CN109762136B - Polyurethane foaming composition, polyurethane foam, and preparation method and application thereof - Google Patents
Polyurethane foaming composition, polyurethane foam, and preparation method and application thereof Download PDFInfo
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- CN109762136B CN109762136B CN201910074566.1A CN201910074566A CN109762136B CN 109762136 B CN109762136 B CN 109762136B CN 201910074566 A CN201910074566 A CN 201910074566A CN 109762136 B CN109762136 B CN 109762136B
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Abstract
The invention discloses a polyurethane foaming composition, polyurethane foam, a preparation method and application thereof, and relates to the technical field of heat insulation materials, so as to ensure that the polyurethane foam prepared from the polyurethane foaming composition not only has good heat insulation performance, but also has lower density and good anti-shrinkage deformation capability. The polyurethane foaming composition comprises: polyol, polyisocyanate, catalyst, organic ammonium salt foaming agent and fluoro-olefin foaming agent. The polyurethane foam is prepared from the polyurethane foaming composition. The polyurethane foaming composition, the polyurethane foam and the preparation method thereof provided by the invention are applied to temperature control equipment.
Description
Technical Field
The invention relates to the technical field of temperature control, in particular to a polyurethane foaming composition, polyurethane foam, and a preparation method and application thereof.
Background
At present, the physical foaming agents used in the process of preparing rigid polyurethane foams mainly include: hydrofluorocarbon foaming agents, hydrocarbon foaming agents and environmentally friendly low temperature chamber effect foaming agents, such as fluoroolefin foaming agents, which have been developed in recent years to meet increasingly stringent environmental and energy requirements.
In order to reduce the production cost of the refrigeration equipment, the rigid polyurethane foam used by the existing refrigeration equipment manufacturers is required to have lower density. If the rigid polyurethane foam prepared by the fluoroolefin foaming agent reaches a lower density, the mechanical properties of the polyurethane foam, such as shrinkage deformation resistance, are sacrificed, so that the refrigeration equipment has certain quality hidden trouble.
Disclosure of Invention
The invention aims to provide a polyurethane foaming composition, polyurethane foam, a preparation method, application and refrigeration equipment of the polyurethane foaming composition, so as to ensure that the polyurethane foam prepared from the polyurethane foaming composition has good heat insulation performance, lower density and good pressure resistance.
In order to achieve the above object, the present invention provides a polyurethane foam composition comprising: polyol, polyisocyanate, catalyst, organic ammonium salt foaming agent and fluoro-olefin foaming agent.
Compared with the prior art, the polyurethane foaming composition provided by the invention contains an organic ammonium salt foaming agent and a fluoro olefin foaming agent besides polyol, polyisocyanate and a catalyst. Under the catalysis of a catalyst, when the polyol and the polyisocyanate are subjected to a foaming reaction, the organic ammonium salt foaming agent can generate a small molecular alcohol amine compound containing active hydrogen; the small molecular alcohol amine compound can be used as a chain extender, the cross-linking reaction of the polyurethane generated by the polyol and the polyisocyanate is controlled to form a compact reticular structure, and the polyurethane foam prepared from the polyurethane foaming composition has good compression resistance and pressure resistance, so that the polyurethane foam prepared from the polyurethane foaming composition has better compression resistance and pressure resistance compared with the existing polyurethane foam under the same density; in other words, the polyurethane foam prepared by using the polyurethane foaming composition provided by the invention has lower density compared with the existing polyurethane foam under the same compression resistance and pressure resistance. Moreover, the organic ammonium salt foaming agent and the fluoroolefin foaming agent contained in the polyurethane foaming composition provided by the invention can effectively promote the heat insulation performance of the polyurethane foam prepared from the polyurethane foaming composition, so that the polyurethane foam prepared from the polyurethane foaming composition has good heat insulation performance, lower density and good pressure resistance.
Moreover, in the polyurethane foaming composition provided by the invention, the organic ammonium salt foaming agent can assist in improving the heat insulation performance of the polyurethane foam, so that compared with a polyurethane foaming composition with a fluoro-olefin foaming agent added alone, the polyurethane foaming composition provided by the invention contains less fluoro-olefin foaming agent, and the production cost for preparing the polyurethane foam by adopting the polyurethane foaming composition provided by the invention is lower.
The invention also provides polyurethane foam which is prepared from the polyurethane foaming composition.
Compared with the prior art, the beneficial effects of the polyurethane foam provided by the invention are the same as those of the polyurethane foaming composition, and are not repeated herein.
The invention also provides a preparation method of the polyurethane foam, which comprises the following steps:
the polyurethane foam is prepared from a polyurethane foam composition.
Compared with the prior art, the preparation method of the polyurethane foam provided by the invention has the same beneficial effects as those of the polyurethane foaming composition, and is not repeated herein.
The invention also provides the application of the polyurethane foam or the polyurethane foam prepared by the preparation method of the polyurethane foam in temperature control equipment.
Compared with the prior art, the application provided by the invention has the same beneficial effects as the polyurethane foaming composition, and the details are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a first flow chart of a method for preparing a polyurethane foam according to an embodiment of the present invention;
FIG. 2 is a flow chart of a second method for preparing polyurethane foam according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
The embodiment of the invention provides a polyurethane foaming composition, which comprises the following components in part by weight: polyol, polyisocyanate, catalyst, organic ammonium salt foaming agent and fluoro-olefin foaming agent.
The fluoroolefin foaming agent has good heat preservation effect, zero Ozone Depletion Potential (ODP), low Global Warming Potential (GWP), good environmental protection property, good heat preservation effect and high price. The fluoroolefin foaming agent includes one or more of trans-1-chloro-3, 3, 3-trifluoropropene (HFO-1233 zd (E), manufacturer Honeywell corporation), cis-1, 1,1,4,4, 4-hexafluoro-2-butene (HFO-1336mzz (Z), manufacturer: Chemours corporation), trans-1, 1,1,4,4, 4-hexafluoro-2-butene (HFO-1336mzz (E), manufacturer: Chemours corporation), but is not limited thereto.
Such organic ammonium salt blowing agents include, but are not limited to, the chemical blowing agent CFA8 (manufacturer: Zibo Zhenghua foam Co.). The ODP value of the chemical foaming agent CFA8 is 0, the potential greenhouse effect value (GWP value) is 1, and the chemical foaming agent can react with isocyanate to generate carbon dioxide gas, so that the prepared polyurethane foam has good heat insulation performance. In recent years, the coating has a small amount of application to spray foam, and has the defects of poor fluidity and poor mold release property when used in a refrigerator and a freezer; and because the chemical foaming agent participates in the reaction to generate a large amount of heat, if the added amount is too large, the post-curing and demolding performance of the polyurethane foam can be influenced, and the phenomenon that a metal back plate of a box body or a metal panel of a door body is separated from the foam through bulging is easily caused.
The chemical foaming agent CFA8 is a chemical foaming agent, and can comprise one or more of organic ammonium formate compounds, organic ammonium orthoformate compounds, organic ammonium carbonate compounds and ammonium hydrazinoalcoholate compounds, and the manufacturers are Zibo Zhenghua foaming materials. Among them, the organic ammonium carbonate compound may be an N-hydroxypropylated ammonium carbonate compound disclosed in CN201710529944.1 or an ammonium diisopropylcarbonate salt produced by Butian New Material technology Co.
The polyisocyanate comprises one or more of polyphenyl polymethylene polyisocyanate (also called polymeric MDI, the manufacturer is Nicotiana Wanhua polyurethane Co., Ltd., the brand number is PM2010), 2, 4-toluene diisocyanate (2,4-TDI) and 2, 6-toluene diisocyanate (2, 6-TDI);
the catalyst is one or more of pentamethyl diethylenetriamine (the manufacturer is Evonik company, and the brand is PC-5'), 70% bis (dimethylaminoethyl) ether solution (the manufacturer is Evonik company, and the brand is A-1), N-dimethylcyclohexylamine (the manufacturer is Evonik company, and the brand is PC-8), and a quaternary ammonium salt catalyst TMR-2 (the manufacturer is Evonik company, and the brand is TMR-2).
As can be seen from the above, the polyurethane foam composition provided in the example of the present invention contains an organic ammonium salt type foaming agent and a fluoro olefin type foaming agent in addition to the polyol, the polyisocyanate and the catalyst. Under the catalysis of a catalyst, when the polyol and the polyisocyanate are subjected to a foaming reaction, the organic ammonium salt foaming agent can generate a small molecular alcohol amine compound containing active hydrogen; due to the active hydrogen contained in the micromolecule alcohol amine compound, the micromolecule alcohol amine compound can be used as a chain extender, the cross-linking reaction of the polyurethane generated by the polyol and the polyisocyanate is controlled to form a compact net structure, and the polyurethane foam prepared by the polyurethane foaming composition has good compression resistance and pressure resistance, so that the polyurethane foam prepared by the polyurethane foaming composition provided by the embodiment of the invention has better compression resistance and pressure resistance compared with the existing polyurethane foam under the same density; in other words, the polyurethane foam prepared by using the polyurethane foaming composition provided by the embodiment of the invention has lower density than the existing polyurethane foam under the same compression resistance and pressure resistance. In addition, the organic ammonium salt foaming agent and the fluoroolefin foaming agent contained in the polyurethane foaming composition provided by the embodiment of the invention can effectively promote the heat insulation performance of the polyurethane foam prepared by the polyurethane foaming composition, so that the polyurethane foam prepared by the polyurethane foaming composition has good heat insulation performance, lower density and good pressure resistance.
Moreover, in the polyurethane foaming composition provided by the embodiment of the invention, the organic ammonium salt foaming agent can assist in improving the heat insulation performance of the polyurethane foam, so that compared with a polyurethane foaming composition with a fluoro olefin foaming agent added alone, the polyurethane foaming composition provided by the embodiment of the invention contains less fluoro olefin foaming agent, and the production cost for preparing the polyurethane foam by using the polyurethane foaming composition provided by the embodiment of the invention is lower. Meanwhile, the organic ammonium salt foaming agent and the fluoroolefin foaming agent are compounded to reduce the content of the organic ammonium salt foaming agent in the polyurethane foaming composition, so that the bubbling occurrence probability caused by the overlarge addition amount of the organic ammonium salt foaming agent is reduced, the pungent smell generated in the foaming reaction of the organic ammonium salt foaming agent is reduced, and the application range of the polyurethane foam prepared by adopting the polyurethane foaming composition provided by the embodiment of the invention is favorably expanded. For example: the polyurethane foam prepared from the polyurethane foaming composition singly added with the organic ammonium salt foaming agent in the prior art has strong pungent smell and is difficult to be used in equipment such as refrigerators and heaters, and the pungent smell generated in the polyurethane foam process prepared from the polyurethane foaming composition provided by the embodiment of the invention is small, so that the prepared polyurethane foam can be used in the refrigerators and the heaters.
Therefore, the polyurethane foam prepared from the polyurethane foaming composition provided by the embodiment of the invention has the advantages of good environmental protection property, low heat conductivity coefficient, good mechanical property and relatively low cost, and can be applied to temperature control equipment such as refrigerators, heaters and the like. Moreover, the density of the polyurethane foam can be lower on the premise of keeping the mechanical property of the polyurethane foam according to the actual requirement. In addition, the components contained in the polyurethane foaming composition have boiling points of more than 18 ℃ and have good process operability.
The above polyol is a polyol composition comprising a polyether polyol and/or a polyester polyol.
When the polyol comprises polyether polyol, the polyether polyol comprises at least two of polypropylene oxide polyether polyol taking sucrose and triethanolamine as composite initiators, polypropylene oxide polyether polyol taking glycerin as an initiator, polypropylene oxide polyether polyol taking toluenediamine as an initiator, polypropylene oxide polyether polyol taking sorbitol as an initiator and polypropylene oxide polyether polyol taking ethylenediamine as an initiator;
the functionality of the polypropylene oxide polyether polyol taking sucrose and triethanolamine as composite initiators is 5, the hydroxyl value is 320 mg/KOH/g-400 mg/KOH/g, and the polypropylene oxide polyether polyol is defined as polyether A.
The functionality of the polypropylene oxide polyether polyol taking glycerol as an initiator is 3, the hydroxyl value is 300 mg/KOH/g-360 mg/KOH/g, and the polypropylene oxide polyether polyol is defined as polyether B.
The functionality of the polypropylene oxide polyether polyol taking the toluenediamine as an initiator is 4, the hydroxyl value is 370 mg/KOH/g-450 mg/KOH/g, and the polypropylene oxide polyether polyol is defined as polyether C.
The functionality of the polypropylene oxide polyether polyol taking sorbitol as an initiator is 6, the hydroxyl value is 400 mg/KOH/g-480 mg/KOH/g, and the polypropylene oxide polyether polyol is defined as polyether D.
The functionality of the polypropylene oxide polyether polyol taking ethylenediamine as an initiator is 4, the hydroxyl value is 630 mg/KOH/g-700 mg/KOH/g, and the polypropylene oxide polyether polyol is defined as polyether E.
When the polyester polyol is included, the polyester polyol is phthalic anhydride polyester polyol obtained by condensing phthalic anhydride and polyhydric alcohol (at least dihydric alcohol), the functionality of the polyester polyol is 2.8, and the hydroxyl value of the polyester polyol is 250mg/KOH/g to 350mg/KOH/g, and the polyester polyol is defined as polyester A.
Illustratively, the polyol is 100 parts by mass, the fluoroolefin foaming agent is 2-6 parts by mass, the organic ammonium salt foaming agent is 1-3 parts by mass, the polyisocyanate is 130-160 parts by mass, and the catalyst is 1.5-2.5 parts by mass.
Further, the polyol is 100 parts by mass, the fluoroolefin foaming agent is 2-5 parts by mass, the organic ammonium salt foaming agent is 1.5-2 parts by mass, the polyisocyanate is 135-155 parts by mass, and the catalyst is 1.7-2.0 parts by mass.
Further, the polyurethane foaming composition also comprises one or more of water, a hydrocarbon foaming agent and a foam stabilizer. The hydrocarbon foaming agent is one or more of cyclopentane, n-pentane, isopentane and butane.
In the prior art, water is used as a chemical foaming agent to foam polyurethane, but the solubility of water in polyol is poor, and the mechanical properties of the prepared polyurethane foam are greatly influenced, such as poor strength, reduced heat insulation and heat preservation performance and the like. When the polymer foaming composition provided by the embodiment of the invention contains water, the ratio of the mass of the water to the mass of the polyhydric alcohol is controlled to be (1.5-2.0): 100, even (1.6-1.8): 100, the influence of water on the mechanical property of polyurethane foam is reduced, and the influence of water as a chemical foaming agent on the mechanical property is eliminated through the organic ammonium salt foaming agent; meanwhile, the organic ammonium salt foaming agent and the fluoroolefin foaming agent are utilized to promote the heat preservation performance of the prepared polyurethane foam so as to offset the influence of water as a chemical foaming agent on the heat preservation performance. Therefore, the polyurethane foaming composition provided by the embodiment of the invention controls the proportion of water contained in the polyurethane foaming composition, so that the water can be used as a chemical foaming agent to fully exert the foaming effect, and the density of the polyurethane foam is reduced.
In the prior art, a hydrocarbon foaming agent can be used as a physical foaming agent to foam polyurethane, and when the polymer foaming composition provided by the embodiment of the invention contains the hydrocarbon foaming agent, the ratio of the mass of the hydrocarbon foaming agent to the mass of the polyol is controlled to be (8-15): 100, even (10-13): 100, the proportion of the hydrocarbon foaming agent to various foaming agents (organic ammonium salt foaming agent and fluoro olefin foaming agent) contained in the polyurethane foaming composition is maximized, so that the addition amount of the organic ammonium salt foaming agent and the fluoro olefin foaming agent can be reduced, the dosage of the expensive fluoro olefin foaming agent can be reduced, the cost of the polyurethane foam is reduced, and the polyurethane foaming composition has good economy; wherein, the hydrocarbon foaming agent can be one or more of cyclopentane, n-pentane, isopentane and butane.
When the polyurethane foaming composition provided by the embodiment of the invention contains the foam stabilizer, the ratio of the mass of the foam stabilizer to the mass of the polyol is (2.0-3.0): 100, even (2.1-2.3): 100. the foam stabilizer comprises: one or more of foam stabilizer B8462, foam stabilizer B8454 and foam stabilizer B8465, all of which are manufactured by Evonik company. At this time, the polyurethane foam prepared by using the polyurethane foaming composition provided by the embodiment of the invention has uniform pore distribution, that is, the foam density distribution of the polyurethane foam is uniform.
It can be understood that the pungent smell generated in the foaming reaction process of the chemical foaming agent CFA8 can be effectively reduced by compounding the polyol, the polyisocyanate, the catalyst, the organic ammonium salt foaming agent, the fluoroolefin foaming agent, the water, the hydrocarbon foaming agent and the foam stabilizer according to the proportion.
The embodiment of the invention also provides polyurethane foam which is prepared from the polyurethane foaming composition.
Compared with the prior art, the beneficial effects of the polyurethane foam provided by the embodiment of the invention are the same as those of the polyurethane foaming composition, and are not repeated herein.
The embodiment of the invention also provides a preparation method of polyurethane foam, which comprises the following steps: the polyurethane foam is prepared by adopting the polyurethane foaming composition.
Compared with the prior art, the preparation method of the polyurethane foam provided by the embodiment of the invention has the same beneficial effects as the polyurethane foaming composition, and the details are not repeated herein.
The preparation of the polyurethane foam from the polyurethane foam composition may be carried out at ambient temperature, for example, 18 to 35 ℃ and, further, 18 to 25 ℃, and may of course be carried out at other temperatures.
Specifically, as shown in fig. 1, the preparation of the polyurethane foam using the polyurethane foaming composition includes:
step S100: the polyol, the fluoroolefin foaming agent and the catalyst contained in the polyurethane foaming composition are uniformly mixed to obtain a first mixture.
Step S200: and uniformly mixing the organic ammonium salt foaming agent contained in the polyurethane foaming composition with the first mixture to obtain a second mixture.
Step S300: and respectively ejecting the polyisocyanate contained in the polyurethane foaming composition and the second mixture by using an ejection head, so that the polyisocyanate and the second mixture are mixed and react to obtain polyurethane foam, wherein the pressure of the ejection head is 110bar-160 bar.
When the polyurethane foaming composition further comprises one or more of water, cyclopentane and a foam stabilizer; as shown in fig. 2, the mixing of the polyol, the fluoro-olefin blowing agent and the catalyst contained in the polyurethane foam composition comprises:
mixing one or more of water, cyclopentane and a foam stabilizer contained in the polyurethane foaming composition with a polyol, a fluoroolefin foaming agent and a catalyst contained in the polyurethane foaming composition to obtain a first mixture; wherein the content of the first and second substances,
if the polyurethane foaming composition contains cyclopentane, the ratio of the mass of cyclopentane to the mass of polyol is (8-15): 100, respectively; if the polyurethane foaming composition contains water, the ratio of the mass part of the water to the mass part of the polyol is (1.5-2.0): 100, respectively; if the polyurethane foaming composition contains a foam stabilizer, the ratio of the mass of the foam stabilizer to the mass of the polyol is (2.0 to 3.0): 100.
the embodiment of the invention also provides application of the polyurethane foam or the polyurethane foam prepared by the preparation method of the polyurethane foam in temperature control equipment.
Compared with the prior art, the beneficial effects of the application provided by the embodiment of the invention are the same as those of the polyurethane foaming composition, and are not repeated herein.
The temperature control device may be a refrigeration device or a heating device, the refrigeration device may be a common refrigerator, an ice chest, or the like, but is not limited thereto, and the heating device may be a common heater, a water heater, or the like, but is not limited thereto.
To demonstrate the beneficial effects of the polyurethane foaming compositions provided by the embodiments of the present invention, the following examples are given.
Comparative example 1
The polyurethane foam composition provided in this comparative example includes, in parts by mass, 100 parts of a polyol composition, 155 parts of polymeric MDI, 2.3 parts of PC-5, 6 parts of HFO-1233zd (e), 1.9 parts of water, 12.5 parts of cyclopentane, and 2.5 parts of foam stabilizer B8462; the polyol composition includes 25 parts polyether a, 25 parts polyether B, 20 parts polyether C, 10 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
Wherein, when the polyurethane foaming composition of the comparative example is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The functionality of the polyether A is 5, the hydroxyl value is 380mg/KOH/g, and the manufacturer is Jiangsu clock mountain chemical industry Co., Ltd; the functionality of the polyether B is 3, the hydroxyl value is 350mg/KOH/g, and the manufacturer is Nanjing Ningwu chemical company; the functionality of the polyether C is 4, the hydroxyl value is 420mg/KOH/g, and the manufacturer is Nanjing Hongbaoli GmbH; the functionality of the polyether D is 6, the hydroxyl value is 460mg/KOH/g, and the manufacturer is Nanjing Ningwu chemical company; the functionality of the polyether E is 4, the hydroxyl value is 680mg/KOH/g, and the manufacturer is Jiangsu clock mountain chemical industry Co., Ltd; the functionality of polyester A was 2.8, the hydroxyl number was 320mg/KOH/g, and the manufacturer was Nanjing Jinling Spodopan chemical Co., Ltd., brand PS-2352.
Comparative example II
The polyurethane foam composition provided in this comparative example includes, in parts by mass, 100 parts of a polyol composition, 144 parts of polymeric MDI, 2.3 parts of PC-5, 6 parts of HFO-1336mzz (e), 1.9 parts of water, 14.0 parts of cyclopentane, and 2.6 parts of foam stabilizer B8462; the polyol composition includes 20 parts polyether a, 15 parts polyether B, 20 parts polyether C, 25 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
Wherein, when the polyurethane foaming composition provided by the comparative example is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. As to the kinds of polyether A, polyether B, polyether C, polyether D, polyether E and polyester A, reference is made to comparative example one.
Comparative example III
The polyurethane foaming composition provided by the comparative example comprises, by mass, 100 parts of a polyol composition, 142 parts of polymeric MDI, 2.3 parts of PC-5, 2 parts of HFO-1233zd (E), 4 parts of a chemical foaming agent CFA8, 1.6 parts of water, 12.5 parts of cyclopentane and 2.6 parts of a foam stabilizer B8462; the polyol composition includes 20 parts polyether a, 25 parts polyether B, 20 parts polyether C, 15 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
Wherein, when the polyurethane foaming composition provided by the comparative example is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The chemical foaming agent CFA8 is diisopropanol ammonium carbonate salt, and the types of polyether A, polyether B, polyether C, polyether D, polyether E and polyester A are referred to in comparative example I.
Comparative example four
The polyurethane foam composition provided in this comparative example includes, in parts by mass, 100 parts of a polyol composition, 144 parts of polymeric MDI, 2.3 parts of PC-5, 1 part of HFO-1336mzz (e), 5.5 parts of a chemical blowing agent CFA8, 1.5 parts of water, 13.5 parts of cyclopentane, and 2.6 parts of a foam stabilizer B8462; the polyol composition includes 25 parts polyether a, 10 parts polyether B, 20 parts polyether C, 25 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
Wherein, when the polyurethane foaming composition provided by the comparative example is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The types of polyether A, polyether B, polyether C, polyether D, polyether E and polyester A are referred to comparative example I, and the type of the chemical foaming agent CFA8 is referred to comparative example III.
Comparative example five
The polyurethane foam prepared in the first comparative example was prepared into a top-freezer bottom-refrigerator double-door refrigerator having a volume of 310L.
Comparative example six
The polyurethane foam prepared in comparative example four was prepared into a top-freezer bottom-refrigerator double-door refrigerator having a volume of 310L.
Example one
The polyurethane foaming composition provided by the embodiment of the invention comprises, by mass, 100 parts of polyol composition, 141 parts of polymeric MDI, 2.0 parts of PC-5, 4 parts of HFO-1233zd (E), 2 parts of chemical foaming agent CFA8, 1.7 parts of water, 12 parts of cyclopentane and 2.6 parts of foam stabilizer B8462; the polyol composition includes 25 parts polyether a, 10 parts polyether B, 20 parts polyether C, 20 parts polyether D, 12 parts polyether E, and 13 parts polyester a.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. As for the kinds of polyether A, polyether B, polyether C, polyether D, polyether E and polyester A, reference is made to comparative example one, and as for the kind of chemical blowing agent CFA8, reference is made to comparative example three.
Example two
The polyurethane foaming composition provided by the embodiment of the invention comprises, by mass, 100 parts of polyol composition, 141 parts of polymeric MDI, 2.0 parts of PC-5, 4 parts of HFO-1336mzz (E), 2 parts of chemical foaming agent CFA8, 1.7 parts of water, 12 parts of cyclopentane and 2.6 parts of foam stabilizer B8462; the polyol composition includes 30 parts polyether a, 20 parts polyether B, 10 parts polyether C, 15 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. As for the kinds of polyether A, polyether B, polyether C, polyether D, polyether E and polyester A, reference is made to comparative example one, and as for the kind of chemical blowing agent CFA8, reference is made to comparative example three.
EXAMPLE III
The polyurethane foaming composition provided by the embodiment of the invention comprises 100 parts by mass of polyol composition, 141 parts by mass of polymeric MDI, 2.1 parts by mass of PC-5, 2 parts by mass of HFO-1233zd (E), 2 parts by mass of HFO-1336mzz (E), 2 parts by mass of chemical foaming agent CFA8, 1.7 parts by mass of water, 12 parts by mass of cyclopentane and 2.6 parts by mass of foam stabilizer B8462; the polyol composition includes 20 parts polyether a, 15 parts polyether B, 20 parts polyether C, 20 parts polyether D, 10 parts polyether E, and 15 parts polyester a.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 25 ℃, and the pressure of a nozzle is 120 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. As for the kinds of polyether A, polyether C, polyether D, polyether E and polyester A, reference is made to comparative example one, and as for the kind of chemical blowing agent CFA8, reference is made to comparative example three.
Example four
The polyurethane foam prepared in example one was made into an upper-freezer and lower-refrigerator double-door refrigerator with a solvent of 310L.
EXAMPLE five
The polyurethane foam prepared in example two was made into an upper-freezer and lower-refrigerator double-door refrigerator with a solvent of 310L.
Firstly, the performance of the polyurethane foams prepared in comparative examples one to four is tested, and the performance of the polyurethane foams prepared in examples one to three is tested; the performance test contents comprise:
density of the molded core: core density (definition) of molded foam; in general, the average core density is determined from the average of a plurality of 50mm by 50mm (de-skinned) samples. Method for testing the density of moulding cores, carried out in accordance with the GB/T6343-95 Standard in kg/m3。
Density distribution definition: to dissect a foamed box body prepared from polyurethane foam, the core density of each part was tested, and the difference between the maximum core density and the minimum core density was measured in kg/m3。
Average thermal conductivity in W/m.K; average compressive strength in Mpa, dimensional stability in%.
Second, the 310L top-freezer-bottom refrigerator double door refrigerators made in comparative example five, comparative example six, example four and example five were subjected to the following performance tests, including:
demoulding time, average moulding core density, average heat conductivity coefficient, average compression strength, deformation of the upper part of the left side of the box body, deformation of the middle part of the left side of the box body, deformation of the lower part of the left side of the box body, appearance quality of the box body and odor grade of the box body. The method comprises the following steps of determining the left side and the right side of a refrigerator body by taking the direction of a refrigerator door as a front measurement, determining the deformation of each part by taking the initial plane of a foaming box as a reference, wherein the default of the deformation at the moment is 0, and when the foaming box is cooled, the foam can contract or expand, and the contraction or expansion degree is the deformation; the box odor grade was evaluated in reference to the automobile odor grade mode SMC 30156-.
The demolding time refers to the time from the injection of the polyurethane foaming composition into the foaming cavity to the opening of the foaming mold, and is s. The specific units of the average molding core density, the average thermal conductivity and the average compressive strength are as described above, and the unit of the deformation of the upper part of the left side surface of the box body, the deformation of the middle part of the left side surface of the box body, the deformation of the lower part of the left side surface of the box body, the deformation of the upper part of the right side surface of the box body, the deformation of the middle part of the right side surface of the box body and the deformation of the lower part of.
The test results of examples one to three and comparative examples one to four were compared, and the comparison results are shown in table 1. The results of the performance tests on 310L top-and-bottom freezer refrigerator made in comparative example five, comparative example six, example four and example five were compared and are shown in Table 2.
TABLE 1 comparative table of the results of the polyurethane foam performance tests
The performance test results of the comparative examples I to III and the comparative examples I and II shown in the table 1 show that the polyurethane foam composition prepared in the examples I to III contains the chemical foaming agent CFA8, so that the density distribution coefficient of the polyurethane foam is smaller, the flowability is obviously improved, and the density distribution is more uniform; in addition, the chemical foaming agent CFA8 contained in the polyurethane foaming composition is beneficial to reducing the density of the foam, the dosage of other foaming agents contained in the polyurethane foaming composition can be reduced, and the effect on the compression strength and the dimensional stability of the polyurethane foam after the density is reduced is not large.
Meanwhile, comparing the performance test results of the first, third and fourth examples shown in table 1, it can be found that: an appropriate amount of chemical foaming agent CFA8 replaces part of HFO-1233zd (E) or HFO-1336mzz, and the thermal insulation performance of the foam is not affected. However, as the content of the chemical blowing agent CFA8 increases, the fluidity of the polyurethane foam tends to decrease, and the heat insulation performance of the polyurethane foam deteriorates.
TABLE 2310L COMPARATIVE TABLE OF PERFORMANCE TEST RESULTS FOR REFRIGERATOR WITH DOUBLE DOORS
Comparing the results of the performance tests of 310L of the top-freezer bottom-refrigerator double-door refrigerators made in example four, example five, comparative example five and comparative example six shown in table 2, it can be found that: when the polyurethane foam prepared by the polyurethane foam composition provided by the embodiment of the invention is applied to the manufacture of a 310L upper-freezing lower-refrigerating double-door refrigerator, the demolding time is 120-150 s. The demold time for the example four prepared was 120s, the demold time for the example five was 150s, while the demold time for the comparative example five was 200s and the demold time for the comparative example six was 150s, it can be seen that the examples four and five had significantly superior flow properties to the comparative example five and the comparative example six; meanwhile, as can be seen from table 2, when the 310L top-freezer and bottom-refrigerator double-door refrigerator is manufactured by using the polyurethane foam composition, the polyurethane foam has lower core density and better compressive strength.
After the refrigerator foaming, demolding and cooling to room temperature, the deformation of the top, the middle and the bottom of the left side face and the right side face of the refrigerator body are measured, and the deformation of the upper part of the left side face of the refrigerator body, the deformation of the middle part of the left side face of the refrigerator body, the deformation of the lower part of the left side face of the refrigerator body, the deformation of the upper part of the right side face of the refrigerator body, the deformation of the middle part of the right side. As can be seen from table 2: the side deformation of the refrigerators in the fourth embodiment and the fifth embodiment of the invention is similar to that of the refrigerator in the fifth comparative embodiment, and therefore, when a 310L upper-freezing lower-refrigerating double-door refrigerator is manufactured, the demolding time is shortened and the deformation is not influenced, so that the polyurethane foaming composition provided by the embodiment of the invention can improve the demolding performance in the process of manufacturing the 310L upper-freezing lower-refrigerating double-door refrigerator, and the production efficiency is obviously improved.
Since the polyurethane foam composition used in comparative example six contained the chemical foaming agent CFA8 in a large amount and a large amount of heat was generated during the foaming reaction, the polyurethane foam composition containing the chemical foaming agent CFA8 in a large amount was disadvantageous in terms of mold release during the production of 310L of the top-and-bottom refrigerator double-door refrigerator; meanwhile, the deformation degree of the side plate of the refrigerator in the sixth comparative example is obviously increased, the flowability of polyurethane foam filled in the 310L upper-freezing lower-refrigerating double-door refrigerator is influenced, and the refrigerator has obvious peculiar smell.
EXAMPLE six
The polyurethane foaming composition provided by the embodiment of the invention comprises 100 parts by mass of polyol composition, 130 parts by mass of 2,4-TDI, 1.5 parts by mass of A-1, 2 parts by mass of HFO-1336mzz (S), 1 part by mass of chemical foaming agent CFA8, 2.0 parts by mass of water, 8 parts by mass of n-pentane and 2.0 parts by mass of foam stabilizer B8454; the polyol composition includes 18 parts polyether a, 30 parts polyether C, 10 parts polyether D, 12 parts polyether E, and 30 parts polyester a.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 20 ℃, and the pressure of a nozzle is 110 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The chemical foaming agent CFA8 is an organic ammonium orthoformate compound, the functionality of polyether A is 5, and the hydroxyl value is 320 mg/KOH/g; polyether C has a functionality of 4 and a hydroxyl number of 370 mg/KOH/g; polyether D has a functionality of 6 and a hydroxyl number of 480 mg/KOH/g; polyether E has a functionality of 4 and a hydroxyl number of 630 mg/KOH/g; the functionality of polyester A was 2.8 and the hydroxyl number was 350 mg/KOH/g.
EXAMPLE seven
The polyurethane foaming composition provided by the embodiment of the invention comprises, by mass, 100 parts of polyol composition, 160 parts of 2,6-TDI, 2.5 parts of TMR-2, 5 parts of HFO-1336mzz (E), 1.5 parts of chemical foaming agent CFA8, 1.5 parts of water, 15 parts of isopentane and 3.0 parts of foam stabilizer B8465; the polyol composition includes 15 parts polyether a, 20 parts polyether B, 25 parts polyether C, 30 parts polyether D, and 10 parts polyether E.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 18 ℃, and the pressure of a spray head is 160 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The chemical foaming agent CFA8 is a hydrazinoalcohol ammonium salt compound, the functionality of polyether A is 5, and the hydroxyl value is 400 mg/KOH/g; the functionality of the polyether B is 3, and the hydroxyl value is 360 mg/KOH/g; polyether C has a functionality of 4 and a hydroxyl number of 450 mg/KOH/g; polyether D has a functionality of 6 and a hydroxyl number of 400 mg/KOH/g; polyether E had a functionality of 4 and a hydroxyl number of 650 mg/KOH/g.
Example eight
The polyurethane foaming composition provided by the embodiment of the invention comprises, by mass, 100 parts of a polyol composition, 85 parts of 2,6-TDI, 70 parts of polymeric MDI, 1.7 parts of PC-8, 6 parts of HFO-1233zd (E), 3 parts of a chemical foaming agent CFA8, 1.6 parts of water, 2 parts of butane, 2.1 parts of cyclopentane and 0.3 part of a foam stabilizer B8462; the polyol composition includes a polyester a.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 22 ℃, and the pressure of a nozzle is 140 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The chemical blowing agent CFA8 was an N-hydroxypropylated ammonium carbonate salt compound, polyester A contained two polyesters each having a functionality of 2.8, one polyester having a hydroxyl number of 250mg/KOH/g and the other polyester having a hydroxyl number of 300 mg/KOH/g.
Example nine
The polyurethane foaming composition provided by the embodiment of the invention comprises 100 parts by mass of polyol composition, 135 parts by mass of 2,6-TDI, 1.0 part by mass of PC-8, 0.5 part by mass of A-1, 5 parts by mass of HFO-1233zd (E), 2.5 parts by mass of chemical foaming agent CFA8, 1.8 parts by mass of water, 13 parts by mass of cyclopentane, 2.0 parts by mass of foam stabilizer B8465 and 0.3 part by mass of foam stabilizer B8462; the polyol composition includes 15 parts polyether a, 25 parts polyether B, and 30 parts polyether E.
When the polyurethane foaming composition provided by the embodiment of the invention is used for preparing polyurethane foam, the preparation temperature is 20 ℃, and the pressure of a nozzle is 130 bar; the foaming equipment is a high-pressure foaming machine, model 1250P/MT26, and the manufacturer is Hennecke company. The chemical foaming agent CFA8 is an organic ammonium formate compound, the functionality of polyether A is 5, and the hydroxyl value is 350 mg/KOH/g; polyether B has a functionality of 3 and a hydroxyl number of 300 mg/KOH/g; polyether E had a functionality of 4 and a hydroxyl number of 700 mg/KOH/g.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A polyurethane foam composition for use in a temperature control device, comprising: polyol, polyisocyanate, catalyst, organic ammonium salt foaming agent, fluoroolefin foaming agent, water and cyclopentane;
the foaming agent comprises, by mass, 100 parts of polyol, 2-4 parts of fluoroolefin foaming agent, 2 parts of organic ammonium salt foaming agent, 130-160 parts of polyisocyanate and 1.5-2.5 parts of catalyst, wherein the organic ammonium salt foaming agent is a mixture of organic ammonium salt foaming agent and polyisocyanate;
the mass ratio of the water to the polyol is (1.5-2.0): 100, the mass ratio of the cyclopentane to the polyol is (8-15): 100, respectively;
wherein the fluoroolefin foaming agent comprises one or more of trans-1-chloro-3, 3, 3-trifluoropropene, cis-1, 1,1,4,4, 4-hexafluoro-2-butene, and trans-1, 1,1,4,4, 4-hexafluoro-2-butene;
the organic ammonium salt foaming agent comprises one or more of organic ammonium formate compounds, organic ammonium orthoformate compounds, organic ammonium carbonate compounds and ammonium hydrazinoalkoxide compounds;
the polyol is a mixture of polyether polyol and polyester polyol, and the polyether polyol comprises at least two of polypropylene oxide polyether polyol taking sucrose and triethanolamine as composite initiators, polypropylene oxide polyether polyol taking glycerin as an initiator, polypropylene oxide polyether polyol taking toluenediamine as an initiator, polypropylene oxide polyether polyol taking sorbitol as an initiator and polypropylene oxide polyether polyol taking ethylenediamine as an initiator;
when the polypropylene oxide polyether polyol takes sucrose and triethanolamine as a composite initiator, the functionality of the polypropylene oxide polyether polyol is 5, and the hydroxyl value is 320-400 mg KOH/g;
when the polypropylene oxide polyether polyol takes glycerol as an initiator, the functionality of the polypropylene oxide polyether polyol is 3, and the hydroxyl value is 300-360 mg KOH/g;
when the polypropylene oxide polyether polyol takes toluenediamine as an initiator, the functionality of the polypropylene oxide polyether polyol is 4, and the hydroxyl value is 370mg KOH/g-450 mg KOH/g;
when sorbitol is used as an initiator, the functionality of the polypropylene oxide polyether polyol is 6, and the hydroxyl value is 400-480 mg KOH/g;
when the polypropylene oxide polyether polyol takes ethylenediamine as an initiator, the functionality of the polypropylene oxide polyether polyol is 4, and the hydroxyl value is 630-700 mg KOH/g;
the polyester polyol is phthalic anhydride polyester polyol formed by condensing phthalic anhydride and polyhydric alcohol, the functionality of the phthalic anhydride polyester polyol is 2.8, and the hydroxyl value of the phthalic anhydride polyester polyol is 250-350 mg KOH/g.
2. The polyurethane foaming composition of claim 1, wherein the polyisocyanate comprises one or more of polyphenyl polymethylene polyisocyanate, 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate;
the catalyst comprises one or more of pentamethyldiethylenetriamine, 70% bis (dimethylaminoethyl) ether solution, N-dimethylcyclohexylamine and a quaternary ammonium salt catalyst TMR-2.
3. The polyurethane foaming composition according to claim 1 or 2, further comprising a foam stabilizer, wherein the ratio of the mass of the foam stabilizer to the mass of the polyol is (2.0 to 3.0): 100.
4. a polyurethane foam prepared from the polyurethane foam composition according to any one of claims 1 to 3.
5. A method of preparing a polyurethane foam, comprising:
preparing a polyurethane foam using a polyurethane foaming composition according to any one of claims 1 to 3.
6. The method of claim 5, wherein the preparing the polyurethane foam using the polyurethane foaming composition comprises:
uniformly mixing polyol, a fluoroolefin foaming agent, a catalyst, water and cyclopentane contained in the polyurethane foaming composition to obtain a first mixture;
uniformly mixing an organic ammonium salt foaming agent contained in the polyurethane foaming composition with the first mixture to obtain a second mixture;
respectively ejecting polyisocyanate contained in the polyurethane foaming composition and the second mixture by using an ejection head under negative pressure, so that the polyisocyanate and the second mixture are mixed and react to obtain polyurethane foam;
wherein the mass ratio of the cyclopentane to the polyol is (8-15): 100, the ratio of the mass parts of the water to the mass of the polyhydric alcohol is (1.5-2.0): 100.
7. the method of producing a polyurethane foam according to claim 6, wherein the polyurethane foaming composition further comprises a foam stabilizer;
the mixing of the polyol, the fluoroolefin foaming agent, the catalyst, the water and the cyclopentane contained in the polyurethane foaming composition comprises the following steps: mixing a foam stabilizer contained in the polyurethane foaming composition with a polyol, a fluoroolefin foaming agent, a catalyst, water and cyclopentane contained in the polyurethane foaming composition;
wherein the ratio of the mass of the foam stabilizer to the mass of the polyol is (2.0 to 3.0): 100.
8. use of a polyurethane foam according to claim 4 or prepared according to the process for preparing a polyurethane foam according to any one of claims 5 to 7 in a temperature-control device.
9. Use according to claim 8, wherein the temperature control device is a heating device or a cooling device.
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| CN110172173B (en) * | 2019-06-04 | 2021-07-09 | 红宝丽集团股份有限公司 | Composition for reaction with isocyanate |
| CN110483828A (en) * | 2019-09-03 | 2019-11-22 | 海信容声(广东)冰箱有限公司 | A kind of foaming agent, polyurethane foamed composite object, polyurethane foam and its preparation method and application |
| CN110885418A (en) * | 2019-12-16 | 2020-03-17 | 山东一诺威新材料有限公司 | Polyurethane rigid foam for on-line tube heat collector and preparation method thereof |
| CN111378197A (en) * | 2020-03-27 | 2020-07-07 | 山东省云山鼎节能工程有限公司 | Spraying type polyurethane rigid foam and preparation method thereof |
| JP2023543145A (en) * | 2020-09-21 | 2023-10-13 | サン－ゴバン パフォーマンス プラスティックス コーポレイション | Polyurethane foam and its formation method |
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