CN109535688A - A kind of polyurethane foam heat insulation material and preparation method thereof - Google Patents
A kind of polyurethane foam heat insulation material and preparation method thereof Download PDFInfo
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- CN109535688A CN109535688A CN201811388515.8A CN201811388515A CN109535688A CN 109535688 A CN109535688 A CN 109535688A CN 201811388515 A CN201811388515 A CN 201811388515A CN 109535688 A CN109535688 A CN 109535688A
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- 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
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- 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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
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- C08K7/00—Use of ingredients characterised by shape
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- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses a kind of polyurethane foam heat insulation materials, it is composed of the following parts by weight: 80~100 parts of base polyurethane prepolymer for use as, 100~120 parts of isocyanates, 15~20 parts of spirulina small molecular peptide, 5~10 parts of phase-change material micro-capsule, 15~30 parts of deionized water, 5~8 parts of stearic acid modified perlite, 3~5 parts of epoxidized methyl acetorieinoleate.The deficiencies of polyurethane foam heat insulation material mechanical property of the invention and heat insulation are good, water resistance, color inhibition, overcome the foams embrittlement of Water-Blown Rigid Polyurethane Foams, and thermal coefficient is bigger than normal.
Description
Technical field
The invention belongs to organic composite material technical fields, and in particular to a kind of polyurethane foam heat insulation material.
Background technique
Polyurethane material is the abbreviation of polyurethanes, it is a kind of high molecular material.Polyurethane is a kind of emerging
High-molecular organic material is known as " the fifth-largest plastics ", is widely used in the numerous necks of national economy because of the performance of its brilliance
Domain.Foamed plastics is one of principal item of polyurethane synthetic material, it is mainly characterized by porosity, thus relative density
Small, specific strength is high.According to raw material difference used and formula variation, soft, semi-rigid and hard polyurethane foams modeling can be made into
Material etc. is several；If polyester-type, polyether-type and castor oil type polyurethane foam plastic can be divided into again by polyalcohol assortment used
Material etc.；If classifying again by foaming method has the types such as blocky, molding and spraying polyurethane foam plastic.
Rigid polyurethane foam is a kind of novel synthetic material with heat preservation with water-proof function, thermal coefficient
It is low, only 0.022~0.033W/(m* Κ), it is equivalent to the half of extruded sheet, is that thermal coefficient is minimum in current all thermal insulation materials
's.Rigid polyurethane foam be mainly used in exterior walls of buildings heat preservation, waterproofing and thermal insulation of roofing integration, heat preservation of refrigeration storage every
Heat, pipe insulation material, building board, refrigerator car and the heat-insulated material of freezer etc..Rigid polyurethane foam generally uses low boiling
Point hydrocarbon compound fluorochlorohydrocarbon (CFCS) is used as foaming agent, however discovered in recent years is to destroy earth's ozone layer by such compound
Arch-criminal, hydrochlorofluorocarbons (HCFC) class also has certain ozone remove function and generates greenhouse effects, so original poly- ammonia
Ester foaming system must be substituted.
Chinese patent if China Patent No. is 201510513841.7 discloses a kind of full water foamed plant oil base hard
The preparation method of polyurethane foam plastics substitutes petroleum based polyether polyol by using vegetable oil-based polyols, is catalyzed with amine
Agent, tin catalyst, water and foam stabilizer high-speed stirred are uniform, add isocyanates, pour into mold rapidly after high-speed stirred is uniform
Plant oil base rigid polyurethane foam is made in middle foaming.The present invention prepares hard polyurethane foams modeling using full water foamed
Material does not contain chloro-fluoro-carbon kind foaming agent, and ozone layer destroying effect ODP value is zero.The present invention is gradually substituted with vegetable oil-based polyols
Petroleum based polyether polyol can effectively improve the biological degradability of polyurethane foam plastics, obtained plant oil base hard polyurethane
Ester foamed plastic excellent combination property is compared with similar product has apparent economical and environmentally friendly advantage, will generate huge warp
Benefit of helping and social benefit.
For another example Chinese Patent Application No. is that the Chinese patent application of 200910038593.X discloses a kind of hard polyaminoester
Foamed plastics and preparation method thereof, rigid polyurethane foam, it is characterized in that rigid polyurethane foam is by isocyanates
It is formed with thick polyether reactant, nucleating agent and foaming agent is added in reaction process, thick polyethers is by polyether polyol, water, catalyst
It being formed with stabilizer, polyether polyol is made of the mixing of various of monomer polyethers, and the average hydroxyl value of polyether polyol is 300~
700mgKOH/g, the hydroxy functionality of polyether polyol are 2~8, monomeric polyether by ethylene oxide and/or propylene oxide with have
The initiator for reaction of 2~8 reactive hydrogen atoms generates, and initiator includes polyalcohol and polyamines, and polyalcohol includes glycerol, three hydroxyl first
Base propane, triethanolamine, pentaerythrite, sorbierite and sucrose alcohol；Foaming agent be pentane class, HFC-134a, HFC-245fa and
Any one of HFC-365mfc, wherein pentane class includes pentane, pentamethylene and isopentane.The present invention has hard polyurethane
Ester foamed plastic complies fully with the good feature of steady dissolution of environmental requirement and polyether polyol.
Above-mentioned patent improves polyurethane foam as foaming agent using the substitution such as water or pentane class fluorochlorohydrocarbon, hydrochlorofluorocarbons
Material, wherein making foaming agent, the CO actually generated with water and isocyanates reaction with water2Gas makees foaming agent, ozone
Damage effect ODP value is zero, is had no toxic side effect, therefore water is to make attractive foaming agent；Moreover, full water foamed foam system
Standby simple process, the requirement to equipment is very low, can continue to use original foaming system equipment, have a vast market foreground.But it is complete
There are many deficiencies for water blown rigid polyurethane foamed plastics, and such as foams embrittlement, thermal coefficient is bigger than normal, and system viscosity is too big,
Poor fluidity etc., to limit the promotion and application of Water-Blown Rigid Polyurethane Foams.
Summary of the invention
In view of the above deficiencies, of the invention the invention discloses a kind of polyurethane foam heat insulation material and preparation method thereof
Polyurethane foam heat insulation material mechanical property and heat insulation are good, overcome the foam of Water-Blown Rigid Polyurethane Foams
The deficiencies of body embrittlement, thermal coefficient is bigger than normal.
The present invention is achieved by the following technical scheme:
A kind of polyurethane foam heat insulation material, is composed of the following parts by weight: 80~100 parts of base polyurethane prepolymer for use as,
100~120 parts of isocyanates, 15~20 parts of spirulina small molecular peptide, 5~10 parts of phase-change material micro-capsule, deionized water 15~
30 parts, 5~8 parts of stearic acid modified perlite, 3~5 parts of epoxidized methyl acetorieinoleate.
Further, the preparation method of above-mentioned base polyurethane prepolymer for use as comprising following steps:
(1) raw material of following parts by weight is weighed: 70~90 parts of polymer polyatomic alcohol, 5~15 parts of fire retardant, neutralizer 5~10
Part, 1~3 part of polyaspartic ester, 10~15 parts of modified nano-titanium dioxide, 15~20 parts of isocyanates；The polymerization
Object polyalcohol is polyester polyol or polyether polyol；The isocyanates is toluene di-isocyanate(TDI), diphenyl methane two
One or more mixtures of isocyanates, multiple polymethylene polyphenyl polyisocyanates；The fire retardant is N, N
~bis- (2~ethoxy) aminomethy-lenephosphonic acids diethylesters, bis- (4~hydroxy phenyl) phenyl phosphine oxides, tetrabromo-benzene anhydride diol and
One or more mixtures of dibromoneopentyl glycol；The neutralizer is pentamethyl-diethylenetriamine, N, N- diformazan
One or more mixtures of basic ring hexylamine, triethylene diamine and triethylamine；
(2) polymer polyatomic alcohol as described in step (1), fire retardant and neutralizer are mixed under the conditions of 30 DEG C~60 DEG C
It is even, obtain mixture；
(3) isocyanates and polyaspartic ester are added into mixture described in step (2), then in temperature 50~80
DEG C nitrogen protection under the conditions of be stirred to react, modified nano-silica is added in carry out to be reacted 5~10 hours backward reaction systems
Change titanium, obtains base polyurethane prepolymer for use as after the reaction was continued 2~3 hours.
Further, above-mentioned modified nano-titanium dioxide is to mix butyl titanate, urea, isoamyl acetate and stannous chloride
Obtained after 600 DEG C of calcinings after conjunction, nitrogen in modified nano-titanium dioxide, tin doping molar fraction be 3%~5%.
The present invention adulterates the nitrogen and tin of 3%~5% molar fraction in nano-titanium dioxide, and nano-titanium dioxide is changed
Property reduces its photo-catalysis capability, and being then added in polyurethane material can be to avoid the TiO under light action2It is anti-with the hydrone of absorption
It answers, the alkyl radical and peroxide alkyl radical for generating high activity extract a hydrogen atom from high molecular polymer chain, raw
So that high molecular material is generated degradation circulation at alkyl diradical, causes the deterioration of polyurethane material.This is because TiO2Light is urged
Having main steps that for changing generates light induced electron to form hole, and a large amount of doped tins and nitrogen can prevent the photoelectron generated from timely
Transfer, the hole-recombination in the short time and with formation, to reduce light-catalysed activity, while modified nano-titanium dioxide
Still there is excellent ultraviolet reflection, scattering power, and its dispersibility increases and may be uniformly dispersed in polyurethane material
In not only improved the color inhibition ability of material but also will not influence material degradation deterioration.
Further, above-mentioned spirulina small molecular peptide is by the way that spirulina algae-residue is passed through conventional extraction, conventional complex enzyme
What enzymolysis process was prepared.
Can be delivered on Zhejiang Agriculture journal according to Wu Mengmeng etc. " small point of spirulina of the spirulina small molecular peptide
The research of sub- polypeptide preparation process " it is prepared by method described in document.
It is because small-molecular peptides are a kind of lifes between amino acid and protein that the present invention, which selects spirulina small molecular peptide,
Compound matter, it is smaller than protein molecular weight, and bigger than amino acid molecular amount, is the segment of a protein, and molecular weight is smaller,
Chain length is shorter, with polyurethane prepolymer similar compatibility, can be used for small point of the blending and modifying of polyurethane material, especially spirulina
Sub- peptide contains-NH2,-NH-, the labile functional groups such as-COOH, carry out the blending including physics and chemical modification for it
Modification provides material base.So base polyurethane prepolymer for use as can preferably mix with spirulina small molecular peptide, so that small-molecular peptides
Effectively stretching, extension, is mutually intertwined with polyurethane molecular, and prepolymer molecule is reacted to macromolecular and light with small-molecular peptides
Degree crosslinking, improves the mechanical property of composite material；- NH in small-molecular peptides simultaneously2, the hydrophilic radicals such as-NH- and-OH
With in polyurethane-NCO group reacts and to form urine key or ammonia ester bond, so not only reducing hydrophilic radical, but also increase
- CH3, the hydrophobic groupings such as phenyl ring, thus the water imbibition for substantially increasing the water resistance of polyurethane material, reducing material.
Further, above-mentioned stearic acid modified perlite is made by following methods: first by perlite it is levigate after cross 200~
300 meshes, are then heated to 100~120 DEG C, naturally cool to room temperature later and obtain expanded perlite, then will expansion treasure
Zhu Yan is calcined 1~2 hour at 700~800 DEG C, reduces temperature to 40~45 DEG C, stearic acid and acetone 1:2 in mass ratio is added
The solution being mixed to get, it is insulated and stirred 30~40 minutes, conventional obtained by drying to stearic acid modified perlite.
The present invention is used further to prepare polyurethane foamed material by the perlite of expansion is modified, can solve because expansion is precious
The problems such as pearl rock water absorption rate is high, poor water resistance.By the modification to perlite, stearic acid is supported on to the surface of particle, so that
Its surface is changed into hydrophobicity by hydrophily, and smaller on the influence of the specific surface area of perlite particle, aperture and pore structure,
Improve the heat preservation and fire protecting performance of polyurethane material.
Further, above-mentioned phase-change material micro-capsule is by the way that water-soluble melamine resin performed polymer is added to capsule-core and benzene
It is stirred to get in the mixed emulsion of ethylene maleic acid anhydride copolymer lotion, the partial size of phase-change material micro-capsule is 1~5 μm；
The capsule-core is any one or two or more mixtures in n-eicosane, Heneicosane and n-docosane.
The preparation method of above-mentioned polyurethane foam heat insulation material comprising following steps:
(1) base polyurethane prepolymer for use as is weighed according to the amount of formula, spirulina small molecular peptide, phase-change material micro-capsule, deionized water, firmly
Resin acid modified pearl rock, epoxidized methyl acetorieinoleate, isocyanates；
(2) deionized water, small point of spirulina is successively added into base polyurethane prepolymer for use as under 600~1000 r/min stirring conditions
Sub- peptide, phase-change material micro-capsule, stearic acid modified perlite and epoxidized methyl acetorieinoleate continue to stir after raw material mixing
It obtains mixture within 10~15 minutes, isocyanic acid is then added into said mixture under 1500~2000r/min stirring condition
Ester mixing, pour into preset mold and foam at once after mixing, wherein mold preheating temperature be 30~40 DEG C, foamed time be 5~
Foamed material is finally put into vacuum oven and cures by 10min, and 90~100 DEG C of curing temperature, curing time 12h, i.e.,
It can get polyurethane foam heat insulation material.
The technical program has the advantages that compared with prior art
1, the present invention utilizes spirulina small molecular peptide and base polyurethane prepolymer for use as similar compatibility feature, and the two blending and modifying improves
The elongation percentage of polyurethane foam heat insulation material reduces water absorption rate, improves waterproof performance, while also improving polyurethane foam insulation
The mechanical property of material makes it have preferable tensile strength；And spirulina small molecular peptide can be improved the viscosity of foam, drop
Low bubble mobility, to have certain foam stabilizing effect.
2, present invention addition modified nano-titanium dioxide utilizes its own good purple into polyurethane foam heat insulation material
Outside line protective capacities improves the color inhibition ability of polyurethane foamed material, while avoiding the deterioration degradation of induction polyurethane, especially
It is suitble to the polyurethane material using aromatic isocyanate for raw material preparation, improves its product quality, and due to aromatic series
Isocyanates is cheap, can reduce product cost.
3, present invention selection addition phase-change material micro-capsule, because of their phase transition temperature and polyurethane material operating temperature
Mutually suitable, heat storage capacity stabilization, non-toxic and corrosivity；Simultaneously using water-soluble melamine resin as wall material coating phase-change materials system
Standby at microcapsules, partial size is smaller to be evenly distributed on phase-change material in polyurethane material, after limitation phase-change material liquefaction arbitrarily
Flowing solves phase-change material and adjacent material interface problem, extends the materials'use service life.
4, the stearic acid modified perlite added in the present invention can effectively improve fire prevention and the guarantor of polyurethane foamed material
Warm nature energy, and it has certain adsorptivity to phase-change material micro-capsule, can prevent microcapsules from reuniting and settle, be unevenly distributed
It is even.
5, the epoxidized methyl acetorieinoleate added in the present invention has good surface-active, and it is poly- can to reduce hard
Urethane foam system viscosity improves mobility, and epoxidized methyl acetorieinoleate and spirulina small molecular peptide collective effect,
Foam stabilizing effect is played in hard polyurethane foam system；And addition epoxidized methyl acetorieinoleate also have it is cold-resistant,
Freeze proof effect improves the weather resistance of polyurethane foamed material.
Specific embodiment
The present invention is further illustrated by the following examples, but not as limitation of the present invention.In the following example not
Dated specific experiment condition and method, used technological means are usually conventional hand well-known to those skilled in the art
Section.
Embodiment 1:
A kind of polyurethane foam heat insulation material, is composed of the following parts by weight: 90 parts of base polyurethane prepolymer for use as, isocyanic acid
120 parts of ester, 18 parts of spirulina small molecular peptide, 10 parts of phase-change material micro-capsule, 20 parts of deionized water, stearic acid modified perlite 5
Part, 4 parts of epoxidized methyl acetorieinoleate.
The preparation method of above-mentioned base polyurethane prepolymer for use as comprising following steps:
(1) raw material of following parts by weight is weighed: 80 parts of polymer polyatomic alcohol, 10 parts of fire retardant, 5 parts of neutralizer, poly- lucid asparagus
3 parts of propylhomoserin ester, 10 parts of modified nano-titanium dioxide, 18 parts of isocyanates；The polymer polyatomic alcohol be polyester polyol or
Polyether polyol；The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the more benzene of multiple methylene
One or more mixtures of Quito isocyanates；The fire retardant is N, N~bis- (2~ethoxy) amino methylene
One of base diethyl phosphonate, bis- (4~hydroxy phenyl) phenyl phosphine oxides, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol or two
Kind or more mixture；The neutralizer is pentamethyl-diethylenetriamine, N, N- dimethyl cyclohexyl amine, triethylene diamine and three
One or more mixtures of ethamine；
(2) polymer polyatomic alcohol as described in step (1), fire retardant and neutralizer are uniformly mixed under the conditions of 40 DEG C, are obtained
Mixture；
(3) isocyanates and polyaspartic ester are added into mixture described in step (2), then in temperature 70 C
It is stirred to react under the conditions of nitrogen protection, carries out modified nano-titanium dioxide being added in backward reaction system in 8 hours wait react, continue
Reaction obtained base polyurethane prepolymer for use as after 3 hours.
Above-mentioned modified nano-titanium dioxide is passed through after mixing butyl titanate, urea, isoamyl acetate and stannous chloride
Obtained after crossing 600 DEG C of calcinings, nitrogen in modified nano-titanium dioxide, tin doping molar fraction be 5%.
Above-mentioned spirulina small molecular peptide is by the way that spirulina algae-residue is passed through conventional extraction, conventional complex enzyme zymohydrolysis technique
It is prepared.
Above-mentioned stearic acid modified perlite is made by following methods: first by levigate 250 meshes excessively afterwards of perlite, then will
It is heated to 120 DEG C, naturally cools to room temperature later and obtains expanded perlite, then that expanded perlite is calcined to 2 at 750 DEG C is small
When, reduction temperature is to 45 DEG C, the solution that addition stearic acid and acetone 1:2 in mass ratio are mixed to get, and insulated and stirred 35 minutes, often
It advises obtained by drying to stearic acid modified perlite.
Above-mentioned phase-change material micro-capsule is by the way that water-soluble melamine resin performed polymer is added to capsule-core and styrene-
It is stirred to get in the mixed emulsion of copolymer-maleic anhydride lotion, the partial size of phase-change material micro-capsule is 3 μm；The capsule-core
For any one or the two or more mixtures in n-eicosane, Heneicosane and n-docosane.
The preparation method of above-mentioned polyurethane foam heat insulation material comprising following steps:
(1) base polyurethane prepolymer for use as is weighed according to the amount of formula, spirulina small molecular peptide, phase-change material micro-capsule, deionized water, firmly
Resin acid modified pearl rock, epoxidized methyl acetorieinoleate, isocyanates；
(2) under 800 r/min stirring conditions successively into base polyurethane prepolymer for use as be added deionized water, spirulina small molecular peptide,
Phase-change material micro-capsule, stearic acid modified perlite and epoxidized methyl acetorieinoleate continue 15 points of stirring after raw material mixing
Clock obtains mixture, and isocyanates mixing, horse after mixing is then added into said mixture under 1800r/min stirring condition
On pour into preset mold and foam, wherein mold preheating temperature is 35 DEG C, and foamed time 10min finally puts foamed material
It is cured into vacuum oven, 100 DEG C of curing temperature, curing time 12h can be obtained polyurethane foam heat insulation material.
Embodiment 2:
A kind of polyurethane foam heat insulation material, is composed of the following parts by weight: 100 parts of base polyurethane prepolymer for use as, isocyanide
110 parts of acid esters, 15 parts of spirulina small molecular peptide, 8 parts of phase-change material micro-capsule, 30 parts of deionized water, stearic acid modified perlite 8
Part, 5 parts of epoxidized methyl acetorieinoleate.
The preparation method of above-mentioned base polyurethane prepolymer for use as comprising following steps:
(1) raw material of following parts by weight is weighed: 70 parts of polymer polyatomic alcohol, 50 parts of fire retardant, 8 parts of neutralizer, poly- lucid asparagus
2 parts of propylhomoserin ester, 12 parts of modified nano-titanium dioxide, 20 parts of isocyanates；The polymer polyatomic alcohol be polyester polyol or
Polyether polyol；The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the more benzene of multiple methylene
One or more mixtures of Quito isocyanates；The fire retardant is N, N~bis- (2~ethoxy) amino methylene
One of base diethyl phosphonate, bis- (4~hydroxy phenyl) phenyl phosphine oxides, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol or two
Kind or more mixture；The neutralizer is pentamethyl-diethylenetriamine, N, N- dimethyl cyclohexyl amine, triethylene diamine and three
One or more mixtures of ethamine；
(2) polymer polyatomic alcohol as described in step (1), fire retardant and neutralizer are uniformly mixed under the conditions of 60 DEG C, are obtained
Mixture；
(3) isocyanates and polyaspartic ester are added into mixture described in step (2), then at 80 DEG C of temperature
It is stirred to react under the conditions of nitrogen protection, carries out modified nano-titanium dioxide being added in backward reaction system in 5 hours wait react, continue
Reaction obtained base polyurethane prepolymer for use as after 2 hours.
Above-mentioned modified nano-titanium dioxide is passed through after mixing butyl titanate, urea, isoamyl acetate and stannous chloride
Obtained after crossing 600 DEG C of calcinings, nitrogen in modified nano-titanium dioxide, tin doping molar fraction be 4%.
Above-mentioned spirulina small molecular peptide is by the way that spirulina algae-residue is passed through conventional extraction, conventional complex enzyme zymohydrolysis technique
It is prepared.
Above-mentioned stearic acid modified perlite is made by following methods: first by levigate 300 meshes excessively afterwards of perlite, then will
It is heated to 100 DEG C, naturally cools to room temperature later and obtains expanded perlite, then that expanded perlite is calcined to 1 at 800 DEG C is small
When, reduction temperature is to 40 DEG C, the solution that addition stearic acid and acetone 1:2 in mass ratio are mixed to get, and insulated and stirred 40 minutes, often
It advises obtained by drying to stearic acid modified perlite.
Above-mentioned phase-change material micro-capsule is by the way that water-soluble melamine resin performed polymer is added to capsule-core and styrene-
It is stirred to get in the mixed emulsion of copolymer-maleic anhydride lotion, the partial size of phase-change material micro-capsule is 1 μm；The capsule-core
For any one or the two or more mixtures in n-eicosane, Heneicosane and n-docosane.
The preparation method of above-mentioned polyurethane foam heat insulation material comprising following steps:
(1) base polyurethane prepolymer for use as is weighed according to the amount of formula, spirulina small molecular peptide, phase-change material micro-capsule, deionized water, firmly
Resin acid modified pearl rock, epoxidized methyl acetorieinoleate, isocyanates；
(2) under 1000 r/min stirring conditions successively into base polyurethane prepolymer for use as be added deionized water, spirulina small molecular peptide,
Phase-change material micro-capsule, stearic acid modified perlite and epoxidized methyl acetorieinoleate continue 12 points of stirring after raw material mixing
Clock obtains mixture, and isocyanates mixing, horse after mixing is then added into said mixture under 2000r/min stirring condition
On pour into preset mold and foam, wherein mold preheating temperature is 40 DEG C, and foamed material is finally put by foamed time 5min
It is cured in vacuum oven, 95 DEG C of curing temperature, curing time 12h can be obtained polyurethane foam heat insulation material.
Embodiment 3:
A kind of polyurethane foam heat insulation material, is composed of the following parts by weight: 80 parts of base polyurethane prepolymer for use as, isocyanic acid
100 parts of ester, 20 parts of spirulina small molecular peptide, 5 parts of phase-change material micro-capsule, 15 parts of deionized water, stearic acid modified perlite 7
Part, 3 parts of epoxidized methyl acetorieinoleate.
The preparation method of above-mentioned base polyurethane prepolymer for use as comprising following steps:
(1) raw material of following parts by weight is weighed: 90 parts of polymer polyatomic alcohol, 15 parts of fire retardant, 10 parts of neutralizer, poly- lucid asparagus
1 part of propylhomoserin ester, 15 parts of modified nano-titanium dioxide, 15 parts of isocyanates；The polymer polyatomic alcohol be polyester polyol or
Polyether polyol；The isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the more benzene of multiple methylene
One or more mixtures of Quito isocyanates；The fire retardant is N, N~bis- (2~ethoxy) amino methylene
One of base diethyl phosphonate, bis- (4~hydroxy phenyl) phenyl phosphine oxides, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol or two
Kind or more mixture；The neutralizer is pentamethyl-diethylenetriamine, N, N- dimethyl cyclohexyl amine, triethylene diamine and three
One or more mixtures of ethamine；
(2) polymer polyatomic alcohol as described in step (1), fire retardant and neutralizer are uniformly mixed under the conditions of 30 DEG C, are obtained
Mixture；
(3) isocyanates and polyaspartic ester are added into mixture described in step (2), then in temperature 50 C
It is stirred to react under the conditions of nitrogen protection, carries out modified nano-titanium dioxide being added in backward reaction system in 10 hours wait react, after
Continuous reaction obtained base polyurethane prepolymer for use as after 2 hours.
Above-mentioned modified nano-titanium dioxide is passed through after mixing butyl titanate, urea, isoamyl acetate and stannous chloride
Obtained after crossing 600 DEG C of calcinings, nitrogen in modified nano-titanium dioxide, tin doping molar fraction be 3%.
Above-mentioned spirulina small molecular peptide is by the way that spirulina algae-residue is passed through conventional extraction, conventional complex enzyme zymohydrolysis technique
It is prepared.
Above-mentioned stearic acid modified perlite is made by following methods: first by levigate 200 meshes excessively afterwards of perlite, then will
It is heated to 120 DEG C, naturally cools to room temperature later and obtains expanded perlite, then that expanded perlite is calcined to 2 at 700 DEG C is small
When, reduction temperature is to 42 DEG C, the solution that addition stearic acid and acetone 1:2 in mass ratio are mixed to get, and insulated and stirred 30 minutes, often
It advises obtained by drying to stearic acid modified perlite.
Above-mentioned phase-change material micro-capsule is by the way that water-soluble melamine resin performed polymer is added to capsule-core and styrene-
It is stirred to get in the mixed emulsion of copolymer-maleic anhydride lotion, the partial size of phase-change material micro-capsule is 5 μm；The capsule-core
For any one or the two or more mixtures in n-eicosane, Heneicosane and n-docosane.
The preparation method of above-mentioned polyurethane foam heat insulation material comprising following steps:
(1) base polyurethane prepolymer for use as is weighed according to the amount of formula, spirulina small molecular peptide, phase-change material micro-capsule, deionized water, firmly
Resin acid modified pearl rock, epoxidized methyl acetorieinoleate, isocyanates；
(2) under 600 r/min stirring conditions successively into base polyurethane prepolymer for use as be added deionized water, spirulina small molecular peptide,
Phase-change material micro-capsule, stearic acid modified perlite and epoxidized methyl acetorieinoleate continue 10 points of stirring after raw material mixing
Clock obtains mixture, and isocyanates mixing, horse after mixing is then added into said mixture under 1500r/min stirring condition
On pour into preset mold and foam, wherein mold preheating temperature is 30 DEG C, and foamed material is finally put by foamed time 8min
It is cured in vacuum oven, 90 DEG C of curing temperature, curing time 12h can be obtained polyurethane foam heat insulation material.
Comparative example 1: polyether polyol, 1.6 parts of weight triethylenediamines, the 3 parts of weight sis of 100 parts of weight are weighed first
Alkanes foam stabiliser and 1.2 parts of weight waters, mechanical stirring is uniformly mixed at room temperature, continues to add 1 part of weight tin dilaurate two
Butyl tin, after mixing evenly, adding 130 parts of weight methyl diphenylene diisocyanates, (index of Response of isocyanates is
1.1), high-speed stirred pours into rapidly free foaming in mold, solidifies 6 at curing 3 hours, 70 DEG C at 25 DEG C to after starting foaming
Hour, obtain rigid polyurethane foam.
Comparative example 2:(1) preparation urethane composition A: weigh 200g combined polyether, 7.5g hypo-aluminum orthophosphate, 7.5g phenyl
Phosphinic acids aluminium, 7.5g dimethyl methyl phosphonate and the (2- methyl -5- ethyl-2-oxo -1,3,2- dioxa of 7.5g methylphosphonic acid two
Phospha cyclohexyl -5- methylene) ester compound flame retardant, 14g HCFC-141b, 2g L-6900L, 3g dimethyl ethanol
It is uniformly mixed and made into urethane composition A by HT-5050 the and 50g glass fibre of amine, 1.5g；
(2) material temperature and mold temperature are controlled: the temperature of the material temperature and mold of isocyanates and urethane composition A is controlled 25
DEG C, 300g isocyanates is then weighed, is added in urethane composition A material, and stirred evenly with electric mixer；
(3) foaming of PU hard bubble: the solution being uniformly mixed in step 2 is poured into mold, makes its foaming, to foam curing
Demoulding is placed in baking oven, cures 2h at 70 DEG C, polyurethane foam plastics can be obtained.
Polyurethane foam plastics performance test:
According to GB/T20219-2015 insulation polyurethane foam described in coated with hard polyurethane foam plastics national standard
Plastics performance test method carries out polyurethane foamed material preparation-obtained in above-described embodiment 1~3 and comparative example 1~2
The test of compressive strength, rate of closed hole, initial thermal conductivity coefficient and water absorption rate, concrete outcome are shown in Table 1,
1 polyurethane foam plastics the performance test results of table
By above-mentioned test result it is found that polyurethane foamed material obtained in Examples 1 to 3 compressive strength, rate of closed hole,
It is superior to polyurethane foamed material obtained in comparative example 1~2 in terms of initial thermal conductivity coefficient and water absorption rate, so of the invention is poly-
Urethane thermal insulation material has outstanding mechanical property and heat insulation performance, and water-tolerant.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (7)
1. a kind of polyurethane foam heat insulation material, it is characterised in that: it is composed of the following parts by weight: polyurethane prepolymer
80~100 parts of body, 100~120 parts of isocyanates, 15~20 parts of spirulina small molecular peptide, 5~10 parts of phase-change material micro-capsule,
15~30 parts of deionized water, 5~8 parts of stearic acid modified perlite, 3~5 parts of epoxidized methyl acetorieinoleate.
2. polyurethane foam heat insulation material according to claim 1, it is characterised in that: the system of the base polyurethane prepolymer for use as
Preparation Method comprising following steps:
(1) raw material of following parts by weight is weighed: 70~90 parts of polymer polyatomic alcohol, 5~15 parts of fire retardant, neutralizer 5~10
Part, 1~3 part of polyaspartic ester, 10~15 parts of modified nano-titanium dioxide, 15~20 parts of isocyanates；The polymerization
Object polyalcohol is polyester polyol or polyether polyol；The isocyanates is toluene di-isocyanate(TDI), diphenyl methane two
One or more mixtures of isocyanates, multiple polymethylene polyphenyl polyisocyanates；The fire retardant is N, N
~bis- (2~ethoxy) aminomethy-lenephosphonic acids diethylesters, bis- (4~hydroxy phenyl) phenyl phosphine oxides, tetrabromo-benzene anhydride diol and
One or more mixtures of dibromoneopentyl glycol；The neutralizer is pentamethyl-diethylenetriamine, N, N- diformazan
One or more mixtures of basic ring hexylamine, triethylene diamine and triethylamine；
(2) polymer polyatomic alcohol as described in step (1), fire retardant and neutralizer are mixed under the conditions of 30 DEG C~60 DEG C
It is even, obtain mixture；
(3) isocyanates and polyaspartic ester are added into mixture described in step (2), then in temperature 50~80
DEG C nitrogen protection under the conditions of be stirred to react, modified nano-silica is added in carry out to be reacted 5~10 hours backward reaction systems
Change titanium, obtains base polyurethane prepolymer for use as after the reaction was continued 2~3 hours.
3. polyurethane foam heat insulation material according to claim 2, it is characterised in that: the modified nano-titanium dioxide
It is to be obtained after 600 DEG C of calcinings after mixing butyl titanate, urea, isoamyl acetate and stannous chloride, modified Nano two
Nitrogen in titanium oxide, tin doping molar fraction be 3%~5%.
4. polyurethane foam heat insulation material according to claim 2, it is characterised in that: the spirulina small molecular peptide stated is logical
It crosses and spirulina algae-residue is prepared by conventional extraction, conventional complex enzyme zymohydrolysis technique.
5. polyurethane foam heat insulation material according to claim 4, it is characterised in that: the stearic acid modified perlite
It is made by following methods: first by levigate 200~300 meshes excessively afterwards of perlite, being then heated to 100~120 DEG C, later certainly
It so is cooled to room temperature to obtain expanded perlite, then expanded perlite is calcined 1~2 hour at 700~800 DEG C, reduce temperature
To 40~45 DEG C, the solution that stearic acid and acetone 1:2 in mass ratio are mixed to get is added, it is insulated and stirred 30~40 minutes, conventional
It is obtained by drying to arrive stearic acid modified perlite.
6. polyurethane foam heat insulation material according to claim 5, it is characterised in that: the phase-change material micro-capsule is
By the way that water-soluble melamine resin performed polymer is added in capsule-core and the mixed emulsion of styrene-maleic anhydride copolymer lotion
It stirs to get, the partial size of phase-change material micro-capsule is 1~5 μm；The capsule-core is n-eicosane, Heneicosane and positive two
Any one in dodecane or two or more mixtures.
7. polyurethane foam heat insulation material described in any one of -6 according to claim 1, it is characterised in that: the poly- ammonia
The preparation method of ester cellular insulant comprising following steps:
(1) base polyurethane prepolymer for use as is weighed according to the amount of formula, spirulina small molecular peptide, phase-change material micro-capsule, deionized water, firmly
Resin acid modified pearl rock, epoxidized methyl acetorieinoleate, isocyanates；
(2) deionized water, small point of spirulina is successively added into base polyurethane prepolymer for use as under 600~1000r/min stirring condition
Sub- peptide, phase-change material micro-capsule, stearic acid modified perlite and epoxidized methyl acetorieinoleate continue to stir after raw material mixing
It obtains mixture within 10~15 minutes, isocyanic acid is then added into said mixture under 1500~2000r/min stirring condition
Ester mixing, pour into preset mold and foam at once after mixing, wherein mold preheating temperature be 30~40 DEG C, foamed time be 5~
Foamed material is finally put into vacuum oven and cures by 10min, and 90~100 DEG C of curing temperature, curing time 12h, i.e.,
It can get polyurethane foam heat insulation material.
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| CN201811388515.8A CN109535688A (en) | 2018-11-21 | 2018-11-21 | A kind of polyurethane foam heat insulation material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194828A (en) * | 2019-06-28 | 2019-09-03 | 北京理工大学 | A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover |
| CN110305290A (en) * | 2019-06-28 | 2019-10-08 | 北京理工大学 | A kind of high tenacity low-density polyurethane method for producing elastomers of the energy-absorbing material containing phase transformation |
| CN111647122A (en) * | 2020-06-10 | 2020-09-11 | 东莞市腾崴塑胶制品有限公司 | Sponge with temperature adjusting function |
-
2018
- 2018-11-21 CN CN201811388515.8A patent/CN109535688A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110194828A (en) * | 2019-06-28 | 2019-09-03 | 北京理工大学 | A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover |
| CN110305290A (en) * | 2019-06-28 | 2019-10-08 | 北京理工大学 | A kind of high tenacity low-density polyurethane method for producing elastomers of the energy-absorbing material containing phase transformation |
| CN111647122A (en) * | 2020-06-10 | 2020-09-11 | 东莞市腾崴塑胶制品有限公司 | Sponge with temperature adjusting function |
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Application publication date: 20190329 |