CN101565541A - Method for preparing polyurethane/phenolic aldehyde foam thermal insulation material - Google Patents
Method for preparing polyurethane/phenolic aldehyde foam thermal insulation material Download PDFInfo
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- CN101565541A CN101565541A CNA2008101050002A CN200810105000A CN101565541A CN 101565541 A CN101565541 A CN 101565541A CN A2008101050002 A CNA2008101050002 A CN A2008101050002A CN 200810105000 A CN200810105000 A CN 200810105000A CN 101565541 A CN101565541 A CN 101565541A
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Abstract
The invention provides a method for preparing a polyurethane/phenolic aldehyde foam thermal insulation material and belongs to the field of the foam thermal insulation material. The invention aims to solve the problems of poor fire resistant property and strong brittleness in the prior polyurethane foam and phenolic aldehyde foam respectively. The method comprises the following steps that: a prepolymer of alkali phenolic resin, isocyanate and polyether glycol are used as raw materials, and the prepolymer is added with a surfactant and a foaming agent for free foaming at room temperature to prepare the polyurethane/phenolic aldehyde foam thermal insulation material, wherein the weight ratio of the isocyanate to the alkali phenolic resin is 3-1:1, the consumption of the polyether glycol is 20 to 50 percent of the weight of the isocyanate, the consumption of the surface active agent is 4 to 10 percent of the weight of the alkali phenolic resin, and the consumption of the foaming agent is 1 to 10 percent of the weight of the alkali phenolic resin. The method has the advantages of the suitability for places where the foaming-in-place insulation is necessary, stable process reaction, good operability and easily bought raw materials; and the foam thermal insulation material prepared by the method has the advantages of little surface pulverization, good toughness, good fire resistant property, and the like.
Description
Technical field
The invention belongs to the cellular insulant field, be specifically related to that a kind of reaction efficiency height, technology are simple, workable, the preparation method of the polyurethane/phenolic aldehyde foam thermal insulation material that pollutes little, good toughness.
Background technology
Resol is the general designation of the resin that forms with phenol and aldehyde polycondensation, as one of three big synthetic thermosetting resins, is the synthetic resins kind of developing and realize suitability for industrialized production the earliest.From its originator U.S. scientist Dr.Leo Backeland in 1905 resol is dropped into for the first time and to commercially produce, existing so far centenary history.Because its starting material source is wider, production technique and equipment are not too complicated, and product performance are good, obtained widespread use in many productions and sphere of life.For example can prepare coating, tackiness agent, acid resistant adhesive mortar, phenoplast, phenol formaldehyde foam etc. [the inscription on ancient bronze objects root of Dahurian angelica. molding sand chemistry [M]. Shanghai: Shanghai science tech publishing house, 1985; Zhu Yongmao, Yin Yichu. phenolic foams and sandwich sheet development progress [J] thereof. thermosetting resin, 2003,18 (5): 30-32; Yin Yichu. the most advanced and sophisticated matrix material of 21st century and processed and applied technology [J]. macromolecular material, 1992,4:32-35].Also just because of this, it causes that people extensively pay attention to and further investigation [Drumm MF, LeBlanc JR, Solomon DH.Stepgrowth polymerizations[M] .3rd ed.New York:Marcel Dekker, 1972; Solomon DH.The chemistry of organic film formers[M] .NewYork:Krieger, 1977; Knop A, Pilato LA.Phenolic resins[M] .Berlin:Springer, 1985].Though phenolic foamed plastics is used for structural material satisfactory performance is arranged, good as dimensional stability, have flame retardant resistance, a foam density wide ranges etc., but the characteristics of its crisp brittleness are unsatisfactory as heat preserving and insulating material, therefore suppressed the development of phenolic foamed plastics.
In recent years, because the premium properties of polyurethane material makes its development very rapid, application surface progressively enlarges.The same with other organic polymer material, urethane is the stronger polymkeric substance of a kind of combustibility, porous plastics particularly, density is little, specific surface area is big, heat insulating ability is good, but combustion problem hinders polyurethane material development [Zhu Guoqiang, Dong Ming, Gu Zhihong, the flame retardant resistance Development of A Soft Polyurethane Foamed Plastic, polyurethane industrial, 1996 (1); Xu Hongyan, Chen Su, the applied research of JS-N 350 polyether glycols in high resilience cold-curing foam, Nanjing petrochemical complex, 1989 (6); Su Dongliang, Li Haizhou, Huang Rushen, Qi Tianyou, flexible urethane foam Study on Technology, fire prevention and product information, 1997 (12)].
Main in toughening metlbond foam making of mentioning among the Chinese patent CN200310113967 and the U.S. Pat 6476090 " phenolic foam " by whipping agent, auxiliary agent improvement foam; Mainly by cashew nut oil modified foaming properties, the processing of foam efflorescence and phenol waste water is improved Chinese patent CN200610024607.9, but the tough property improvement of foam is general.
Bibliographical information is arranged by adopting the method for polyurethane-modified phenol formaldehyde foam, but the add-on of its elastic polyurethane performed polymer only is 3%, and urethane can not well dissolve each other with resol (Cheng Jue. Liang Mingli. Golden Customs Thailand, the research of Phenolic Foam Modified by Urethane Oligomer fragility rhythm, plastics industry, the 32nd the 1st phase of volume, in January, 2004).
Summary of the invention
The object of the present invention is to provide that a kind of reaction efficiency height, technology are simple, workable, the preparation method of the polyurethane-modified phenolic aldehyde foam thermal insulation material that pollutes little, good toughness.The invention solves the mutual solubility of urethane and phenolic aldehyde, improved the add-on of elastic polyurethane performed polymer, formed mutual crosslinked inierpeneirating network structure.
Method provided by the present invention is achieved through the following technical solutions:
1) add tensio-active agent, whipping agent in alkalescent phenol resin, stirring forms component A, and wherein, dosage of surfactant is 4～10% of an alkalescent phenol resin quality, and foaming agent consumption is 1～10% of an alkalescent phenol resin quality;
2) take by weighing isocyanic ester, add polyether glycol and stir, under 60～80 ℃, reaction 0.5～1h, wherein, the polyether glycol consumption is 20～50% of an isocyanic ester quality, forms end isocyanato elasticity performed polymer, obtains B component;
3) in mould component A and B are mixed, foam, make polyurethane/phenolic aldehyde foam thermal insulation material, wherein, the mass ratio of isocyanic ester and resol is 3～1: 1, and whole foaming process at room temperature carries out, and is easy and simple to handle, quick.
Wherein, the tensio-active agent described in the step 1) is one or several in tween series or the silicone oil series, and the consumption of tensio-active agent is preferably 5～7% of alkalescent phenol resin quality.
Whipping agent described in the step 1) is ether, water, alcohol or sour; In preferred sherwood oil, water, ethanol, ethylene glycol, acetate or the formic acid one or several; Preferable amount is 1～6% of an alkalescent phenol resin quality.Come the density of control foam by the adjusting foaming agent consumption.
Step 2) isocyanic ester described in is TDI (tolylene diisocyanate), MDI ('-diphenylmethane diisocyanate), one or more of PAPI (poly-methyl polyphenyl isocyanic ester).
Step 2) polyether glycol described in is one or more in the polyoxyethylene glycol series, and preferable amount is 30～40% of an isocyanic ester quality.
Adopt isocyanic ester and polyether glycol pre-polymerization, form the end isocyano (NCO) prepolymer, then with resol in the crisscross crosslinked structure of methylol reaction formation.
Step 2) reaction conditions in is preferable over 70～75 ℃ of reaction 0.6～0.8h.
In the polyurethane/phenolic aldehyde foam thermal insulation material described in the step 3), preferred 3: 2 of the mass ratio of isocyanic ester and resol.
The present invention has following beneficial effect:
1) the prepared polyurethane/phenolic aldehyde foam thermal insulation material of the present invention combines phenol formaldehyde foam and polyurethane foam advantage separately, has both solved the crisp brittleness shortcoming of phenol formaldehyde foam, has also improved the flammable shortcoming of polyurethane foam simultaneously, has played fire retardation.
2) the present invention adopts alkalescent phenol resin, compares with common phenolic aldehyde, and alkaline phenol formaldehyde and urethane melt fully mutually, does not have agglomeration to occur, and has solved the shortcoming of resol and urethane consistency difference.
3) component A and B mixed foaming stage all carry out at normal temperatures, and be easy and simple to handle, need not other means such as heating, interpolation auxiliary agent, and contaminative is little, and the polyurethane/phenolic aldehyde foam thermal insulation material of preparation mixes, and no noted phase separation phenomena has formed unified foam structure.
Embodiment
Alkalescent phenol resin is the commercial goods, and viscosity (25 ℃) is 100～2000mpa.s.
Umber described in the following embodiment is total mass number.
Embodiment 1
1) take by weighing 20 parts of resol in the container, add 2.0 parts of silicone oil (DC-193) successively, 1.2 parts of acetate mix and stir 1min, make it to mix, and obtain component A;
2) take by weighing 30 parts of PAPI in the container, add 11 parts of polyoxyethylene glycol-400, stir, thorough mixing, 70 ℃ are reacted 48min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 680cm
3, froth quality: 35.719g, foam density: 0.0525g/cm
3
Embodiment 2
1) take by weighing 10 parts of resol in the container, add 0.7 part of Tween-60 successively, 0.6 part of ethylene glycol and alcoholic acid mixed solution (the two mass ratio 3: 2) mix and stir 1min, make it to mix, and obtain component A;
2) take by weighing 30 parts of MDI in the container, add 6 parts of polyoxyethylene glycol-400, stir, thorough mixing, 80 ℃ are reacted 60min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 472cm
3, froth quality: 25.297g, foam density: 0.0536g/cm
3
Embodiment 3
1) take by weighing 20 parts of resol in the container, add 1.0 parts of silicone oil (DC-193) successively, the mixed solution (the two mass ratio 1: 1) of 0.2 part of acetate and sherwood oil mixes and stirs 1min, makes it to mix, and obtains component A;
2) take by weighing 30 parts of TDI in the container, add 11 parts of polyoxyethylene glycol-400, stir, thorough mixing, 75 ℃ are reacted 36min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 268cm
3, froth quality: 36.054g, foam density: 0.1345g/cm
3
Embodiment 4
1) take by weighing 15 parts of resol in the container, add 1.2 parts of silicone oil (DC-193) successively, the mixed solution (the two mass ratio 1: 3) of 0.5 part of water and formic acid mixes and stirs 1min, makes it to mix, and obtains component A;
2) take by weighing 30 parts of PAPI in the container, add 15 parts of polyoxyethylene glycol-400, stir, thorough mixing, 60 ℃ are reacted 30min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 297cm
3, froth quality: 30.812g, foam density: 0.1037g/cm
3
Embodiment 5
1) take by weighing 20 parts of resol in the container, add 0.8 part of silicone oil (DC-193) successively, 2.0 parts of sherwood oils and ethylene glycol mixtures (the two mass ratio 1: 3) are mixed and are stirred 1min, make it to mix, and obtain component A;
2) take by weighing 30 parts of PAPI in the container, add 11 parts of polyoxyethylene glycol-200, stir, thorough mixing, 73 ℃ are reacted 45min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 736cm
3, froth quality: 35.152g, foam density: 0.0478g/cm
3
Embodiment 6
1) take by weighing 30 parts of resol in the container, add 1.2 parts of silicone oil (DC-193) successively, the mixed solution (the two mass ratio 3: 2) of 0.6 part of ethanol and acetate mixes and stirs 1min, makes it to mix, and obtains component A;
2) take by weighing 30 parts of PAPI in the container, add 11 parts of polyoxyethylene glycol-200, stir, thorough mixing, 73 ℃ are reacted 45min down, obtain B component;
3) B component is poured among the component A, stirred rapidly, pour in the mould and foam, obtain polyurethane/phenolic aldehyde foam thermal insulation material.
The foam that obtains is evenly fine and close, and phenolic aldehyde urethane does not have phenomenon of phase separation; Foam materials volume: 313cm
3, froth quality: 43.537g, foam density: 0.1391g/cm
3
Claims (11)
1, a kind of preparation method of polyurethane/phenolic aldehyde foam thermal insulation material is characterized in that, may further comprise the steps:
1) add tensio-active agent, whipping agent in alkalescent phenol resin, stirring forms component A, and wherein, dosage of surfactant is 4～10% of an alkalescent phenol resin quality, and foaming agent consumption is 1～10% of an alkalescent phenol resin quality;
2) take by weighing isocyanic ester, add polyether glycol and stir, under 60～80 ℃, reaction 0.5～1h, wherein, the polyether glycol consumption is 20～50% of an isocyanic ester quality, forms end isocyanato elasticity performed polymer, obtains B component;
3) in mould component A and B are mixed, under room temperature, foam, make polyurethane/phenolic aldehyde foam thermal insulation material, wherein, the mass ratio of isocyanic ester and alkalescent phenol resin is 3～1: 1.
2, method according to claim 1 is characterized in that, the tensio-active agent described in the step 1) is one or several in tween series or the silicone oil series.
3, method according to claim 1 is characterized in that, the consumption of tensio-active agent is 5～7% of an alkalescent phenol resin quality in the step 1).
4, method according to claim 1 is characterized in that, the whipping agent described in the step 1) is ether, water, alcohol or sour.
5, method according to claim 4 is characterized in that, described whipping agent is one or several in sherwood oil, water, ethanol, ethylene glycol, acetate or the formic acid.
6, method according to claim 1 is characterized in that, the consumption of the whipping agent described in the step 1) is 1～6% of an alkalescent phenol resin quality.
7, method according to claim 1 is characterized in that step 2) described in isocyanic ester be among TDI, MDI or the PAPI one or more.
8, method according to claim 1 is characterized in that step 2) described in polyether glycol be in the polyoxyethylene glycol series one or more.
9, method according to claim 1 is characterized in that step 2) in the consumption of polyether glycol be 30～40% of isocyanic ester quality.
10, method according to claim 1 is characterized in that step 2) in isocyanic ester and polyether glycol in 70～75 ℃, reaction 0.6～0.8h forms B component.
11, method according to claim 1 is characterized in that, in the polyurethane/phenolic aldehyde foam thermal insulation material described in the step 3), the mass ratio of isocyanic ester and resol is 3: 2.
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| CN101831168A (en) * | 2010-05-14 | 2010-09-15 | 上海克络蒂材料科技发展有限公司 | Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof |
| CN101851993A (en) * | 2010-05-14 | 2010-10-06 | 上海克络蒂材料科技发展有限公司 | Fireproof flame-retardant polyurethane external wall thermal-insulation system material |
| CN101885856A (en) * | 2010-07-02 | 2010-11-17 | 北京化工大学 | Method for preparing isocyanate terminated polyether/phenolic resin foamed plastic |
| CN102152561A (en) * | 2010-12-06 | 2011-08-17 | 上海万国科技发展有限公司 | Phenolic modified polyurethane polyisocyanurate PIR energy-saving insulation board |
| CN102504190A (en) * | 2011-12-05 | 2012-06-20 | 广州市海珥玛植物油脂有限公司 | Method for producing flame-retardant modified phenolic foam plastics from waste oil and slop oil |
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| CN101831168A (en) * | 2010-05-14 | 2010-09-15 | 上海克络蒂材料科技发展有限公司 | Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof |
| CN101851993A (en) * | 2010-05-14 | 2010-10-06 | 上海克络蒂材料科技发展有限公司 | Fireproof flame-retardant polyurethane external wall thermal-insulation system material |
| CN101831168B (en) * | 2010-05-14 | 2012-01-25 | 上海克络蒂材料科技发展有限公司 | Polyurethane rigid foam exterior wall thermal insulation material with high flame retardancy and preparation method thereof |
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| CN102152561A (en) * | 2010-12-06 | 2011-08-17 | 上海万国科技发展有限公司 | Phenolic modified polyurethane polyisocyanurate PIR energy-saving insulation board |
| CN102504190A (en) * | 2011-12-05 | 2012-06-20 | 广州市海珥玛植物油脂有限公司 | Method for producing flame-retardant modified phenolic foam plastics from waste oil and slop oil |
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| CN104403263A (en) * | 2014-11-17 | 2015-03-11 | 锦州市好为尔保温材料有限公司 | Toughened and reinforced phenolic foam plate |
| CN104403263B (en) * | 2014-11-17 | 2016-07-06 | 锦州市好为尔保温材料有限公司 | A kind of toughness reinforcing reinforced phenolic foam board |
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| CN110156946A (en) * | 2019-05-30 | 2019-08-23 | 哈尔滨工业大学 | A kind of shape memory phenolic resin and preparation 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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