CN101885856B - Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic - Google Patents
Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic Download PDFInfo
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- CN101885856B CN101885856B CN2010102251097A CN201010225109A CN101885856B CN 101885856 B CN101885856 B CN 101885856B CN 2010102251097 A CN2010102251097 A CN 2010102251097A CN 201010225109 A CN201010225109 A CN 201010225109A CN 101885856 B CN101885856 B CN 101885856B
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- terminated polyether
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Abstract
The invention discloses a method for preparing isocyanate terminated polyether/phenolic resin foamed plastic and belongs to the field of foam heat insulating materials. The method comprises the following steps of: adding a surfactant and a foaming agent into special expandable phenolic resin to form a component A; and uniformly mixing and stirring the component A and an isocyanate terminated polyether pre-polymer serving as a component B; pouring the mixture into a mold; and foaming and curing the mixture at normal temperature, wherein the mass ratio of -NCO contained in the isocyanate terminated polyether pre-polymer to the expandable phenolic resin is 0.1-0.6:1; the foaming agent is a physical foaming agent of which the boiling point is low; the -NCO group content of the isocyanate terminated polyether pre-polymer is between 18.5 and 19.5 mass percent; and the viscosity of the isocyanate terminated polyether pre-polymer is between 0.15 and 0.65 Pa.S at the temperature of 25 DEG C. The speed of the reaction of the phenolic resin and an isocyanate group is stable and foam density is appropriate (between 56 and 109 kg/m<3>) and can be adjusted through the using amount of the foaming agent.
Description
Technical field
The present invention is specifically related to that simple, workable, the no burn into of a kind of technology is heat-resisting, the pneumatogen that utilizes of not efflorescence, good toughness prepares the method for the two component system cellular insulants of isocyanate terminated polyether/phenolic resin, belongs to the cellular insulant field.
Background technology
Phenolic foamed plastics is aspect excellent characteristic such as low smokiness, hypotoxicity and dimensional stability during with its heat insulating ability, flame retardancy, burning; Come extremely to pay attention at recent two decades, extensively be used as [Wang Junxiao, Liu new people such as heat-insulating material, sound-proof material, wrapping material, building and ornament materials and high absorbency material; Pan Jiongxi; Wang Hongwu. sandwich sheet is with the research [J] of hard phenol formaldehyde foam performance. modern plastics processed and applied, 2005,17 (1): 29-31; Ma Xiaoxiong, He Bin, Hu Xinyuan, Yang Yong. anti-accident tr is with phenol formaldehyde foam preparation and performance evaluation [J] thereof. engineering plastics, 2008,36 (7): 60-63; Liu new people, Guo Qingjie, Cao Changqing, Wang Zhiqi. phenolic foamed plastics preparation for building and performance study [J]. Chinese plastics, 2006,20 (8): 47-50].But resol self has the constructional feature of many phenyl ring, makes it show big, the easy atomizing shortcoming of fragility, and this has greatly suppressed the development of phenolic foamed plastics.Therefore, improve the toughness of resol and the big focus that easy powder phenomenon-tion becomes domestic and international research.Phenol formaldehyde foam toughness reinforcing, can realize through following two kinds of approach: a kind of is to add outer toughner in system, and Guo Jintang etc. are through adding properties-correcting agent polyvinyl butyral acetal; Phenol formaldehyde foam is carried out blending and modifying; It is big that the phenol formaldehyde foam flexural strength that obtains obviously becomes, toughness increase to some extent (Guo Jintang, Wang Xinying. fire-retardant and the Research on Toughening [J] of resol. combustion science is with technological; 2003,87 (4): 34-37); The bright grade of mark has been studied the toughening modifying of PVC/NBR-40 thermoplastic elastomer to phenolic foamed plastics; The foamy compressive strength increases; (mark is bright but the foam thermal conductivity significantly raises thereupon; The research [J] of thunder Weihe beautiful woman .PVC/NBR-40 thermoplastic elastomer toughening phenolic foamed plastics. Shenyang Institute of Aeronautical Engineering?'s journal, 1998,15 (1): 25-28).Another kind is chemical toughening modifying, and Li Shaotang etc. adopt cashew nut oil and resol copolymerization, and the preparation phenol formaldehyde foam, the foam density 100kg/m after the modification
3, tensile strength and elongation at break increase, but the foamy oxygen index is reduced to 35.1 by 40.8; And the reduction of foam size stability (Zhou Li paints for Li Shaotang, Jiang Qiuyun. cashew nut oil plasticizing phenol formaldehyde and foam thereof [J]. and glass reinforced plastic/matrix material; 2006, (2): 37-39); Tall winter equality adopts the epoxy resin modification phenol formaldehyde foam, and the phenolic foam board amount of deflection of preparation is brought up to (Qiao Dongping, Li Weimin more than the 30mm by the 8.2mm before not toughness reinforcing; Refined duckweed; Hear eastwards, fourth is sharp, Xiu-Li Han. the research [J] of flexible-epoxy toughening metlbond foam plastics. and the Henan chemical industry; 2006, (23): 22-23); Often harbour the amorous thoughts of spring etc. ROHM positive butyl ester toughening modifying resol and phenol formaldehyde foam are studied; The foamy compressive strength is increased to 0.4MPa by 0.2MPa and [often harbours the amorous thoughts of spring; Lv Tongjian; Yang Yingying. the research [J] of the positive butyl ester toughening metlbond foam of ROHM plastics. Chinese plastics, 2005,19 (12): 53-56; Often harbour the amorous thoughts of spring the flat chastity of learning, the synthetic and Study on Compatibility [J] of Qiu Xing space .PF/PnBA. polymer material science and engineering, 1993,9 (2): 33-37; Often harbour the amorous thoughts of spring champion Li. the preparation method of phenolic foamed plastics [P]. Chinese patent: 1085576,1994-04-20].Above-mentioned research has all obtained certain toughening effect, but all can bring the consistency of properties-correcting agent and phenolic resin as matrix resin poor, and system viscosity is too high, causes the foams expansion ratio low, and has influenced the negative effect of the curing reaction of resol.
Adopting urethane and polyurethane prepolymer modified phenolic foam is a kind of effective method for toughening; Because isocyanate terminated basic polyether prepolymer has good chain kindliness; End group can form cross-linked network with reactive modified phenolic resin simultaneously, causes a lot of scholars' concern in recent years.Complex systems such as usefulness resoles such as Zhang Liucheng, polyethers, isocyanate terminated base polyurethane prepolymer, tosic acid, phosphoric acid, trolamine foam; Foamy compressive strength (the Zhang Liucheng that increases; Platform can literary composition. the development of phenolic aldehyde-PUR syntactic foamed plastics [J]. and plastic engineering; 1991, (1): 19-23); Zhou Chunhua etc. add 8% base polyurethane prepolymer for use as in phenolic resin system; Prepare foam with acid as solidifying agent; Foamy shock strength and compressive strength improved 50% and 96.5% respectively (Zhou Chunhua, Liu Wei separate podocarpus nagi etc. the research of phenolic resin foam plastics toughening modifying [J]. University Of Ji'nan's journal; 2004, (18): 243-245).This research department once adopted polyurethane prepolymer toughening modifying phenol formaldehyde foam; When the massfraction of prepolymer was 3%, it is unmodified 40% that modification foamy efflorescence degree is merely, and the foam rebound degree is greater than 60% (Cheng Jue; Liang Mingli; Golden light is safe. Phenolic Foam Modified by Urethane Oligomer Study of Brittleness [J]. and plastics industry, 2004, (32): 7-9).Above-mentioned study on the modification all is employed in the method for adding polyurethane prepolymer in the system of resol/acid; Though all obtained certain toughening effect, the problem of polyurethane prepolymer and resol consistency difference still exists, and the addition of permission seldom; And the multiple active hydrogen substance that contains is arranged in the phenolic resin system; Complicated with isocyanate reaction, so polyurethane prepolymer do not have the effect that improves curing cross-linked density, the foamy powder phenomenon-tion improved little.
Anthony Joseph Papa etc. has synthesized-the end capped polyurethane prepolymer of NCO with the phosphorated polyether glycol; Foam with the resol blend again; Improved toughness (the Anthony J P of phenol formaldehyde foam effectively; Richard L R, Frank E C.phenolic foam modified with phosphorus-containingisocyanate-terminated [P] .USP4119584.1978-10-10); This research department adopt polyurethane prepolymer and alkalescent phenol resin pair component systems prepared novel foam material (Cheng Jue, model is brave, Yang Wantai. a kind of preparation method of polyurethane/phenolic aldehyde foam thermal insulation material. Chinese patent, 200810105000.2009-10-28).Different with interpolation modification in the past; This method of modifying is to replace the solidifying agent of acid as resol with polyurethane prepolymer; Form two component systems with resol; The consistency of the two is good, side reaction is few, polyurethane prepolymer consumption big (30%-60%), and activity of cross-linking reaction is high, cross-linked network is complete, obtains a kind of toughness, non-chalking novel foam body.But this system adopts small amount of acid to make whipping agent, causes the curing molding excessive velocities, and density foam is high, is not easy to regulate.
Summary of the invention
The object of the invention provides the method that a kind of pneumatogen prepares isocyanate terminated polyether/phenolic resin foamed plastic; Adopt isocyanate terminated polyether (polyurethane prepolymer) to replace traditional solidifying agent (acid); Form two component systems with expandable phenolic resin and prepare a kind of brand-new foams, adopt pneumatogen in the system, do not re-use organic/inorganic acid as whipping agent; Side reaction is few, and reaction is control easily; Adopt extraordinary expandable phenolic resin, solved the problem of the consistency difference of polyurethane prepolymer and bodily form resol, and this resol and isocyanate groups speed of response are steady, the density foam of preparation is moderate, at 56kg/m
3-109kg/m
3Between, foams have good temperature tolerance, toughness and non-chalking characteristic.
The preparation method of a kind of isocyanate terminated polyether/phenolic resin foamed plastic of the present invention is characterized in that, may further comprise the steps:
1) in extraordinary expandable phenolic resin, add tensio-active agent, whipping agent, stir, form component A, wherein, dosage of surfactant is the 4%-12.5% of expandable phenolic resin quality, and foaming agent consumption is the 1-10% of expandable phenolic resin quality;
2) take by weighing the isocyanate terminated polyether performed polymer, as B component;
3) component A and B are mixed and stir 10s-20s and stir; Pour mould into, foaming at normal temp solidifies, and makes the isocyanate terminated polyether/phenolic resin cellular insulant; Wherein, The quality of contained in the isocyanate terminated polyether prepolymer-NCO and the mass ratio of expandable phenolic resin are 0.1-0.6: 1, and whole foaming process at room temperature carries out, and operating procedure is simple.
Wherein, the extraordinary expandable phenolic resin described in the step 1) is alkaline expandable phenolic resin, and water cut is 3.5%-6.7%, and viscosity is 0.9Pa.S-4.8Pa.S, 25 ℃.
Tensio-active agent described in the step 1) is one or several in tween series or the silicone oil series, and the preferable amount of tensio-active agent is the 8%-10% of expandable phenolic resin quality.
Whipping agent described in the step 1) is a lower boiling class pneumatogen; Preferred HFCs (hydrogen fluorohydrocarbon), pentane class, liquid CO
2In one or several; Preferable amount is the 1.5%-6.5% of expandable phenolic resin quality.Come the density of control foam through the adjusting foaming agent consumption.
Step 2) the isocyanate terminated polyether prepolymer described in is that polyethers propylene oxide glycol (PPG1000) and '-diphenylmethane diisocyanate (MDI) adopt ordinary method preparation or commercially available all can by a certain percentage;-NCO group content is 18.5%-19.5% (massfraction), and viscosity is 0.15Pa.S-0.65Pa.S (25 ℃).
In the isocyanate terminated polyether/phenolic resin cellular insulant described in the step 3), in the adding system-the preferred 0.2-0.5 of mass ratio of NCO and resol: 1.
The present invention has following beneficial effect:
1) the prepared isocyanate terminated polyether/phenolic resin cellular insulant of the present invention; Combine phenol formaldehyde foam and polyurethane foam advantage separately; Both solve the poor toughness of phenol formaldehyde foam, easy efflorescence shortcoming, also improved the shortcoming of the poor heat resistance of polyurethane foam simultaneously.
2) the present invention adopts extraordinary expandable phenolic resin; Compare with common resol; This expandable phenolic resin adopts basic catalyst catalysis, and water cut is low, viscosity is low, holds fully mutually with polyurethane prepolymer; Do not have agglomeration to occur, solved the shortcoming of resol and polyurethane prepolymer consistency difference.
3) adopt the pneumatogen foaming, resol and isocyanate groups speed of response are steady, the moderate (56kg/m of density foam
3-109kg/m
3), can regulate through foaming agent consumption.
4) component A and B mixed foaming stage all carry out at normal temperatures, and operating procedure is simple, need not other means such as heating, interpolation auxiliary agent, and contaminative is little
5) the isocyanate terminated polyether/phenolic resin lagging material of preparation has formed the whole network structure, and volume stability is good.
Embodiment
Alkalescence expandable phenolic resin (commercially available), water cut is 3.5%-6.7%, and viscosity is 0.9Pa.S-4.8Pa.S (25 ℃), and mean polymerisation degree is 2-3; Isocyanate terminated polyether prepolymer (commercially available) ,-NCO group content are 18.5%-19.5% (massfraction), and viscosity is 0.15Pa.S-0.65Pa.S (25 ℃).
Umber described in the following embodiment is mass fraction.
Embodiment 1
1) take by weighing 20 parts of alkaline expandable phenolic resins (water cut 4.9%, viscosity are 2.8Pa.S, 25 ℃) in the container, add 2.0 parts of polysorbate60s successively, 0.3 part of HFCs mixes and stirs 30s, obtains component A;
2) take by weighing 48 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 10s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 109.24Kg/m
3, flexural strain is 21% when reaching yield-point, and maximum stress in bend is 0.42MPa, and it is 2.47% that 150 ℃ of environment toast 2 hours mass loss rates down.
Embodiment 2
1) take by weighing 20 parts of alkaline expandable phenolic resins (water cut 3.5%, viscosity are 0.9Pa.S, 25 ℃) in the container, add 1.8 parts of tween 80s successively, 0.5 part of pentamethylene mixes and stirs 45s, makes it to mix, and obtains component A;
2) take by weighing 40 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 15s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 89.11Kg/m
3, flexural strain is 22% when reaching yield-point, and maximum deflection should be 0.35MPa, and it is 3.12% that 150 ℃ of environment toast 2 hours mass loss rates down.
Embodiment 3
1) take by weighing 40 parts of alkaline expandable phenolic resins (water cut 6.7%, viscosity are 4.8Pa.S, 25 ℃) in the container, add 4.5 parts of silicone oil successively, 1.5 parts of Skellysolve As mix and stir 65s, make it to mix, and obtain component A;
2) take by weighing 78 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 12s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 80.37Kg/m
3, flexural strain is 25% when reaching yield-point, and maximum stress in bend is 0.32MPa, and it is 3.91% that 150 ℃ of environment toast 2 hours mass loss rates down.
Embodiment 4
1) take by weighing 10 parts of alkaline expandable phenolic resins (water cut 5.5%, viscosity are 3.2Pa.S, 25 ℃) in the container, add 1 part of silicone oil successively, 0.7 part of pentamethylene mixes and stirs 50s, makes it to mix, and obtains component A;
2) take by weighing 23 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 16s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 56.42Kg/m
3, flexural strain is 26% when reaching yield-point, and maximum stress in bend is 0.19MPa, and it is 4.98% that 150 ℃ of environment toast 2 hours mass loss rates down.
Embodiment 5
1) takes by weighing 30 parts of alkaline expandable phenolic resins (water cut 4.6%, viscosity are 2.4Pa.S, 25 ℃) in the container, add 3.5 parts of polysorbate60s successively, 1.6 parts of liquid CO
2, mix and stir 58s, make it to mix, obtain component A;
2) take by weighing 57 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 17s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 62.89Kg/m
3, flexural strain is 29% when reaching yield-point, and maximum stress in bend is 0.23MPa, and it is 4.63% that 150 ℃ of environment toast 2 hours mass loss rates down.
Embodiment 6
1) take by weighing 20 parts of alkaline expandable phenolic resins (water cut 4.0%, viscosity are 1.6Pa.S, 25 ℃) in the container, add 2.5 parts of tween 80s successively, 0.5 part of HFCs mixes and stirs 34s, makes it to mix, and obtains component A;
2) take by weighing 49 parts of isocyanate terminated polyether prepolymers, as B component;
3) B component is poured among the component A, mechanical stirring 18s pours in the mould and foams, and obtains the isocyanate terminated polyether/phenolic resin cellular insulant.
The foam that obtains is evenly fine and close, not efflorescence of foam surface, and volume stability is good; Foam densities is 78.26Kg/m
3, flexural strain is 24% when reaching yield-point, and maximum stress in bend is 0.29MPa, and it is 3.35% that 150 ℃ of environment toast 2 hours mass loss rates down.
Claims (2)
1. the preparation method of an isocyanate terminated polyether/phenolic resin foamed plastic is characterized in that, may further comprise the steps:
1) in extraordinary expandable phenolic resin, adds tensio-active agent, whipping agent, stir, form component A;
2) take by weighing the isocyanate terminated polyether performed polymer, as B component;
3) component A and B are mixed and stir 10s-20s and stir; Pour mould into, foaming at normal temp solidifies, and makes the isocyanate terminated polyether/phenolic resin cellular insulant; Wherein, the mass ratio of the quality of contained-NCO and expandable phenolic resin is 0.1-0.6 in the isocyanate terminated polyether prepolymer: 1;
Wherein, the extraordinary expandable phenolic resin described in the step 1) is alkaline expandable phenolic resin, and water cut is 3.5%-6.7%, and viscosity is 0.9Pa.S-4.8Pa.S, 25 ℃;
Step 2) the isocyanate terminated polyether prepolymer described in is to be prepared by polyethers propylene oxide glycol PPG1000 and '-diphenylmethane diisocyanate (MDI), and-NCO group mass content is 18.5%-19.5%, and viscosity is 0.15Pa.S-0.65Pa.S, 25 ℃;
Described whipping agent is HFCs, pentane class, liquid CO
2In one or several, consumption is the 1.5%-6.5% of expandable phenolic resin quality;
Tensio-active agent is one or several in tween series or the silicone oil series, and consumption is the 8-10% of expandable phenolic resin quality.
2. the preparation method of a kind of isocyanate terminated polyether/phenolic resin foamed plastic of claim 1; It is characterized in that; In the isocyanate terminated polyether/phenolic resin cellular insulant described in the step 3), in the adding system-the preferred 0.2-0.5 of mass ratio of NCO and resol: 1.
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| CN102731961B (en) * | 2011-10-18 | 2014-03-19 | 蓝云飞 | Phenolic foam composite insulation material and production method thereof |
| CN103012712B (en) * | 2012-12-25 | 2014-11-05 | 河北同成科技股份有限公司 | Method for preparing organic and inorganic hybridization modified polyurethane chemical grouting material |
| CN104086794A (en) * | 2014-07-01 | 2014-10-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of polyurethane prepolymer-toughened modified phenolic foam plastic |
| CN105348485B (en) * | 2015-11-26 | 2019-05-14 | 华南理工大学 | Mixed and modified water dispersive polyisocyanate curing agent of ketone resin/hydrophilic polyether and the preparation method and application thereof |
| CN105694357B (en) * | 2016-01-17 | 2018-01-09 | 浙江省林业科学研究院 | The preparation method of polyether-modified biomass resin foamed rapidly at normal temperature |
| CN105601856B (en) * | 2016-02-15 | 2018-09-28 | 安徽美克思科技有限公司 | A kind of preparation method of isocyanate-modified phenolic resin foam |
| CN106279611A (en) * | 2016-08-15 | 2017-01-04 | 黄宝兴 | The preparation method of phenolic urethanes cellular insulant |
| CN106317766B (en) * | 2016-09-08 | 2018-05-15 | 沈阳化工大学 | A kind of resin modified phenolic resin foam preparation method of cyanic acid ester group |
| CN110372990A (en) * | 2019-07-17 | 2019-10-25 | 江苏中电创达建设装备科技有限公司 | A kind of Phonelic foam sandwich board preparation method and the battenboard with this method production |
| CN112940444B (en) * | 2021-01-26 | 2023-10-27 | 黄山锦绣建设工程有限公司 | Energy-saving environment-friendly building curtain wall and installation method thereof |
| CN112898730A (en) * | 2021-01-27 | 2021-06-04 | 彭圳凡 | Heat insulation material for building exterior wall and preparation method thereof |
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| JP2003246673A (en) * | 2002-02-27 | 2003-09-02 | Nisshinbo Ind Inc | Glassy carbon foam and production method thereof |
| CN101565541B (en) * | 2008-04-25 | 2010-12-08 | 北京化工大学 | Method for preparing polyurethane/phenolic aldehyde foam thermal insulation material |
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