CN112592453A - Hard polyurethane foam plastic with constant temperature function and preparation method thereof - Google Patents
Hard polyurethane foam plastic with constant temperature function and preparation method thereof Download PDFInfo
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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
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
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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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/58—Epoxy resins
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- 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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- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- 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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- C—CHEMISTRY; METALLURGY
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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Abstract
The invention discloses a hard polyurethane foam plastic with a constant temperature function, which is prepared from the following components in parts by weight: 70-90 parts by weight of polyisocyanate; 50-80 parts of polyol; 4-10 parts of foaming agent; 0.5-1 part by weight of catalyst; 1-5 parts of a pore forming agent; 1-2 parts of foam stabilizer; 1-2 parts of a crosslinking agent; 1-3 parts of an external foaming agent; 5-10 parts of phase change heat storage material; 3-7 parts of expanded graphite; the rigid polyurethane foam plastic and the preparation method thereof can obviously improve the flame retardant property of the rigid polyurethane foam plastic, ensure that the rigid polyurethane foam plastic still has good mechanical property at lower density, simultaneously have the functions of heat preservation and temperature regulation, and greatly improve the usability of the rigid polyurethane foam plastic in the field of building materials.
Description
Technical Field
The invention relates to the technical field of foamed plastics, in particular to rigid polyurethane foamed plastics with a constant temperature function and a preparation method thereof.
Background
The rigid polyurethane foam (RPUF) is a structural material with excellent heat insulation performance, can bear a certain load without obvious deformation, and has the advantages of small density, high specific strength, good dimensional stability, high temperature resistance, good adhesion with other matrixes and the like. Therefore, the polyurethane rigid foam has been rapidly developed and widely used in various fields of national economy, and has become one of indispensable high polymer materials. In foreign countries, the polyurethane rigid foam is mainly applied to the field of building heat preservation. While the polyurethane hard foam is mainly applied to the heat preservation fields of refrigerators, freezers, pipelines and the like in China, and the application of the polyurethane hard foam in the heat preservation field of buildings is still at the beginning stage. With the enhancement of energy-saving and environment-friendly consciousness of people and the continuous improvement of national energy-saving standards, the application of the polyurethane rigid foam in the field of building heat insulation is increased explosively, and the rigid foam field becomes the largest future demand bright point of the polyurethane industry.
At present, the obstacles restricting the wide application of rigid polyurethane foam plastic mainly comprise that the flame retardance is insufficient, and the linkage change of reaction is caused by adding a flame retardant substance in the ingredients, so that the mechanical strength and the quality stability of the foam plastic are influenced; secondly, the material can only be used for heat preservation, but does not have the function of temperature regulation, and can only be suitable for extremely cold regions due to seasonal temperature change when being used for building materials, and the application range is not large; thirdly, although the mechanical strength and the heat preservation performance are better, the density of the rigid polyurethane foam for construction is usually more than 150kg/m3The density is still higher, the raw material cost and the transportation and installation cost are both higher, and if the density is reduced, the toughness, the tensile and shear strength and the heat preservation performance are obviously reduced. These deficiencies greatly limit their widespread use in the field of construction materials.
Disclosure of Invention
The invention aims to provide rigid polyurethane foam plastic with a constant temperature function and a preparation method thereof, which can obviously improve the flame retardant property of the rigid polyurethane foam plastic, ensure that the rigid polyurethane foam plastic still has good mechanical property at lower density, and simultaneously have the functions of heat preservation and temperature regulation, thereby greatly improving the usability of the rigid polyurethane foam plastic in the field of building materials.
In order to achieve the above effects, the present invention provides the following technical solutions:
the rigid polyurethane foam plastic with the constant temperature function comprises the following components in parts by weight:
70-90 parts by weight of polyisocyanate;
50-80 parts of polyol;
4-10 parts of foaming agent;
0.5-1 part by weight of catalyst;
1-5 parts of a pore forming agent;
1-2 parts of foam stabilizer;
1-2 parts of a crosslinking agent;
1-3 parts of an external foaming agent;
5-10 parts of phase change heat storage material;
3-7 parts of expanded graphite.
Preferably, the phase-change heat storage material is CaCl2.6H2O。
Preferably, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI).
Preferably, the polyol is a polyester polyol or a polyether polyol.
Preferably, the catalyst is bis-dimethylaminoethyl ether or triethylenediamine.
Preferably, the foam stabilizer is silicone oil; the cross-linking agent is triol or tetraol; the foaming agent is HCFC-141 b.
Preferably, the formula also comprises 1-5 parts by weight of epoxy resin; the epoxy resin is dispersed and filled in a hollow structure formed by a core wrapping process or a capsule taking palmitic acid or stearic acid as a carrier, and the diameter of a single pill is not more than 5 mm.
Preferably, the epoxy resin is a thermosetting epoxy resin or a latent epoxy resin.
The preparation method of the rigid polyurethane foam with the constant temperature function is used for preparing the organosilicon foam, and comprises the following steps:
mixing and stirring polyisocyanate, polyol, a cross-linking agent, a phase change heat storage material and expanded graphite; then adding a foaming agent, a cross-linking agent, a cell opening agent, a foam stabilizer, an external foaming agent and a pill structure, stirring for the second time, and finally adding a catalyst, stirring quickly and foaming.
Preferably, after foaming is finished, the temperature is kept for 5-10min, and then the temperature is gradually reduced to room temperature.
The invention provides a hard polyurethane foam plastic with a constant temperature function and a preparation method thereof, and the hard polyurethane foam plastic has the following beneficial effects:
1. the invention adds the phase-change heat storage material into the rigid polyurethane foam, the phase-change temperature of the phase-change heat storage material is about 29 ℃, the phase-change heat storage material is very suitable for the field of buildings or furniture, the advantages of the rigid polyurethane foam with the phase-change heat storage performance are combined, and the rigid polyurethane foam has a certain constant temperature function, because the rigid polyurethane foam has stronger heat preservation capability, in order to increase the function combination with the phase-change heat storage material, the expanded graphite is also added, the phase-change heat storage material and the rigid polyurethane foam can be organically combined by adding the expanded graphite, the heat conduction area and the heat conductivity of the phase-change energy storage material can be greatly increased, so that the reaction and the regulation are more sensitive and effective to the external temperature, meanwhile, the expanded graphite can obviously increase the flame retardance of the rigid polyurethane foam, the volume of the rigid polyurethane foam rapidly expands at high temperature, and the formed worm-shaped carbon residue can rapidly, a compact carbon layer is formed to protect a foam main body under the carbon layer and obstruct the propagation of flame, which belongs to a physical expansion flame-retardant mechanism, and the foam flame-retardant material self-expands into carbon to be flame-retardant when being heated, and has the advantages of high expansion speed, high expansion rate and good flame-retardant effect; and the phase-change energy storage material can also effectively improve the heat resistance and the flame retardant property of the hard polyurethane and prolong the flame retardant time of the hard polyurethane.
2. The invention uses the core or capsule pill to wrap the thermosetting or latent epoxy resin to disperse the epoxy resin in the material, because the internal temperature of the hard polyurethane foam plastic can be increased to over one hundred ℃ during the foaming process, the pill can be melted to release the epoxy resin in the pill, at the moment, the foaming of the material is started, the volume is rapidly expanded, and the internal air holes and the porous veins are gradually formed; at the moment, the pellet is melted, the epoxy resin in the pellet is released and is connected in a extending way along the porous veins, so that reticular bones are formed in the foamed material, the structural strength of the foam plastic is obviously enhanced, and the resilience of the prepared foam plastic is obviously improved because the epoxy resin has better elasticity; the epoxy resin coated on the pellet structure can prevent the epoxy resin from being cured in advance, and can also prevent the epoxy resin from being excessively dispersed in the material due to the direct addition of the epoxy resin, and finally, the epoxy resin can exist independently and can not form a reticular skeleton.
3. In the foaming process, after micro bubble nuclei are formed, gas in the system is gradually increased, so that the volume of bubbles is gradually increased, and the reaction system solution or the resin solution becomes the walls of the bubbles. The expansion of the cells causes the cell walls to become thin slowly, so that the viscosity of the system is required to be high enough, the strength of the cell walls is ensured to be high enough, and the phenomenon of foam collapse is prevented. However, if the viscosity is too high, the fluidity of the system solution is easily deteriorated, the system cannot timely compensate for thin pore walls, so that pores overflow, and the obtained plastic has small pores and high density. In the prior art, in order to obtain a product with light weight and large compression modulus, a formula is adjusted to obtain a reaction liquid with appropriate viscosity, and the appropriate formula is a trade secret of a large enterprise, and the formula and the preparation process are influenced by large factors, so that the yield is difficult to ensure, the cost is increased, and the threshold is too high; the invention additionally forms a reticular skeleton structure in the material in the middle and later foaming stages, so that the structural strength in the material is increased, and the gas can be guided to pass through, so that the strength requirement on the pore wall is greatly reduced, the fault tolerance rate is high, the viscosity of the existing formula can be reduced in the production process without influencing the size of the pores, the production cost and the threshold for producing high-quality foam plastic can be greatly reduced, and the production cost is reduced.
4. The rigid polyurethane foam plastic has much lower density than the traditional rigid polyurethane foam plastic for buildings, but still has stronger mechanical strength including tensile strength, shear strength and elastic recovery performance due to the vein structure formed by the epoxy resin, has the traditional advantages of the rigid polyurethane foam plastic, and also has certain temperature regulation capability and good flame retardant property.
Detailed Description
The technical scheme in the embodiment of the invention is clearly and completely described below; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
Example 1:
the invention provides a rigid polyurethane foam plastic with a constant temperature function, which comprises the following components in parts by weight:
70 parts by weight of polyisocyanate;
80 parts by weight of polyol;
4 parts of foaming agent;
0.5 part by weight of a catalyst;
1 part by weight of a pore forming agent;
1 part by weight of foam stabilizer;
1 part by weight of a crosslinking agent;
1 part by weight of external foaming agent;
5 parts of a phase change heat storage material;
3 parts of expanded graphite.
Further, the phase change heat storage material is CaCl2.6H2O。
Further, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI).
Further, the polyol is polyester polyol or polyether polyol.
Further, the catalyst is bis-dimethylaminoethyl ether or triethylenediamine.
Further, the foam stabilizer is silicone oil; the cross-linking agent is triol or tetraol; the foaming agent is HCFC-141 b.
Further, the formula also comprises 1 part by weight of epoxy resin; the epoxy resin is dispersed and filled in a hollow structure formed by a core wrapping process or a capsule taking palmitic acid or stearic acid as a carrier, and the diameter of a single pill is not more than 5 mm.
Further, the epoxy resin is a thermosetting epoxy resin or a latent epoxy resin.
The preparation method of the rigid polyurethane foam with the constant temperature function is used for preparing the organosilicon foam, and comprises the following steps:
mixing and stirring polyisocyanate, polyol, a cross-linking agent, a phase change heat storage material and expanded graphite; then adding a foaming agent, a cross-linking agent, a cell opening agent, a foam stabilizer, an external foaming agent and a pill structure, stirring for the second time, and finally adding a catalyst, stirring quickly and foaming.
Further, after foaming is finished, the temperature is kept for 5-10min, and then the temperature is gradually reduced to the room temperature.
Example 2:
the rigid polyurethane foam plastic with the constant temperature function comprises the following components in parts by weight:
90 parts by weight of polyisocyanate;
50 parts by weight of a polyol;
10 parts by weight of a foaming agent;
1 part by weight of a catalyst;
5 parts of a pore forming agent;
2 parts by weight of a foam stabilizer;
2 parts of a crosslinking agent;
3 parts of an external foaming agent;
10 parts of a phase change heat storage material;
7 parts of expanded graphite.
Further, the phase change heat storage material is CaCl2.6H2O。
Further, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI).
Further, the polyol is polyester polyol or polyether polyol.
Further, the catalyst is bis-dimethylaminoethyl ether or triethylenediamine.
Further, the foam stabilizer is silicone oil; the cross-linking agent is triol or tetraol; the foaming agent is HCFC-141 b.
Preferably, the formula also comprises 5 parts by weight of epoxy resin; the epoxy resin is dispersed and filled in a hollow structure formed by a core wrapping process or a capsule taking palmitic acid or stearic acid as a carrier, and the diameter of a single pill is not more than 5 mm.
Further, the epoxy resin is a thermosetting epoxy resin or a latent epoxy resin.
The preparation method of the rigid polyurethane foam with the constant temperature function is used for preparing the organosilicon foam, and comprises the following steps:
mixing and stirring polyisocyanate, polyol, a cross-linking agent, a phase change heat storage material and expanded graphite; then adding a foaming agent, a cross-linking agent, a cell opening agent, a foam stabilizer, an external foaming agent and a pill structure, stirring for the second time, and finally adding a catalyst, stirring quickly and foaming.
Further, after foaming is finished, the temperature is kept for 5-10min, and then the temperature is gradually reduced to the room temperature.
Example 3:
the rigid polyurethane foam plastic with the constant temperature function comprises the following components in parts by weight:
80 parts by weight of polyisocyanate;
70 parts by weight of polyol;
7 parts by weight of a foaming agent;
0.7 part by weight of a catalyst;
3 parts of a pore forming agent;
1.5 parts by weight of a foam stabilizer;
1.5 parts by weight of a crosslinking agent;
2 parts of an external foaming agent;
7 parts of a phase change heat storage material;
5 parts of expanded graphite.
Further, the phase change heat storage material is CaCl2.6H2O。
Further, the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI).
Further, the polyol is polyester polyol or polyether polyol.
Further, the catalyst is bis-dimethylaminoethyl ether or triethylenediamine.
Further, the foam stabilizer is silicone oil; the cross-linking agent is triol or tetraol; the foaming agent is HCFC-141 b.
Preferably, the formula also comprises 3 parts by weight of epoxy resin; the epoxy resin is dispersed and filled in a hollow structure formed by a core wrapping process or a capsule taking palmitic acid or stearic acid as a carrier, and the diameter of a single pill is not more than 5 mm.
Further, the epoxy resin is a thermosetting epoxy resin or a latent epoxy resin.
The preparation method of the rigid polyurethane foam with the constant temperature function is used for preparing the organosilicon foam, and comprises the following steps:
mixing and stirring polyisocyanate, polyol, a cross-linking agent, a phase change heat storage material and expanded graphite; then adding a foaming agent, a cross-linking agent, a cell opening agent, a foam stabilizer, an external foaming agent and a pill structure, stirring for the second time, and finally adding a catalyst, stirring quickly and foaming.
Further, after foaming is finished, the temperature is kept for 5-10min, and then the temperature is gradually reduced to the room temperature.
The rigid polyurethane foam prepared in the 3 examples is compared with the rigid polyurethane foam for construction sold by a certain tap enterprise purchased in the market in performance tests, and the test results are summarized as follows:
from the above, it can be seen that the density of the rigid polyurethane foam obtained by adopting the formula and the process of the invention is greatly reduced compared with that of the control sample, but at the same time, although various test parameters are not as good as that of the control sample, various mechanical properties can be kept to be close to those of the control sample, and on the whole, the mechanical properties are extremely excellent relative to the density, and the rigid polyurethane foam has the conditions of mass production, transportation and installation with low cost.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The rigid polyurethane foam plastic with the constant temperature function is characterized by comprising the following components in parts by weight:
70-90 parts by weight of polyisocyanate;
50-80 parts of polyol;
4-10 parts of foaming agent;
0.5-1 part by weight of catalyst;
1-5 parts of a pore forming agent;
1-2 parts of foam stabilizer;
1-2 parts of a crosslinking agent;
1-3 parts of an external foaming agent;
5-10 parts of phase change heat storage material;
3-7 parts of expanded graphite.
2. The rigid polyurethane foam with the constant temperature function as claimed in claim 1, wherein the phase-change heat storage material is CaCl2.6H2O。
3. Rigid polyurethane foam with thermostatic function according to claim 1, characterized in that the polyisocyanate is one or more mixtures of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or polymethylene polyphenyl polyisocyanate (PAPI).
4. The rigid polyurethane foam having a thermostatic function according to claim 1, wherein the polyol is a polyester polyol or a polyether polyol.
5. The rigid polyurethane foam having a thermostatic function according to claim 1, characterized in that the catalyst is bis-dimethylaminoethyl ether or triethylenediamine.
6. The rigid polyurethane foam with a constant temperature function according to claim 1, wherein the foam stabilizer is silicone oil; the cross-linking agent is triol or tetraol; the foaming agent is HCFC-141 b.
7. The rigid polyurethane foam with a constant temperature function as claimed in claim 1, further comprising 1-5 parts by weight of an epoxy resin; the epoxy resin is dispersed and filled in a hollow structure formed by a core wrapping process or a capsule taking palmitic acid or stearic acid as a carrier, and the diameter of a single pill is not more than 5 mm.
8. The rigid polyurethane foam with a constant temperature function according to claim 7, wherein the epoxy resin is a heat-curable epoxy resin or a latent epoxy resin.
9. A process for producing a rigid polyurethane foam having a constant temperature function, for producing the silicone foam according to claim 7, comprising:
mixing and stirring polyisocyanate, polyol, a cross-linking agent, a phase change heat storage material and expanded graphite; then adding a foaming agent, a cross-linking agent, a cell opening agent, a foam stabilizer, an external foaming agent and a pill structure, stirring for the second time, and finally adding a catalyst, stirring quickly and foaming.
10. The preparation method of rigid polyurethane foam with constant temperature function as claimed in claim 9, wherein the temperature is kept for 5-10min and then gradually reduced to room temperature after foaming is completed.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114057974A (en) * | 2021-10-08 | 2022-02-18 | 山东北理华海复合材料有限公司 | Polyurethane low-heat-release foaming composite material and preparation method thereof |
Citations (3)
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Application publication date: 20210402 |