CN112063004A - Environment-friendly high-heat-preservation polyurethane heat-preservation layer and foaming method - Google Patents
Environment-friendly high-heat-preservation polyurethane heat-preservation layer and foaming method Download PDFInfo
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- CN112063004A CN112063004A CN202010969928.6A CN202010969928A CN112063004A CN 112063004 A CN112063004 A CN 112063004A CN 202010969928 A CN202010969928 A CN 202010969928A CN 112063004 A CN112063004 A CN 112063004A
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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
- C08J9/04—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
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/48—Polyethers
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
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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
- C08J9/04—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
- C08J9/06—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 chemical blowing agent
- C08J9/08—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 chemical blowing agent developing carbon dioxide
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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
- C08J9/143—Halogen containing compounds
- C08J9/147—Halogen containing compounds containing carbon and halogen atoms only
- C08J9/148—Halogen containing compounds containing carbon and halogen atoms only perfluorinated
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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
- 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
- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
- C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
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- C—CHEMISTRY; METALLURGY
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- 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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Abstract
The invention discloses an environment-friendly high-heat-insulation polyurethane heat-insulation layer, and relates to the technical field of polyurethane foaming. The invention comprises the following components in parts by weight: 100 parts of white material; 25-35 parts of a foaming agent; 0.5-2.5 parts of foaming auxiliary agent; 150 portions of black material and 165 portions; the foaming agent is foaming agent LBA with the chemical name HCFO-1233 zd; the foaming auxiliary agent is MFT with the chemical name of CZ95190 and is an isomer of perfluoroolefin. According to the invention, the foaming agent LBA is used as the foaming agent, and the foaming auxiliary agent MFT is used as the foaming auxiliary agent, so that the GWP value is effectively reduced, and finer cells are obtained, thereby effectively improving the environmental protection performance and the heat insulation performance of the heat insulation layer.
Description
Technical Field
The invention belongs to the technical field of polyurethane foaming, and particularly relates to an environment-friendly high-heat-insulation polyurethane heat-insulation layer and a foaming method.
Background
With the development of technology, environmental protection is gradually paid attention to, and household electrical appliances such as refrigerators and freezers are also developed towards green environmental protection. The mainstream foaming technology of the refrigerator and freezer box body at present adopts 245fa and cyclopentane to be mixed as a foaming agent. 245fa is chemically known as HFC-245fa, the molecular formula is CF3CH2CHF2, the gas phase thermal conductivity at 25 ℃ is 12.2mw/mk, and the global warming potential (all of which are abbreviated as GWP hereinafter) is 990; the chemical name of the cyclopentane is C5, the molecular formula is C5H10, the gas phase thermal conductivity at 25 ℃ is 12.0mw/mk, and the global warming potential is 11. Therefore, the GWP value of 245fa is particularly high, the foaming agent is not environment-friendly, the gas-phase thermal conductivity of 245fa and cyclopentane is more than 12mw/mk, and the thermal insulation performance is poor.
Polyurethane foam is a closed-cell, approximately homogeneous substance, and the thermal insulation performance of the polyurethane foam mainly relates to three aspects: the content of the foaming agent in the foam holes is mainly related to the dosage of the foaming agent and the reaction speed; secondly, the type of the foaming agent in the foam holes is mainly the gas phase heat conductivity of the foaming agent, and the lower the heat conductivity is, the better the heat preservation performance is; and thirdly, the number of the foam holes is larger, the nucleation rate is higher, the more the foam holes are, the smaller the pore diameter of the foam holes is, and the better the heat preservation performance is.
245fa is the mainstream foaming agent at present, and the heat preservation principle is as follows: 245fa has a molecular formula in which 3 carbon atoms carry 5 fluorine atoms, which can increase the nucleation rate of polyurethane foam during the foaming process. 245fa has poorer gas phase thermal conductivity at 25 ℃ than cyclopentane, but the comprehensive thermal insulation performance is better than that of cyclopentane because 5 fluorine atoms are contained in the molecular formula of 245fa, thus improving the nucleation rate of foam, increasing the foam cells, reducing the pore diameter of the cells, further reducing the heat conduction of solid parts and lowering the overall thermal conductivity.
However, 245fa and cyclopentane are still poor in environmental protection performance and thermal insulation performance when used as foaming agents, and therefore, improvement of the existing foaming formula is urgently needed to further improve the environmental protection performance and the thermal insulation performance of foaming.
Disclosure of Invention
The invention aims to provide an environment-friendly high-heat-insulation polyurethane heat-insulation layer, wherein a foaming agent LBA is used as a foaming agent, and a foaming auxiliary agent MFT is used as a foaming auxiliary agent, so that the GWP value is effectively reduced, the heat-insulation performance is improved, and the problems of poor environment-friendly performance and poor heat-insulation performance of the conventional heat-insulation layer are solved.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to an environment-friendly high-heat-preservation polyurethane heat-preservation layer, which comprises the following components in parts by weight:
the foaming agent is foaming agent LBA with the chemical name HCFO-1233 zd; the foaming auxiliary agent is a foaming auxiliary agent MFT with the chemical name of CZ95190 and is an isomer of perfluoroolefin.
Further, the white material comprises polyether polyol, water, a catalyst and a stabilizer.
Further, the black material is isocyanate, the viscosity of the black material is 300-400(25 ℃)/mPa.s, and the content of the isocyanate is 30-32%.
A foaming method of an environment-friendly high-heat-insulation polyurethane heat-insulation layer comprises the following steps:
the method comprises the following steps: mixing white materials, a foaming agent and a foaming auxiliary agent in parts by mass in a white material premixing tank at the material temperature of 18 ℃ to obtain a mixed white material;
step two: under the condition that the material temperature is 18 ℃, putting the black material into a black material premixing tank, and uniformly stirring to obtain a premixed black material;
step three: simultaneously injecting the mixed white material and the premixed black material into an inner cavity of a material injection gun head, and injecting the mixture into a box body mould to be foamed through a gun head nozzle after the mixture is fully mixed;
step four: and after cooling and solidification, demolding to form the hard polyurethane heat insulating layer in the box body.
The invention has the following beneficial effects:
according to the invention, the foaming agent LBA is used as the foaming agent, and the foaming auxiliary agent MFT is used as the foaming auxiliary agent, so that the GWP value is effectively reduced, and finer cells are obtained; meanwhile, the LBA foaming agent has a low boiling point and has better heat insulation performance at a low temperature, so that the environmental protection performance and the heat insulation performance of the heat insulation layer are effectively improved.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
Example 1
The invention relates to an environment-friendly high-heat-preservation polyurethane heat-preservation layer, which comprises the following components in parts by weight:
the white material comprises polyether polyol, water, a catalyst and a stabilizer, and specifically comprises the following raw materials in percentage by mass:
wherein the black material is isocyanate, the viscosity of the black material is 300-400(25 ℃)/mPa.s, and the content of the isocyanate is 30-32%.
A foaming method of an environment-friendly high-heat-insulation polyurethane heat-insulation layer comprises the following steps:
the method comprises the following steps: mixing the white material, the foaming agent LBA and the foaming auxiliary agent MFT in parts by mass in a white material premixing tank at the material temperature of 18 ℃ to obtain a mixed white material.
Step two: and (3) under the condition that the material temperature is 18 ℃, putting the black material into a black material premixing tank, and uniformly stirring to obtain the premixed black material.
Step three: and injecting the mixed white material and the premixed black material into an inner cavity of a material injection gun head at high speed and high pressure, and injecting the mixture into a to-be-foamed box body mould through a gun head nozzle after the mixture is fully mixed.
Step four: after the foaming raw material is cooled and solidified for a period of time in the mould, demoulding is carried out, and a rigid polyurethane heat-insulating layer is formed in the box body.
Comparative example
The formula of the heat-insulating layer comprises the following raw materials in parts by mass:
the white and black materials were the same as in example 1.
The foaming method of the heat-insulating layer comprises the following steps:
the method comprises the following steps: mixing the white material, the LBA and the cyclopentane in parts by mass in a white material premixing tank at the material temperature of 18 ℃ to obtain a mixed white material;
the second to fourth steps are the same as those in example 1.
Then, the polyurethane heat-insulating layers obtained in the embodiment 1 and the comparative example are subjected to comparison test, and the technical parameters are shown in the table 1 for performance comparison; wherein, the ratio of black to white in table 1 refers to the ratio of black to white in parts.
As can be seen from the above table, the thermal conductivity of the polyurethane insulation layer of the environment-friendly high-insulation foaming system prepared in example 1 is only 15.6mw/mk, which is the lowest in the industry at present; meanwhile, the foam has very small cell size, which means that the foam with the same area contains more cells, and the increase of the number of the cells can effectively reduce the heat convection, thereby reducing the overall heat conductivity of the polyurethane heat-insulating layer and effectively improving the heat-insulating property.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. The environment-friendly high-heat-insulation polyurethane heat-insulation layer is characterized by comprising the following components in parts by mass:
the foaming agent is foaming agent LBA with the chemical name HCFO-1233 zd;
the foaming auxiliary agent is a foaming auxiliary agent MFT with the chemical name of CZ95190 and is an isomer of perfluoroolefin.
2. The environment-friendly high-insulation polyurethane insulation layer as claimed in claim 1, wherein the white pigment comprises polyether polyol, water, catalyst and stabilizer.
3. The environment-friendly high-thermal-insulation polyurethane thermal-insulation layer as claimed in claim 1, wherein the black material is isocyanate with viscosity of 300-.
4. A foaming method of the environment-friendly high-insulation polyurethane heat-insulating layer as claimed in any one of claims 1 to 3, which comprises the following steps:
the method comprises the following steps: mixing white materials, a foaming agent and a foaming auxiliary agent in parts by mass in a white material premixing tank at the material temperature of 18 ℃ to obtain a mixed white material;
step two: under the condition that the material temperature is 18 ℃, putting the black material into a black material premixing tank, and uniformly stirring to obtain a premixed black material;
step three: simultaneously injecting the mixed white material and the premixed black material into an inner cavity of a material injection gun head, and injecting the mixture into a box body mould to be foamed through a gun head nozzle after the mixture is fully mixed;
step four: and after cooling and solidification, demolding to form the hard polyurethane heat insulating layer in the box body.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010969928.6A CN112063004A (en) | 2020-09-15 | 2020-09-15 | Environment-friendly high-heat-preservation polyurethane heat-preservation layer and foaming method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574387A (en) * | 2020-12-14 | 2021-03-30 | 长虹美菱股份有限公司 | Low-cost environment-friendly polyurethane foaming material and foaming process thereof |
| CN112812354A (en) * | 2020-12-30 | 2021-05-18 | 长虹美菱股份有限公司 | Polyurethane foaming agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106838A (en) * | 1993-12-10 | 1995-08-16 | 日清纺绩株式会社 | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US20160200889A1 (en) * | 2013-09-19 | 2016-07-14 | Dow Global Technologies Llc | Vacuum assisted process to make closed cell rigid polyurethane foams using mixed blowing agents |
| CN107163221A (en) * | 2017-06-28 | 2017-09-15 | 合肥美菱股份有限公司 | A kind of refrigerator for the high-quality polyurethane foam system of refrigerator and based on it |
| CN110105520A (en) * | 2019-05-05 | 2019-08-09 | 深圳市盈石科技有限公司 | A kind of heat preservation hard polyurethane foams and preparation method thereof |
-
2020
- 2020-09-15 CN CN202010969928.6A patent/CN112063004A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106838A (en) * | 1993-12-10 | 1995-08-16 | 日清纺绩株式会社 | Halogen-free blowing agents that include cycloaliphatic hydrocarbons and are suitable for isocyanate-based polymeric foams |
| US20160200889A1 (en) * | 2013-09-19 | 2016-07-14 | Dow Global Technologies Llc | Vacuum assisted process to make closed cell rigid polyurethane foams using mixed blowing agents |
| CN107163221A (en) * | 2017-06-28 | 2017-09-15 | 合肥美菱股份有限公司 | A kind of refrigerator for the high-quality polyurethane foam system of refrigerator and based on it |
| CN110105520A (en) * | 2019-05-05 | 2019-08-09 | 深圳市盈石科技有限公司 | A kind of heat preservation hard polyurethane foams and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574387A (en) * | 2020-12-14 | 2021-03-30 | 长虹美菱股份有限公司 | Low-cost environment-friendly polyurethane foaming material and foaming process thereof |
| CN112812354A (en) * | 2020-12-30 | 2021-05-18 | 长虹美菱股份有限公司 | Polyurethane foaming agent |
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Application publication date: 20201211 |