be specifically related to a kind of modified polyurethane hard bubble and the application of this material in exterior wall is waterproof thermal-insulated.
Background technology
Hard polyurethane vinegar porous plastics (Hard Polyurethane Foamed Plastics, PU) be called for short hard polyurethane foam, it is the ideal material of the position thermal-insulation energy-conservation such as roof, top ceiling, wallboard, floor of buildings, particularly when heat insulating usefulness requirement height, the heat insulating layer requires thin, so that increase the buildings useful area, processing, construction, maintenance require easily under the situation, and the superiority of urethane is especially remarkable.Hard polyurethane foam is widely used in building energy saving field now.Some countries, the first place that the consumption of hard polyurethane foam aspect building occupied total amount.As the U.S., for building hard bubbling in 1996 accounts for 49% of total consumption that hard bubbles, and equipment such as family expenses, commercial refrigerator only account for 23.5%.
Hard polyurethane foam is formed by two kinds of component hybrid reactions of A, B, is a kind of two component polyurethane.The B component is generally carbimide, and the A component is generally the combination material of polyol, generally based on polyethers, adds auxiliary agents such as appropriate amount of catalysts, whipping agent, suds-stabilizing agent, fire retardant and forms.Use air compressor machine to be source of the gas in the construction, spray by spraying machine, make A, B two components produce chemical reaction, rapid expansion in moment, formation combines the firm cruel layer of poly-ammonia that hard bubbles with roofing, thereby reaches waterproof thermal-insulated effect.
Compare with lagging material with five existing big class (asphalt felt, polymer coiled material, perlite, polystyrene, concrete) waterproof, polyurethane rigid foam plastic has the performance of a lot of excellences: little as density, has microvoid structure, the specific tenacity height, thermal conductivity is little, and light weight, sound insulation, heat insulation, corrosion-resistant, heatproof add and be not easy burning behind the fire retardant, unicellular structure is difficult for suction etc.At present, hard polyurethane foam is occupied an leading position in the industrial heat preservation field.
Polyurethane rigid foam plastic particularly adopts the spraying coating process scene to foam as external-wall heat-insulation material, compares with general polyurethane rigid foam plastic, and technical difficulty is bigger.Because thermal insulation layer will be adhesively fixed on the whole surface of exterior wall through spraying, and outside surface will stand wind, drenches with rain, cold and heat freezes test molten and that sight is exposed to the sun, and the environment of use and the environment of construction all compare harshness.Therefore, require strictly more on the exterior wall heat preservation construction, require highlyer in the selection of material, polyurethane rigid foam plastic can not be applied on the exterior-wall heat insulation usually, because in construction process or in the harsh use, occurs some serious problems easily.As: the hard polyurethane foam and the metope that spray to wall face are bonding not firm, through causing part or whole coming off after a while.Influence heat insulation effect and work-ing life.Because the improper meeting of selection causes foam heat-insulation layer crack or large-area cracking, have a strong impact on the heat insulation effect of thermal insulation layer in addition.The bonding strength of basal layer and urethane is can't reach the ideal effect by urethane itself.Prior art is generally respectively brushed one deck priming paint as adhesive linkage at basic unit's body of wall and anti-parting, increases the bonding strength between layer of polyurethane and the body of wall.
Summary of the invention
The purpose of this invention is to provide that a kind of bonding strength is big, the hard polyurethane foam of good toughness, be applied to the external wall waterproof insulation, save the operation of construction, solved the cost that bonding not firm, the local difficult problem easy to crack of current polyurethane rigid foam material has reduced insulation simultaneously.
The technical solution used in the present invention is:
A kind of modified polyurethane hard bubble comprises component (A) and component (B), it is characterized in that component (A) is a polyol combination material, and component (B) is an isocyanic ester;
Comprise properties-correcting agent in the component (A), properties-correcting agent is mainly made by poly-hexanodioic acid hexylene glycol polyester and tolylene diisocyanate.
Described modified polyurethane hard bubble is characterized in that component (A) is made up of the component of following parts by weight:
30～70 parts of glycerine propylene oxide polyether glycols, 10～40 parts of quadrol propylene oxide polyether glycols, 10～40 parts of rosin propylene oxide polyester polyols, 5～20 parts of properties-correcting agent, 5～15 parts of linking agents, 3～5 parts of organosilicon stablizers, 4～10 parts of Primary Catalystss, 1～8 part of cocatalyst, 5～20 parts of fire retardants, 10～40 parts of whipping agents.
Component (B) is an isocyanic ester.
Principle of the present invention is: isocyanic ester and glycerine propylene oxide polyether glycol, quadrol propylene oxide polyether glycol, rosin propylene oxide polyester polyol are hard polyurethane foam principal reaction raw materials; Water is chain propagation agent, simultaneously also as the raw material sources of carbon dioxide; Linking agent have promote molecular structure crosslinked, improve foam curing speed, reduce the brittle effect of porous plastics, linking agent can improve the foamy mechanical property, as elasticity, tensile strength etc.; The effect of Primary Catalysts and cocatalyst is to promote foaming and gel reaction; Fire retardant is to make foam have fire retardation; Whipping agent vaporization back is as the source of steam bubble, and takes away the heat in the reaction, and it advances people's foam micropore to reduce thermal conductivity; Properties-correcting agent is that poly-hexanodioic acid hexylene glycol polyester and isocyanic ester are made, and main effect is the bonding force that improves polyurethane insulation coating.
Described a kind of modified polyurethane hard bubble is characterized in that component (B) is one or several in tolylene diisocyanate (being called for short TDI), '-diphenylmethane diisocyanate (being called for short MDI), terephthalylidene vulcabond (being called for short HDI), the polymethine polyphenyl polyisocyanate (being called for short PAPI).
Described modified polyurethane hard bubble is characterized in that linking agent is one or several in glycol ether, trolamine, four (the poly-second one hydroxypropyl) quadrol.
Described modified polyurethane hard bubble is characterized in that Primary Catalysts is one or several in triethylene diamine, dimethyl ethylenimine, the dibutyl tin laurate.
Described modified polyurethane hard bubble is characterized in that a kind of in cocatalyst Potassium ethanoate, the potassium oleate.
Described modified polyurethane hard bubble is characterized in that fire retardant dimethyl methyl phosphonate (being called for short TCPP), three (chloro isopropyl) phosphoric acid ester (being called for short DMMP), three (β-chloroethyl) phosphoric acid ester (being called for short TCEP).
Described modified polyurethane hard bubble is characterized in that a kind of in whipping agent fluoro trichloromethane, Freon 113, the pentamethylene.
It is characterized in that the preparation of properties-correcting agent, comprise the following steps:
(1) in 900-1300 part dimethyl formamide, adds 300～500 parts of poly-hexanodioic acid hexylene glycol polyester, 600～800 parts of isocyanic ester, 200～300 parts of Acetylacetone acid iron;
(2) dimethylamine of adding catalytic amount under nitrogen protection, reacts 3h～4h down at 130～160 ℃;
(3) add 50～150 parts of TriMethylolPropane(TMP)s, be cooled to 100～110 ℃ of reaction 3～5h;
(4) decompression dehydration to solution solid content is 40～50%;
(5) add vinyl acetic monomer, reaction solution is diluted to solid content 20～35%.
Described a kind of modified polyurethane hard bubble is characterized in that the component (A) and the weight ratio of component (B) are 1～4: 1～3.
Described properties-correcting agent is characterized in that the component of poly-hexanodioic acid hexylene glycol polyester is 820～1200.
The application of modified polyurethane hard bubble in exterior-wall heat insulation comprises coating mortar, it is characterized in that sand-cement slurry mainly made by properties-correcting agent, fine sand, cement.
The application of described modified polyurethane hard bubble in exterior-wall heat insulation, the weight ratio that it is characterized in that properties-correcting agent, fine sand, cement is 1～2: 3～7: 1～3.
The application of described modified polyurethane hard bubble in exterior wall is waterproof thermal-insulated is characterized in that construction technology comprises the following steps:
(1) cleaning basic unit body of wall;
(2) to body of wall spraying modified polyurethane hard bubble, after spraying finishes, local levelling;
(3) brushing coating mortar;
(4) carry out the outer ornamental work of metope.
The application of modified polyurethane hard bubble in exterior wall is waterproof thermal-insulated is characterized in that modified polyurethane hard bubble can be applied to external wall outer insulation or exterior wall internal insulation.
Spraying hard-foam polyurethane construction environment temperature should not be lower than 10 ℃, and wind-force is not more than 5 grades, and wind speed should not during spraying, should have draught exclusion device greater than 5m/s.Coating mortar construction environment temperature should not be lower than 5 ℃.Forbid the rainy day to be constructed, the Pluvial construction should be carried out rainproof measure.
Modified polyurethane hard bubble of the present invention has following beneficial effect:
1) simultaneous interpretation blanket insurance temperature water-proof material is compared, and modified polyurethane hard bubble of the present invention has that density is little, thermal conductivity is little, water-intake rate is little and have thermal-insulating waterproof rot-resistant function.Specifically see Table 1 modified polyurethane material and general performance of heat protective material contrast table.
Table 1 modified polyurethane material and general performance of heat protective material contrast table
| Density, Kg/m 2 | Thermal conductivity W/mK | Water-intake rate volume % | Ultimate compression strength, MPa | Insulation layer thickness | Performance and purposes | |
| Modified polyurethane hard bubble | 45～55 | ≤0.023 | 1％ | 0.3MPa | Thermal-insulating waterproof is anticorrosion | |
| Pitch | --------- | -0.175 | 0.1 | --------- | 5mm | Anticorrosionly be not incubated |
| The pitch perlite | --------- | 0.175 | 0.1 | --------- | 30～50mm | Anticorrosionly be not incubated |
| Glass wool | 160～190 | 0.047-0.050 | ＜0.2 | ＞0.5 | 50mm | Insulation, waterproof layer does not pass a test |
| Slag wool | --------- | 0.047～0.058 | --------- | --------- | 50mm | Be incubated non-watertight |
| Polyvinyl chloride | 60～70 | 0.037 | 0.3 | 0.16 | --------- | --------- |
| Polystyrene | 50 | 0.037 | 0.4 | 0.18 | --------- | --------- |
2) the conventional polyurethanes bonding strength of hard bubbling is generally 1.6-1.8cm/kg, and the bonding strength of modified polyurethane hard bubble of the present invention is 2.0-2.3cm/kg, modified polyurethane hard bubble bonding strength of the present invention is big, does not need other spraying and adhesive bonding lacquer in construction, has reduced cost.
3) adopt modified cement mortar in the exterior-wall heat insulation construction technology of the present invention, the bonding strength of polyurethane insulation coating and body of wall is significantly improved, saved the tack coat between polyurethane insulation coating and the cement sand bed, shortened working procedure, reduced cost.
Embodiment:
Embodiment 1
(1) preparation of properties-correcting agent
In the 900Kg dimethyl formamide, add the poly-hexanodioic acid hexylene glycol polyester of 300Kg, 600Kg tolylene diisocyanate, 200Kg Acetylacetone acid iron, stir; The dimethylamine that adds catalytic amount under nitrogen protection, reacts 4h down at 130 ℃; Add the 50Kg TriMethylolPropane(TMP), be cooled to 100 ℃ of reaction 5h; Decompression dehydration to solution solid content is 40%; Add vinyl acetic monomer, reaction solution is diluted to solid content 20%, make properties-correcting agent.
Adopting the component of poly-hexanodioic acid hexylene glycol polyester is 820.
(2) B component adopts tolylene diisocyanate;
Component A is mixed and made into by the component of following weight: glycerine propylene oxide polyether glycol 300Kg, quadrol propylene oxide polyether glycol 100Kg, rosin propylene oxide polyester polyol 100Kg, properties-correcting agent 50Kg, linking agent 50Kg, organosilicon stablizer 30Kg, Primary Catalysts 40Kg, cocatalyst 10Kg, fire retardant 50Kg, whipping agent 100Kg;
Component (A) is 1: 1 with the weight ratio of component (B).
(3) application of modified polyurethane in external wall outer insulation
A) preparation modified cement mortar: in the 300Kg fine sand, add 100Kg hard polyurethane foam properties-correcting agent, after stirring, add 100Kg cement continuation stirring 3min again and pour out, standby.
B) the big-wall vertical line is hung in basic unit's body of wall cleaning, draws sea line, carries out levelling with modified cement mortar;
C) spray the modified polyurethane lagging material 3 times on screed-coat, finishing surpasses the protuberance of regulation;
D) after 1-2 hour, smear the modified mortar levelling;
E) outer decoration construction.
Embodiment 2
(1) preparation of properties-correcting agent
In the 1000Kg dimethyl formamide, add the poly-hexanodioic acid hexylene glycol polyester of 400Kg, 650Kg tolylene diisocyanate, 230Kg Acetylacetone acid iron, stir; The dimethylamine that adds catalytic amount under nitrogen protection, reacts 3.5h down at 140 ℃; Add the 80Kg TriMethylolPropane(TMP), be cooled to 105 ℃ of reaction 4h; Decompression dehydration to solution solid content is 45%; Add vinyl acetic monomer, reaction solution is diluted to solid content 25%, make properties-correcting agent.
Adopting the component of poly-hexanodioic acid hexylene glycol polyester is 1000.
(2) B component adopts '-diphenylmethane diisocyanate;
Component A is mixed and made into by the component of following weight: glycerine propylene oxide polyether glycol 400Kg, quadrol propylene oxide polyether glycol 200Kg, rosin propylene oxide polyester polyol 200Kg, properties-correcting agent 70Kg, linking agent 70Kg, organosilicon stablizer 40Kg, Primary Catalysts 50Kg, cocatalyst 30Kg, fire retardant 80Kg, whipping agent 200Kg;
Component (A) is 1: 3 with the weight ratio of component (B).
(3) application of modified polyurethane in exterior wall internal insulation, the part by weight of properties-correcting agent, fine sand, cement are 2: 3: 1.
All the other are with embodiment 1.
Embodiment 3
(1) preparation of properties-correcting agent
In the 1100Kg dimethyl formamide, add the poly-hexanodioic acid hexylene glycol polyester of 450Kg, 700Kg tolylene diisocyanate, 250Kg Acetylacetone acid iron, stir; The dimethylamine that adds catalytic amount under nitrogen protection, reacts 3.5h down at 150 ℃; Add the 100Kg TriMethylolPropane(TMP), be cooled to 105 ℃ of reaction 3.5h; Decompression dehydration to solution solid content is 40%; Add vinyl acetic monomer, reaction solution is diluted to solid content 30%, make properties-correcting agent.
Adopting the component of poly-hexanodioic acid hexylene glycol polyester is 1100.
(2) B component adopts the terephthalylidene vulcabond;
Component A is mixed and made into by the component of following weight: glycerine propylene oxide polyether glycol 550Kg, quadrol propylene oxide polyether glycol 300Kg, rosin propylene oxide polyester polyol 300Kg, properties-correcting agent 150Kg, linking agent 100Kg, organosilicon stablizer 50Kg, Primary Catalysts 70Kg, cocatalyst 50Kg, fire retardant 130Kg, whipping agent 300Kg;
Component (A) is 4: 1 with the weight ratio of component (B).
The part by weight of properties-correcting agent, fine sand, cement is 2: 7: 1.
All the other are with embodiment 1.
Embodiment 4
(1) preparation of properties-correcting agent
In the 1300Kg dimethyl formamide, add the poly-hexanodioic acid hexylene glycol polyester of 500Kg, 800Kg tolylene diisocyanate, 300Kg Acetylacetone acid iron, stir; The dimethylamine that adds catalytic amount under nitrogen protection, reacts 3h down at 160 ℃; Add the 150Kg TriMethylolPropane(TMP), be cooled to 110 ℃ of reaction 3h; Decompression dehydration to solution solid content is 50%; Add vinyl acetic monomer, reaction solution is diluted to solid content 35%, make properties-correcting agent.
Adopting the component of poly-hexanodioic acid hexylene glycol polyester is 1200.
(2) B component adopts the polymethine polyphenyl polyisocyanate;
Component A is mixed and made into by the component of following weight: glycerine propylene oxide polyether glycol 700Kg, quadrol propylene oxide polyether glycol 400Kg, rosin propylene oxide polyester polyol 400Kg, properties-correcting agent 200Kg, linking agent 150Kg, organosilicon stablizer 50Kg, Primary Catalysts 100Kg, cocatalyst 80Kg, fire retardant 200Kg, whipping agent 400Kg;
Component (A) is 1: 3 with the weight ratio of component (B).
(3) application of modified polyurethane in exterior wall internal insulation, the part by weight of properties-correcting agent, fine sand, cement are 2: 7: 3.
All the other are with embodiment 1.
Claims (9)
1. a modified polyurethane hard bubble comprises component (A) and component (B), it is characterized in that component (A) is a polyol combination material, and component (B) is an isocyanic ester;
Comprise properties-correcting agent in the component (A), properties-correcting agent is mainly made by poly-hexanodioic acid hexylene glycol polyester and tolylene diisocyanate.
2. a kind of modified polyurethane hard bubble according to claim 1 is characterized in that component (A) is made up of the component of following parts by weight:
30～70 parts of glycerine propylene oxide polyether glycols, 10～40 parts of quadrol propylene oxide polyether glycols, 10～40 parts of rosin propylene oxide polyester polyols, 5～20 parts of properties-correcting agent, 5～15 parts of linking agents, 3～5 parts of organosilicon stablizers, 4～10 parts of Primary Catalystss, 1～8 part of cocatalyst, 5～20 parts of fire retardants, 10～40 parts of whipping agents.
3. a kind of modified polyurethane hard bubble according to claim 1 is characterized in that the component (A) and the weight ratio of component (B) are 1～4: 1～3.
4. a kind of modified polyurethane hard bubble according to claim 1 is characterized in that component (B) is one or several in tolylene diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, the polymethine polyphenyl polyisocyanate.
5. a kind of modified polyurethane hard bubble according to claim 1 is characterized in that the preparation of properties-correcting agent, comprises the following steps:
(1) in 900-1300 part dimethyl formamide, adds 300～500 parts of poly-hexanodioic acid hexylene glycol polyester, 600～800 parts of tolylene diisocyanates, 200～300 parts of Acetylacetone acid iron;
(2) dimethylamine of adding catalytic amount under nitrogen protection, reacts 3h～4h down at 130～160 ℃;
(3) add 50～150 parts of TriMethylolPropane(TMP)s, be cooled to 100～110 ℃ of reaction 3～5h;
(4) decompression dehydration to solution solid content is 40～50%;
(5) add vinyl acetic monomer, reaction solution is diluted to solid content 20～35%.
6. properties-correcting agent according to claim 5 is characterized in that the component of poly-hexanodioic acid hexylene glycol polyester is 820～1200.
7. according to the application of claim 1 preparation modified polyurethane hard bubble in exterior-wall heat insulation, comprise coating mortar, it is characterized in that sand-cement slurry mainly made by properties-correcting agent, fine sand, cement.
8. the application of modified polyurethane hard bubble according to claim 7 in exterior-wall heat insulation, the weight ratio that it is characterized in that properties-correcting agent, fine sand, cement is 1～2: 3～7: 1～3.
9. the application of modified polyurethane hard bubble according to claim 7 in exterior-wall heat insulation is characterized in that construction technology comprises the following steps:
(1) cleaning basic unit body of wall;
(2) to body of wall spraying modified polyurethane hard bubble, after spraying finishes, local levelling;
(3) brushing coating mortar;
(4) carry out the outer ornamental work of metope.
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| CNB2005100453680A CN100420704C (en) | 2005-12-16 | 2005-12-16 | Modified polyurethane hard bubble and its uses |
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| CNB2005100453680A CN100420704C (en) | 2005-12-16 | 2005-12-16 | Modified polyurethane hard bubble and its uses |
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| CN101845289A (en) * | 2010-06-01 | 2010-09-29 | 辽宁鼎力科技有限责任公司 | Double-component polyurethane foaming adhesive for attaching XPS and EPS walls and preparation method thereof |
| CN102101942A (en) * | 2009-12-16 | 2011-06-22 | 郭青 | Reinforced polyurethane rigid foam material and manufacturing method thereof |
| CN102181144A (en) * | 2011-01-31 | 2011-09-14 | 北京东方雨虹防水技术股份有限公司 | Spray rigid polyurethane foam heat insulation waterproof integrated material |
| CN102356108A (en) * | 2009-03-24 | 2012-02-15 | 陶氏环球技术有限责任公司 | Production of rigid polyurethane foams and use thereof |
| CN101250281B (en) * | 2007-02-24 | 2012-07-04 | 拜尔材料科学股份公司 | Method for producing polyurethane flexible foamed material with low bulk density |
| CN102558498A (en) * | 2012-01-04 | 2012-07-11 | 山西兆信生物科技有限公司 | Polyurethane reinforcing and filling materials for coal mine |
| CN105713505A (en) * | 2016-03-24 | 2016-06-29 | 安徽德全新型建材科技有限公司 | Noise-reducing and fireproof external wall panel |
| CN105713506A (en) * | 2016-03-24 | 2016-06-29 | 安徽德全新型建材科技有限公司 | High-temperature-resistant and fire-proof external wallboard |
| CN105820547A (en) * | 2016-03-24 | 2016-08-03 | 安徽德全新型建材科技有限公司 | Fireproof thermal insulation exterior wall board |
| CN105860814A (en) * | 2016-03-24 | 2016-08-17 | 安徽德全新型建材科技有限公司 | External wall panel with excellent fireproof performance |
| CN108299615A (en) * | 2018-02-05 | 2018-07-20 | 杨长文 | A kind of polyurethane foam particle |
| CN108559059A (en) * | 2018-05-14 | 2018-09-21 | 苏州健能新材料科技有限公司 | Polyurethane foams and preparation method thereof |
| CN109836556A (en) * | 2019-01-31 | 2019-06-04 | 四川大学 | A kind of low VOC polyurethane foam material and preparation method containing molysite |
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| CN1052486A (en) * | 1989-12-16 | 1991-06-26 | 广州市建筑材料工业研究所 | The preparation method of material to repair green hygienic ceramic utensils |
| CN1384145A (en) * | 2001-05-09 | 2002-12-11 | 上海凯耳新型建材有限公司 | Polyurethane for heat insulation in outer wall |
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- 2005-12-16 CN CNB2005100453680A patent/CN100420704C/en not_active Expired - Fee Related
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| CN101250281B (en) * | 2007-02-24 | 2012-07-04 | 拜尔材料科学股份公司 | Method for producing polyurethane flexible foamed material with low bulk density |
| CN102356108A (en) * | 2009-03-24 | 2012-02-15 | 陶氏环球技术有限责任公司 | Production of rigid polyurethane foams and use thereof |
| CN102101942B (en) * | 2009-12-16 | 2013-10-30 | 江苏建艺节能科技有限公司 | Reinforced polyurethane rigid foam material and manufacturing method thereof |
| CN102101942A (en) * | 2009-12-16 | 2011-06-22 | 郭青 | Reinforced polyurethane rigid foam material and manufacturing method thereof |
| CN101845289A (en) * | 2010-06-01 | 2010-09-29 | 辽宁鼎力科技有限责任公司 | Double-component polyurethane foaming adhesive for attaching XPS and EPS walls and preparation method thereof |
| CN102181144A (en) * | 2011-01-31 | 2011-09-14 | 北京东方雨虹防水技术股份有限公司 | Spray rigid polyurethane foam heat insulation waterproof integrated material |
| CN102558498A (en) * | 2012-01-04 | 2012-07-11 | 山西兆信生物科技有限公司 | Polyurethane reinforcing and filling materials for coal mine |
| CN105713505A (en) * | 2016-03-24 | 2016-06-29 | 安徽德全新型建材科技有限公司 | Noise-reducing and fireproof external wall panel |
| CN105713506A (en) * | 2016-03-24 | 2016-06-29 | 安徽德全新型建材科技有限公司 | High-temperature-resistant and fire-proof external wallboard |
| CN105820547A (en) * | 2016-03-24 | 2016-08-03 | 安徽德全新型建材科技有限公司 | Fireproof thermal insulation exterior wall board |
| CN105860814A (en) * | 2016-03-24 | 2016-08-17 | 安徽德全新型建材科技有限公司 | External wall panel with excellent fireproof performance |
| CN108299615A (en) * | 2018-02-05 | 2018-07-20 | 杨长文 | A kind of polyurethane foam particle |
| CN108299615B (en) * | 2018-02-05 | 2020-12-15 | 杨长文 | Polyurethane foaming particle |
| CN108559059A (en) * | 2018-05-14 | 2018-09-21 | 苏州健能新材料科技有限公司 | Polyurethane foams and preparation method thereof |
| CN109836556A (en) * | 2019-01-31 | 2019-06-04 | 四川大学 | A kind of low VOC polyurethane foam material and preparation method containing molysite |
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