CN103467701B - Polyurethane heat insulation foaming material and preparation method thereof - Google Patents
Polyurethane heat insulation foaming material and preparation method thereof Download PDFInfo
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- CN103467701B CN103467701B CN201310415709.3A CN201310415709A CN103467701B CN 103467701 B CN103467701 B CN 103467701B CN 201310415709 A CN201310415709 A CN 201310415709A CN 103467701 B CN103467701 B CN 103467701B
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Abstract
The invention discloses a polyurethane heat insulation foaming material and a preparation method thereof. The polyurethane heat insulation foaming material comprises the following components in parts by weight: 100 parts of polyether polyol, 150-170 parts of polymethylene polyphenyl isocyanate, 5-30 parts of expanded perlite, 20-40 parts of a physical foaming agent, 10-15 parts of a flame retardant, 1-3 parts of a catalyst and 1.5-10 parts of a foam stabilizer. The density of hard polyurethane foams prepared by the preparation method is smaller than 65Kg/m<3>, the thermal conductivity is smaller than 21mW/m.K, the compressive strength is greater than 0.42MPa, the compression modulus is greater than 14MPa, and the oxygen index is more than or equal to 23, so that the polyurethane heat insulation foaming material is suitable for the field of heat insulation.
Description
Technical field
The invention belongs to polyurethane material technical field, particularly relate to a kind of polyurethane adiabatic heat-insulation foam material and preparation method thereof.
Background technology
Rigid polyurethane foam, because having lower thermal conductivity, has become irreplaceable heat-insulation material now, has been widely used in the fields such as building, space flight and aviation, communications and transportation, chemical industry.
Along with CFCs(and fluorochlorohydrocarbon) the prohibitting the use of whipping agent, HCFCs(and hydrogen fluorochlorohydrocarbon) whipping agent restriction use, the whipping agent of zero odp (i.e. Ozone Depression Potential ozone depletion potential) becomes study hotspot, and the whipping agent of conventional zero odp is as water, supercritical CO
2, pentane class and HFCs etc.
The shortcoming of pentane foaming agent is inflammable, can blast under certain condition with the mixture of air, so need to increase safety features during preparation, equipment cost is higher.In addition, a gas phase thermal conductivity ratio HCFC-141b(i.e. fluorine ethylene dichloride of pentane) high, to polyurethane foam, there is certain swelling action.In order to reach required intensity and insulativity, the density of the polyurethane foam prepared as whipping agent with pentane is usually than with CFC-11(and trichlorofluoromethane) system is that the density of polyurethane foam prepared by whipping agent is high by about 10%, and the polyurethane foam prepared as whipping agent with pentane is poorly soluble in polyether glycol.Adopt water and supercritical CO
2for polyurethane foam prepared by whipping agent, when low density, intensity, dimensional stability and heat-insulating property are all poor, and need to consume more isocyanic ester in preparation process.In addition, CO
2molecular volume is less, easily slowly overflows from abscess, causes the heat-insulating property of foam to decline.The gas phase thermal conductivity ratio pentane of HFCs class whipping agent is low, with HCFC-141b class close to but slightly higher.The security compared with pentane of HFCs class whipping agent is higher, and low toxicity, zero odp value.HFC-365mfc(in HFCs i.e. 1,1,1,3,3-3-pentafluorobutane) gas phase thermal conductivity is low, only has 10.6mW/mK, and have higher boiling point (40.2 DEG C) when 25 DEG C, can use preparation polyurethane foam at normal temperatures and pressures as whipping agent.
Lower due to compressive strength without the hard polyurethane foams strengthened, limit its range of application.The effective way strengthening polyurethane foam is in reaction raw materials, add inorganic strengthening agent filler, but the mineral filler being used as toughener often has higher thermal conductivity, weakens its heat-insulating property while making the mechanical property of reinforced foam.
CN1404503A discloses a kind of hollow microsphere and strengthens polyurethane foam, and the density of this material is 160-480Kg/m
3.This foam can not use as lagging material, and uses in " in automobile industry " conduct " reinforcement foam materials ".
CN101235128A discloses a kind of continuous fibre enhancement polyurethane foam, and the density of this material is 400-800Kg/m
3, compressive strength is 17-62MPa.This foam is not heat-insulation material, but as " bearing structure material ".
CN101191010A discloses a kind of continuous fibre enhancement polyurethane foam, and the density of this material is 690-768Kg/m
3, compressive strength is 48.8-65.1MPa.This foam is suitable is not heat-insulation material, but for technical fields such as " " warship cabin door, dividing plate, railroad tie, lorry compartment and civil construction materials.
The internal structure of pearlstone is cellular, nonpoisonous and tasteless, be stale-proof do not fire, acid and alkali-resistance, and there is very low thermal conductivity, be widely used in thermal insulating material field.CN101130629A discloses a kind of polyurathamc, pearlstone composite construction energy-saving material and locale spray coating constructing technique, but its perlite particle particle size range used is larger, be 1 ~ 4mm, adding quality is 3 ~ 5 times of polyurethane reaction raw material, and do not indicate used whipping agent kind, heat-insulating property, mechanical property and flame retardant properties that material can reach.
CN101139186A discloses a kind of polyurathamc, expanded perlite composite heat insulation plate and production technique thereof, its perlite particle particle size range used is larger, be 1 ~ 12mm, add 3 ~ 4 times that quality is polyurethane reaction raw material, the polyurethane foamed material thermal conductivity obtained is higher, reach 46 ~ 60mW/mK, and density is larger.
CN102531467A discloses a kind of polyurathamc, pearlstone complex heat-preservation flame-retardant board and preparation method thereof, but its whipping agent used is not the whipping agent of environment-friendly type, and the polyurethane foamed material thermal conductivity obtained is higher, be 24 ~ 42mW/mK, lose the heat-insulating property of the excellence of polyurethane foamed material itself.
People (the Mingxing Ai such as Mingxing Ai, etc, Advanced Materials Research (2010), 96,141-144.) report the hard foamed poly urethane system of pearlstone doping, but its whipping agent used is not the whipping agent of environment-friendly type, and thermal conductivity is greater than 23mW/mK, and the median size of the pearlstone used is 1.0mm, and the flame retardant properties of material does not also characterize.
In sum; the expanded perlite granule size used in hard polyurethane material of the prior art is comparatively large, dispersed bad; the material thermal conductivity of preparation is higher; mechanical property and flame retardant properties indefinite; use the whipping agent of non-environment-friendly type in preparation process, adverse influence can be produced to environment protection.
Therefore, those skilled in the art is devoted to develop that a kind of density is lower, thermal conductivity is low, have urethane/expansion pearlite thermal insulation insulating foam compared with high flame resistance, good mechanical properties, and improve preparation technology, to reduce the disadvantageous effect to environment.
Summary of the invention
The present invention is directed to prior art above shortcomings, provide a kind of polyurethane adiabatic heat-insulation foam material and preparation method thereof, the present invention adopts the agent of HFCs the 3rd class zero odp environment-friendly foaming, composite-grain diameter is less than the pearlstone of 1mm, Halogen efficient flame-retarding agent, lower, environmental protection, the heat-insulating property of polyurethane adiabatic heat-insulation foam material density of preparation is excellent and fire-retardant, has excellent compression performance simultaneously.
The present invention is achieved by the following technical solutions:
The invention provides a kind of polyurethane adiabatic heat-insulation foam material, its component and content are:
(a) polyether glycol 100 weight part;
(b) polymethylene multi-phenenyl isocyanate 150 ~ 170 weight part;
(c) pearlstone 5 ~ 30 weight part;
(d) pneumatogen 20 ~ 40 weight part;
(e) fire retardant 10 ~ 15 weight part;
(f) catalyzer 1 ~ 3 weight part;
(g) suds-stabilizing agent 1.5 ~ 10 weight part.
Preferably, in described polyether glycol, hydroxyl value is 480 ~ 500mgKOH/g, and when 25 DEG C, viscosity is 6500 ~ 9500mPas; In described polymethylene multi-phenenyl isocyanate, the content of isocyano is 30 ~ 32%wt, and when 25 DEG C, viscosity is 350 ~ 700mPas, and functionality is 2.6 ~ 3.1; Described pneumatogen is 1,1,1,3,3-3-pentafluorobutane; Described catalyzer is the mixture of the dibutyl tin laurate of 50%-100% and the trolamine of 0-50%.
Preferably, described pearlstone is powder, and median size is 0.06 ~ 0.8mm.
Preferably, described fire retardant is not halogen-containing fire retardant, comprising: the one in methyl-phosphoric acid dimethyl ester or ethyl phosphonic acid diethyl ester or its combination.
Preferably, described suds-stabilizing agent is tensio-active agent, comprises the silicon class tensio-active agent containing Si-C-structure.
On the other hand, the invention discloses the preparation method of polyurethane adiabatic heat-insulation foam material as above, comprise the following steps:
The first step: by polyether glycol, isocyanic ester and pearlstone drying treatment;
Second step: after carry out successively combination treatment and polymerization foaming process, obtain building mould base; After the demoulding, mould base will be built and carry out maturation process, obtain polyurethane adiabatic heat-insulation foam material.
Preferably, described drying treatment referred to: by polyether glycol, isocyanic ester and pearlstone at 40 DEG C dry 8 hours.
Preferably, described combination treatment refers to: join in polyether glycol after being weighed by formula by pearlstone, fire retardant, catalyzer, suds-stabilizing agent is added by formula, fully stir with mechanical stirring device, mix, add pneumatogen again, use mechanical stirring device fully to stir, mix.
Preferably, described polymerization foaming process refers to: joined rapidly in blending ingredients by isocyanic ester, fully stir simultaneously, be poured into free foaming in mould after 30 ~ 50 seconds, obtain and build mould base.
Preferably, described maturation process refers to: react 40 minutes at 40 DEG C together with mould, then put into baking oven, 50 ~ 100 DEG C of slakings more than 6 hours.
The present invention is by adopting the agent of HFCs the 3rd class zero odp environment-friendly foaming, and composite-grain diameter is less than the pearlstone of 1mm, has prepared that density is lower, environmental protection, heat-insulating property excellent and fire-retardant, has excellent compression performance polyurethane adiabatic heat-insulation foam material simultaneously.
Embodiment
The abbreviation that the present invention uses is as follows: PAPI refers to polymethylene multi-phenenyl isocyanate (Polyaryl-Polymethylene-Isocyanate), DBTDL refers to dibutyl tin laurate (Dibutyltindilaurate), DEEP refers to diethyl ethylphosphate (Diethyl Ethylphosphonate), and DMMP refers to methyl-phosphoric acid dimethyl ester (Dimethyl Methylphosphonate).
Below embodiments of the invention are elaborated.The present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment
The first step: by polyether glycol, isocyanic ester and pearlstone at 40 DEG C dry 8 hours, room temperature is placed stand-by.
Second step: by the formula of embodiment 1-6 in table 1, be that the pearlstone of 0.06 ~ 0.8mm is by joining in polyether glycol after formula weighing by median size, fire retardant, catalyzer, suds-stabilizing agent is added by formula, fully stir with mechanical stirring device, mix, add pneumatogen HFC-365mfc again, use mechanical stirring device fully to stir, mix; Isocyanic ester is joined rapidly in blending ingredients, fully stirs simultaneously, after 30 ~ 50 seconds, be poured into free foaming in mould, obtain and build mould base.React 40 minutes at 40 DEG C together with mould, the demoulding, then puts into baking oven, and 50 ~ 100 DEG C of slakings more than 6 hours, obtain product.
With the implementation step that two of above-described embodiment steps are following examples 1-6 and comparative example 1-2, the raw materials quality mark proportioning with reference to table 1 is as follows:
The raw materials quality mark proportioning of table 1 embodiment 1-6 and comparative example 1-2
The Performance Evaluation that above-described embodiment prepares gained composite foam material is as follows:
Compression performance: tested by GB/T8813-2008 by the sample of integral foam material cut growth 50mm, wide 50mm, high 50mm, compression speed is 5mm/min;
Combustionproperty: the sample of integral foam material cut growth 250mm, wide 20mm, high 20mm is pressed GB/T8333-87 and measure its oxygen index;
Heat-insulating property: tested by the German Nai Chi company hot-fluid conductometer HFM436 of use by the sample of integral foam material cut growth 300mm, wide 300mm, high 10mm, the irregularity degree of sample is less than 0.5mm/m;
Density: the sample of integral foam material cut growth 50mm, wide 50mm, high 50mm is tested by GB/T6343-2009;
The Performance Evaluation of table 2. embodiment 1-6 and comparative example 1-2 is as following table
From the result in table 2, the present invention compares with existing invention, employs environment-friendly type pneumatogen, and the less pearlstone of particle diameter is as weighting material, the polyurethane foamed material of preparation has good heat-insulating property, flame retardant properties and mechanical property, and its Midst density is less than 65Kg/m
3, thermal conductivity is less than 21mW/mK, and compressive strength is greater than 0.42MPa, and modulus of compression is greater than 14MPa, and oxygen index is more than or equal to 23.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that the ordinary skill of this area just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a polyurethane adiabatic heat-insulation foam material, its component and content are:
(a) polyether glycol 100 weight part;
(b) polymethylene multi-phenenyl isocyanate 150 ~ 170 weight part;
(c) pearlstone 5 ~ 30 weight part;
(d) pneumatogen 20 ~ 40 weight part;
(e) fire retardant 10 ~ 15 weight part;
(f) catalyzer 1 ~ 3 weight part;
(g) suds-stabilizing agent 1.5 ~ 10 weight part;
Wherein, the particle diameter of described pearlstone is less than 1mm.
2. polyurethane adiabatic heat-insulation foam material according to claim 1, is characterized in that, in described polyether glycol, hydroxyl value is 480 ~ 500mgKOH/g, and when 25 DEG C, viscosity is 6500 ~ 9500mPas; In described polymethylene multi-phenenyl isocyanate, the content of isocyano is 30 ~ 32%wt, and when 25 DEG C, viscosity is 350 ~ 700mPas, and functionality is 2.6 ~ 3.1; Described pneumatogen is 1,1,1,3,3-3-pentafluorobutane; Described catalyzer is the mixture of the dibutyl tin laurate of 50%-100% and the trolamine of 0-50%.
3. polyurethane adiabatic heat-insulation foam material according to claim 1, is characterized in that, described pearlstone is powder, and median size is 0.06 ~ 0.8mm.
4. polyurethane adiabatic heat-insulation foam material according to claim 1, is characterized in that, described fire retardant is not halogen-containing fire retardant, comprising: the one in methyl-phosphoric acid dimethyl ester or ethyl phosphonic acid diethyl ester or its combination.
5. polyurethane adiabatic heat-insulation foam material according to claim 1, is characterized in that, described suds-stabilizing agent is tensio-active agent, comprises the silicon class tensio-active agent containing Si-C-structure.
6. a preparation method for polyurethane adiabatic heat-insulation foam material as claimed in claim 1, is characterized in that, comprises the following steps:
The first step: by polyether glycol, isocyanic ester and pearlstone drying treatment;
Second step: carry out combination treatment and polymerization foaming process successively, obtain building mould base; After the demoulding, mould base will be built and carry out maturation process, obtain polyurethane adiabatic heat-insulation foam material.
7. the preparation method of polyurethane adiabatic heat-insulation foam material according to claim 6, is characterized in that, described drying treatment refers to: by polyether glycol, isocyanic ester and pearlstone at 40 DEG C dry 8 hours.
8. the preparation method of polyurethane adiabatic heat-insulation foam material according to claim 6, it is characterized in that, described combination treatment refers to: join in polyether glycol after being weighed by formula by pearlstone, fire retardant, catalyzer, suds-stabilizing agent is added by formula, fully stir with mechanical stirring device, mix, then add pneumatogen, use mechanical stirring device fully to stir, mix.
9. the preparation method of polyurethane adiabatic heat-insulation foam material according to claim 6, it is characterized in that, described polymerization foaming process refers to: joined rapidly in blending ingredients by isocyanic ester, fully stir simultaneously, be poured into free foaming in mould after 30 ~ 50 seconds, obtain and build mould base.
10. the preparation method of polyurethane adiabatic heat-insulation foam material according to claim 6, is characterized in that, described maturation process refers to: react 40 minutes at 40 DEG C together with mould, then put into baking oven, 50 ~ 100 DEG C of slakings more than 6 hours.
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| CN113291027A (en) * | 2021-04-15 | 2021-08-24 | 陕西罗德建设科技有限公司 | Heat-insulation and decoration integrated plate and construction method thereof |
| CN114316344B (en) * | 2021-12-30 | 2023-01-13 | 山东世纪联合新材料科技有限公司 | Filling type physical foaming plastic material and preparation method thereof |
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