CN110358042A - A kind of inorganic material-modified rigid polyurethane foam and preparation method thereof - Google Patents
A kind of inorganic material-modified rigid polyurethane foam and preparation method thereof Download PDFInfo
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- CN110358042A CN110358042A CN201910789621.5A CN201910789621A CN110358042A CN 110358042 A CN110358042 A CN 110358042A CN 201910789621 A CN201910789621 A CN 201910789621A CN 110358042 A CN110358042 A CN 110358042A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
This application provides a kind of inorganic material-modified rigid polyurethane foam, raw material include: the white material of 10~15 mass parts, the black material of 10~15 mass parts, the component A of 5~10 mass parts, the component B of 10~15 mass parts, the component C of 10~15 mass parts, 2~8 mass parts additive；Component A be one of graphite, graphene/polymer composites, silica, aluminium hydroxide, white carbon black and silica flour, two or more；Component B is glass bead and/or pearlife；Component C is hollow glass micropearl and/or hollow ceramic microspheres；Present invention also provides a kind of preparation methods of above-mentioned inorganic material-modified rigid polyurethane foam；It is modified by adding inorganic material, the thermal coefficient of modified rigid polyurethane foam material obtained is 0.025-0.030W/ (m.k), and fire-protection rating is A grades, to improve fire-protection rating on the basis of ensure that thermal insulation property.
Description
Technical field
The present invention relates to building thermal insulation material technical fields, more particularly, to a kind of inorganic material-modified rigid polyurethane foam
Foam material and preparation method thereof.
Background technique
Polyurethane material includes soft bubble polyurethane material, hard-foam polyurethane material, half hard bubble polyurethane material, polyurethane bullet
Property body, polyurethane shoe bottom material, polyurethane slurry, polyurethane fiber, polyurethane coating, polyurethane adhesive, polyurethane sealant
Etc..
Rigid polyurethane foam has the function of waterproof, heat preservation, heat-insulated etc. with what white material and black material hybrid reaction were formed
Rigid foam, referred to as hard polyurethane foam, abbreviation hard polyurethane foam.Wherein white material refers to by combination polyalcohol (group
Close polyethers or polyester) and the additives composition such as foaming agent combination material.The main component of black material is isocyanates.White material and black material
It is to form one of necessary raw material of hard polyurethane foam.
The performance of rigid polyurethane foam: 1) thermal coefficient is low, and thermal property is good, when hard polyaminoester density is
35~40kg/m3When, thermal coefficient is only 0.018~0.024w/ (m.k), is approximately equivalent to the half of EPS, is all thermal insulating materials
Thermal coefficient is minimum in material；2) has moisture-proof, waterproof performance, and the rate of closed hole of hard polyaminoester belongs to hydrophobic 90% or more
Property material, thermal coefficient will not be increased because of the moisture absorption, metope will not seep water；3) prevents fires, and fire-retardant, high temperature resistant, polyurethane is adding
It is a kind of fire retardant self-extinguishing, its softening point can reach 250 degrees Celsius or more, only in higher temperature after fire retardant
It just will appear decomposition, in addition, it can form carbon distribution in its foam surface in burning, this lamination carbon, which helps, is isolated following bubble
Foam can be effectively prevented propagation of flame；4) is same reaching since hard polyurethane foam insulation board is with excellent heat-proof quality
Under thermal requirements, building envelope thickness can be reduced, to increase indoor usable floor area；5) non-deformability is strong, no
Easy to crack, facing is stable, safe；6) porosity stable structure, substantially hole-closing structure, not only excellent thermal insulation performance, but also
Freeze thawing resistance, it is sound absorption properties might as well, can accomplish under the lifetime regular service conditions of structure, in drying, humidity or couple corrosion,
And due to insect, fungi or algal grown or due to exogenous influences such as the destructions of rodent, destruction is not will receive.
The Ministry of Public Security, which issues 2011 No. 65 file mandatory provision building heat preserving energy-saving materials, must reach A grades of fire prevention marks
It is quasi-.Thermal insulation material used in exterior wall is mainly organic foam plate at present, is easy burning, and burning behavior class is difficult at B1 or B grades
To meet the design requirement of building fire protection performance.The fire-protection rating of current rigid polyurethane foam is also not achieved A grades.
Therefore, how on the basis of guaranteeing the thermal insulation property of rigid polyurethane foam, rigid polyurethane foam is improved
The technical issues of fire-protection rating of foam material is current those skilled in the art's urgent need to resolve.
Summary of the invention
The object of the present invention is to provide a kind of inorganic material-modified rigid polyurethane foams.Another of the invention
Purpose is to provide a kind of preparation method of inorganic material-modified rigid polyurethane foam.
In order to solve the above technical problems, technical solution provided by the invention are as follows:
A kind of inorganic material-modified rigid polyurethane foam, is made of plurality of raw materials, described inorganic material-modified hard
The raw material of matter polyurethane foamed material includes: the white material of 10~15 mass parts, the black material of 10~15 mass parts, 5~10 mass parts
Component A, the component B of 10~15 mass parts, the component C of 10~15 mass parts, 2~8 mass parts additive；
The component A is graphite, graphene/polymer composites, silica, aluminium hydroxide, white carbon black and stone
One of English powder, two or more；
The partial size of the component A is 50-100 nanometers；
The component B is glass bead and/or pearlife；
The component C is hollow glass micropearl and/or hollow ceramic microspheres；
The partial size of the component B and component C is 10-50 microns.
Preferably, the white material is mixed by plurality of raw materials, and the raw material of the white material includes: the poly- of 9~14 mass parts
Ethoxylated polyhydric alcohol or polyester polyol, the foaming agent of 0.5~1 mass parts, the catalyst of 0.01~0.05 mass parts, 0.1~0.5 matter
Measure the silicone oil of part.
Preferably, the foaming agent is physical blowing agent, and the physical blowing agent is pentamethylene.
Preferably, the catalyst includes amines catalyst and/or metal-based catalysts；
The amines catalyst is N, N- dimethyl cyclohexyl amine, pentamethyl-diethylenetriamine, N, N- dimethyl benzylamine or three
Ethylene diamine；
The metal-based catalysts are organo-tin compound, bismuth organic compound or organic zinc compound.
Preferably, the black material is isocyanates, and the isocyanates is '-diphenylmethane diisocyanate.
Preferably, the additive is one of plasticizer, UV resistant agent, diluent, fire retardant and pigment, two
Kind is a variety of.
A kind of preparation method of inorganic material-modified rigid polyurethane foam described in any one among the above, packet
Include the step of next coming in order carry out:
1) each raw material is uniformly mixed according to the formula of white material and produces white material, it is spare；
2) white material made from step 1), component A, component B, component C and additive are uniformly mixed according to formula；
3) black material is added to step 2) after mixing in mixing liquid obtained, be put into mold after mixing evenly according to
It is secondary to be foamed and cured, inorganic material-modified rigid polyurethane foam is made after the completion.
Preferably, in step 3), speed of agitator 2500-3000r/min, curing temperature is 40-50 DEG C.
This application provides a kind of inorganic material-modified rigid polyurethane foams, are made of plurality of raw materials, the nothing
The raw material of machine material modification rigid polyurethane foam include: the white material of 10~15 mass parts, 10~15 mass parts black material,
The component A of 5~10 mass parts, the component B of 10~15 mass parts, 10~15 mass parts component C, 2~8 mass parts addition
Agent；Component A is one in graphite, graphene/polymer composites, silica, aluminium hydroxide, white carbon black and silica flour
It plants, two or more；The partial size of the component A is 50-100 nanometers；Component B is glass bead and/or pearlife；Component C is
Hollow glass micropearl and/or hollow ceramic microspheres；The partial size of the component B and component C is 10-50 microns；
Present invention also provides a kind of preparation methods of above-mentioned inorganic material-modified rigid polyurethane foam；
The application is by addO-on therapy A, component B and component C these inorganic material, to rigid polyurethane foam material
Material is modified, and the thermal coefficient of modified rigid polyurethane foam material obtained is 0.025-0.030W/ (m.k), fire prevention
Grade is A grades, and fire prevention detection result indicator meets the regulation of GB/T8624, and fire protecting performance reaches A2 grades, thus guaranteeing hard
On the basis of the thermal insulation property of polyurethane foamed material, the fire-protection rating of rigid polyurethane foam is improved.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions only further illustrate feature and advantage of the invention, rather than to the limit of the claims in the present invention
System.
This application provides a kind of inorganic material-modified rigid polyurethane foams, are made of plurality of raw materials, the nothing
The raw material of machine material modification rigid polyurethane foam include: the white material of 10~15 mass parts, 10~15 mass parts black material,
The component A of 5~10 mass parts, the component B of 10~15 mass parts, 10~15 mass parts component C, 2~8 mass parts addition
Agent；
Component A is graphite, graphene/polymer composites, silica, aluminium hydroxide, white carbon black and silica flour
One of, two or more；
The partial size of the component A is 50-100 nanometers；
Component B is glass bead and/or pearlife；
Component C is hollow glass micropearl and/or hollow ceramic microspheres；
The partial size of the component B and component C is 10-50 microns.
In one embodiment of the application, the white material is mixed by plurality of raw materials, and the raw material of the white material includes:
The polyether polyol or polyester polyol of 9~14 mass parts, the foaming agent of 0.5~1 mass parts, 0.01~0.05 mass parts are urged
The silicone oil of agent, 0.1~0.5 mass parts.
In one embodiment of the application, the foaming agent is physical blowing agent, and the physical blowing agent is pentamethylene.
In one embodiment of the application, the catalyst includes amines catalyst and/or metal-based catalysts；
The amines catalyst is N, N- dimethyl cyclohexyl amine, pentamethyl-diethylenetriamine, N, N- dimethyl benzylamine or three
Ethylene diamine；
The metal-based catalysts are organo-tin compound, bismuth organic compound or organic zinc compound.
In one embodiment of the application, the black material is isocyanates, and the isocyanates is that diphenyl-methane two is different
Cyanate.
In one embodiment of the application, the additive be plasticizer, UV resistant agent, diluent, fire retardant with
And one of pigment, two or more.
Present invention also provides inorganic material-modified rigid polyurethane foams described in a kind of any one among the above
The preparation method of material includes the steps that next coming in order carry out:
1) each raw material is uniformly mixed according to the formula of white material and produces white material, it is spare；
2) white material made from step 1), component A, component B, component C and additive are uniformly mixed according to formula；
3) black material is added to step 2) after mixing in mixing liquid obtained, be put into mold after mixing evenly according to
It is secondary to be foamed and cured, inorganic material-modified rigid polyurethane foam is made after the completion.
In one embodiment of the application, in step 3), speed of agitator 2500-3000r/min, curing temperature is
40-50℃。
Graphene/polymer composites used in the present invention are graphene/polymerizations using situ aggregation method production
Object composite material.Preparation method is: in situ in polymerization, graphite or modified graphite are blended with monomer or performed polymer first,
The dispersion of suitable initiator is entered, then adjusts and stablizes the parameters such as time, with heat or radiation-initiated polymerization, graphite is finally made
Alkene/polymer composites.
Above-mentioned '-diphenylmethane diisocyanate, nickname methyl diphenylene diisocyanate referred to as " MDI " have 4,4'- hexichol
The isomers such as methane diisocyanate, 2,4'- '-diphenylmethane diisocyanate, 2,2'- '-diphenylmethane diisocyanate, are aromatic hydrocarbons
Downstream major product is widely used in polyurethane elastomer, the polyurethane materials such as manufacture synthetic fibers, artificial leather, solventless coatings
The production field of material.
AddO-on therapy A in inventive formulation, primarily to by modified, reduce polyurethane material thermal coefficient or
It keeps the thermal coefficient of polyurethane material not improve, excellent thermal insulation property is reached, because of graphite, graphene/polymer
Composite material, silica, aluminium hydroxide, the thermal coefficient of white carbon black and silica flour are relatively low, and combustion rating is A grades.
AddO-on therapy B in inventive formulation, primarily as aggregate, because pearlife material itself is hollow, quality
Gently, belong to incombustible material (A grades), thermal coefficient be 0.035W/ (m.K), mixed with polyurethane material be ideal aggregate (as
Backing material use).
AddO-on therapy C in inventive formulation, primarily to improving the resistance to compression of material of the present invention, tension, combustion rating
Effect, because hollow ceramic microspheres have thermal coefficient low (0.040W/ (m.K)), compression strength is high, and A grades of combustion rating etc. excellent
Performance indicator more, after being used in mixed way with polyurethane, loss rate of quality after burning >=50% has reached the regulation of GB/T8624.
The component A, the component B that are added in the present invention and component C these three materials all have thermal coefficient it is low, it is inorganic not
The superior performance indicators such as combustion, resistance to compression, tensile strength height, compensate for the defect of polyurethane material, improve fire protecting performance, and protect
The original low heat conductivity energy of polyurethane, superior waterproof performance are stayed.
In fact, above-mentioned various ingredients be not it is isolated work, influence be it is mutual, any of which component it is more
It is few that variation is brought to the performance of material.After every kind of component has effect independent, but this component is combined with each other, group divides it
Between mutually excite, mutually promote, synergistic effect clearly, so that the comprehensive performance of material is significantly improved.
There is no limit using in the art to processing equipment unmentioned in the above method and technological parameter by the present invention
Processing equipment and technological parameter known to technical staff.
For a further understanding of the present invention, below with reference to embodiment to a kind of inorganic material-modified hard provided by the invention
Polyurethane foamed material and preparation method thereof is described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
A kind of inorganic material-modified rigid polyurethane foam, is made of plurality of raw materials, described inorganic material-modified hard
The raw material of matter polyurethane foamed material include: the white material of 11Kg, the '-diphenylmethane diisocyanate of 13Kg, 7Kg graphene/it is poly-
Compound composite material, the pearlife of 13Kg, the hollow ceramic microspheres of 11kg, 5Kg diluent (water in diluent finished product at
Meeting drying and volatilizing is fallen during type)；
The raw material of the white material include: the polyether polyol of 10Kg, the pentamethylene of 0.7Kg, 0.03Kg N, N- dimethyl
The silicone oil of cyclohexylamine, 0.27kg.
The preparation method of above-mentioned inorganic material-modified rigid polyurethane foam in the present embodiment 1, including it is following
The step of successively carrying out:
1) each raw material is uniformly mixed according to the formula of white material and produces white material, it is spare；
2) according to being formulated that white material made from step 1), graphene/polymer composites, pearlife, hollow ceramic is micro-
Pearl and diluent are uniformly mixed；
3) black material is added to step 2) after mixing in mixing liquid obtained, be put into mold after mixing evenly according to
It is secondary to be foamed and cured, inorganic material-modified rigid polyurethane foam is made after the completion；
In step 3), speed of agitator 2500-3000r/min, curing temperature is 40-50 DEG C.
The performance test results of the plate of the inorganic material-modified rigid polyurethane foam of 1 embodiment 1 of table preparation
| Project | Performance indicator |
| Perpendicular to tensile strength/MPa of board direction | ≥0.10 |
| Compressive strength/MPa | ≥0.12 |
| Dimensional stability/% | ≤0.4 |
| Volume water absorption rate/% | ≤3 |
| Bending strength/MPa | ≥0.15 |
| Moisture permeable coefficient/ng/ (msPa) | ≤8.0 |
| Burning behavior class | A grades (A2 grades) |
| Density Kg/m3 | 55 |
| Coefficient of softing | 0.6 |
| Thermal coefficient W/ (m.k) | ≤0.028 |
| Dry density contraction/% | ≤0.3 |
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (8)
1. a kind of inorganic material-modified rigid polyurethane foam, which is characterized in that be made of plurality of raw materials, the inorganic material
Material modified rigid polyurethane foam material raw material include: the white material of 10~15 mass parts, the black material of 10~15 mass parts, 5~
The component A of 10 mass parts, the component B of 10~15 mass parts, the component C of 10~15 mass parts, 2~8 mass parts additive；
The component A is graphite, graphene/polymer composites, silica, aluminium hydroxide, white carbon black and silica flour
One of, two or more；
The partial size of the component A is 50-100 nanometers；
The component B is glass bead and/or pearlife；
The component C is hollow glass micropearl and/or hollow ceramic microspheres；
The partial size of the component B and component C is 10-50 microns.
2. inorganic material-modified rigid polyurethane foam according to claim 1, which is characterized in that the white material by
Plurality of raw materials mixes, the raw material of the white material include: 9~14 mass parts polyether polyol or polyester polyol, 0.5~
The foaming agent of 1 mass parts, the catalyst of 0.01~0.05 mass parts, 0.1~0.5 mass parts silicone oil.
3. inorganic material-modified rigid polyurethane foam according to claim 2, which is characterized in that the foaming agent
For physical blowing agent, the physical blowing agent is pentamethylene.
4. inorganic material-modified rigid polyurethane foam according to claim 2, which is characterized in that the catalyst
Including amines catalyst and/or metal-based catalysts；
The amines catalyst is N, N- dimethyl cyclohexyl amine, pentamethyl-diethylenetriamine, N, N- dimethyl benzylamine or triethylene
Diamines；
The metal-based catalysts are organo-tin compound, bismuth organic compound or organic zinc compound.
5. inorganic material-modified rigid polyurethane foam according to claim 1, which is characterized in that the black material is
Isocyanates, the isocyanates are '-diphenylmethane diisocyanate.
6. inorganic material-modified rigid polyurethane foam according to claim 1, which is characterized in that the additive
For one of plasticizer, UV resistant agent, diluent, fire retardant and pigment, two or more.
7. the preparation of inorganic material-modified rigid polyurethane foam described in any one in a kind of claim 1~6
Method, which is characterized in that include the steps that next coming in order carry out:
1) each raw material is uniformly mixed according to the formula of white material and produces white material, it is spare；
2) white material made from step 1), component A, component B, component C and additive are uniformly mixed according to formula；
3) black material is added to step 2) after mixing in mixing liquid obtained, be put into mold after mixing evenly successively into
Row foaming and curing, are made inorganic material-modified rigid polyurethane foam after the completion.
8. preparation method according to claim 7, which is characterized in that in step 3), speed of agitator 2500-3000r/
Min, curing temperature are 40-50 DEG C.
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Cited By (6)
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| CN111484724A (en) * | 2020-02-11 | 2020-08-04 | 常德艾利特新材料科技有限公司 | Polyurethane composite material and preparation method thereof |
| CN111518384A (en) * | 2020-06-28 | 2020-08-11 | 四川金网通电子科技有限公司 | Polyurethane coated flame-retardant sealing rubber strip |
| CN111574678A (en) * | 2020-06-03 | 2020-08-25 | 湖南省普瑞达内装材料有限公司 | Anti-static polyurethane foam base material, preparation method thereof and adhesive tape |
| CN112778482A (en) * | 2020-12-30 | 2021-05-11 | 江苏奥斯佳材料科技股份有限公司 | Polyurethane rigid foam composition, polyurethane rigid foam material and preparation method thereof |
| CN115181240A (en) * | 2022-08-03 | 2022-10-14 | 福建冠翔日用塑料制品有限公司 | Wear-resistant heat-insulating polyurethane rigid foam plastic and preparation method thereof |
| CN117736396A (en) * | 2023-12-19 | 2024-03-22 | 湖南省森研高分子新材料股份有限公司 | Polyurethane heat-insulating foamed plastic and preparation method thereof |
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