CN102875833A - Foamer composition, polyurethane rigid foam, preparation method of foamer composition, refrigeration equipment and thermal insulation component - Google Patents
Foamer composition, polyurethane rigid foam, preparation method of foamer composition, refrigeration equipment and thermal insulation component Download PDFInfo
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- CN102875833A CN102875833A CN201210349456XA CN201210349456A CN102875833A CN 102875833 A CN102875833 A CN 102875833A CN 201210349456X A CN201210349456X A CN 201210349456XA CN 201210349456 A CN201210349456 A CN 201210349456A CN 102875833 A CN102875833 A CN 102875833A
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Abstract
The invention discloses a foamer composition, polyurethane rigid foam, a preparation method of the foamer composition, refrigeration equipment and a thermal insulation component. The foamer composition comprises 5-20 weight parts of pentane, 1-25 weight parts of 245fa and 0-5 weight parts of 134a. With the foamer composition disclosed by the invention, the polyurethane rigid foam can be effectively prepared.
Description
Technical field
The present invention relates to foaming agent composotion, hard polyurethane foam and preparation method, refrigeration equipment, heat insulation module.
Background technology
Hard polyurethane foam is the foam article that is formed by chemical reaction under the whipping agent effect by combination material and organic multiple isocyanate.Whipping agent commonly used is pentane, and part is used the mixture of 245fa, 365mfc or pentane and hydrogen fluorohydrocarbon.Yet present foaming agent composotion still remains to be improved.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.For this reason, the present invention proposes a kind of foaming agent composotion.In one aspect of the invention, the present invention proposes a kind of foaming agent composotion.According to embodiments of the invention, this foaming group agent compound comprises: the pentane of 5～20 weight parts; The 245fa of 1～25 weight part; And the 134a of 0～5 weight part.Thus, utilization can be used for preparing foam effectively according to the foaming agent composotion of the embodiment of the invention, hard polyurethane foam for example, foam can be widely used in domain of control temperature, for example refrigeration equipment, heat insulation module, thus make effectively further that foam has that thermal conductivity is low, dimensional stabilizing, intensity is high, lightweight and the advantage such as environmental protection.
According to some embodiments of the present invention, above-mentioned foaming agent composotion can also have following additional technical feature:
According to one embodiment of present invention, described pentane be selected from pentamethylene, Skellysolve A and iso-pentane one of at least.Thus, utilize the pentane according to the embodiment of the invention can form foaming agent composotion, further can effectively be used for preparing foam.
According to one embodiment of present invention, described foaming agent composotion comprises: the pentane of 8～15 weight parts; The 245fa of 5～20 weight parts; And the 134a of 0～4 weight part.Thus, utilization can be used for preparing foam effectively according to the foaming agent composotion of the embodiment of the invention, hard polyurethane foam for example, thus can make effectively further that foam has that thermal conductivity is low, dimensional stabilizing, intensity is high, lightweight and the advantage such as environmental protection.
According to one embodiment of present invention, described foaming agent composotion comprises: the pentane of 8～12 weight parts; The 245fa of 10～15 weight parts; And the 134a of 0～3 weight part.Thus, the consistency of this foaming agent composotion and polyhydric alcohol composition is better, can freely regulate the ratio of itself and water, reduces the ratio of water in the combination material, thereby reduces in the foam as the carbon dioxide content of whipping agent, reduces the thermal conductivity of foam.In addition, the minimizing of water has reduced the consumption of organic multiple isocyanate in combination material, thereby can make effectively further that foam has that thermal conductivity is low, dimensional stabilizing, intensity is high, lightweight and the advantage such as environmental protection.
In another aspect of the present invention, the present invention proposes a kind of method for preparing hard polyurethane foam.According to embodiments of the invention, the method comprises: foaming agent composotion, polyhydric alcohol composition, catalyzer, water, suds-stabilizing agent and organic multiple isocyanate are mixed, in order to obtain reaction mixture; And described reaction mixture is reacted, in order to obtain described polyurethane foam, wherein, described polyhydric alcohol composition comprise at least a functionality at least 3, hydroxyl value is 300～800 polyvalent alcohol.Thus, utilization prepares hard polyurethane foam according to the method for preparing hard polyurethane foam of the embodiment of the invention, can make effectively that foam has that thermal conductivity is low, dimensional stabilizing, the advantage such as intensity is high, rate of expansion is low, lightweight and environmental protection, thereby can further effectively make foam can be widely used in domain of control temperature, for example refrigeration equipment, heat insulation module.
According to some embodiments of the present invention, the above-mentioned method for preparing hard polyurethane foam can also have following additional technical feature:
According to one embodiment of present invention, described polyhydric alcohol composition comprise be selected from polyether glycol and polyester polyol one of at least.Thus, utilize the method for preparing hard polyurethane foam according to the embodiment of the invention, can improve the solubleness of fluorinated hydrocarbons or pentane foaming agent, thereby can effectively prepare hard polyurethane foam.
According to one embodiment of present invention, described polyvalent alcohol comprises: with tolylene diamine as initiator by with resulting polyether glycol 5～40 weight parts of olefin oxide addition reaction.Thus, utilization can prepare hard polyurethane foam effectively according to the method for preparing hard polyurethane foam of the embodiment of the invention, can improve the solubleness of fluorinated hydrocarbons or pentane foaming agent, reduces the demould time of foam, and reduce the consumption that makes up catalyzer in the material, reduce production costs.In addition, all right reinforced foam intensity, the thermal conductivity of reduction foam.
According to one embodiment of present invention, described polyhydric alcohol composition comprises the aromatic polyester polyol of 5～30 % by weight.Thus, utilization can effectively prepare hard polyurethane foam according to the method for preparing hard polyurethane foam of the embodiment of the invention, can be further reinforced foam intensity effectively, reduce the thermal conductivity of foam and the energy consumption that reduction utilizes the obtained equipment of foam.
According to one embodiment of present invention, described catalyzer comprises kicker, gel catalyst and catalyst for trimerization.Thus, catalyzer can very effective acceleration contains the compound of active hydrogen atom (particularly hydroxyl) compound and the reaction of organically-modified or unmodified polyisocyanates, can further effectively reduce density, thermal conductivity and the rate of expansion of foam.
According to one embodiment of present invention, described kicker is for being selected from pentamethyl-diethylenetriamine, two-the dimethyl amine benzyl ethyl ether, N, N, N, N ', N "-Tetramethyl Ethylene Diamine and 4-methyl hexamethylene diamine at least a; According to one embodiment of present invention, described gel catalyst is be selected from dimethyl cyclohexane and dimethyl benzylamine at least a; According to one embodiment of present invention, described catalyst for trimerization is be selected from first quaternary amine, second quaternary amine, hot quaternary amine and hexahydrotriazine at least a.Thus, this catalyzer can very effective acceleration contains the compound of active hydrogen atom (particularly hydroxyl) compound and the reaction of organically-modified or unmodified polyisocyanates, can further effectively reduce density, thermal conductivity and the rate of expansion of foam.
According to one embodiment of present invention, described suds-stabilizing agent is silicone oil.Thus, this suds-stabilizing agent can effectively reduce surface tension, improve the size of Combination, the even bubble that produces and the structure of regulating foam.
According to one embodiment of present invention, described organic multiple isocyanate is polymethine polyphenyl polyisocyanate (MDI).According to one embodiment of present invention, described organic multiple isocyanate index is 100～120.Thus, polymethine polyphenyl polyisocyanate (MDI) can react with polyhydric alcohol composition, water and foaming agent composotion effectively, the foam generated by chainpropagation, gas generation and interlinkage effect.
According to one embodiment of present invention, described reaction mixture comprises: at first 134a is mixed with 245fa; And then, mix with pentane, polyvalent alcohol again.Thus, utilization can be used for preparing hard polyurethane foam effectively according to the reaction mixture of the embodiment of the invention, and the advantages such as foam has, and thermal conductivity is low, dimensional stabilizing, intensity are high, lightweight, environmental protection, thereby further make foam can be widely used in domain of control temperature.
According to one embodiment of present invention, the viscosity of described reaction mixture under 20 ℃ is 300～800mpas.According to one embodiment of present invention, described reaction mixture reacts in die cavity, and wherein, the stacking factor of described reaction mixture in die cavity is 1.2 to 2.0.According to one embodiment of present invention, described stacking factor is 1.3 to 1.7.According to one embodiment of present invention, demould time is no more than 4 minutes.Thus, utilization can prepare hard polyurethane foam effectively according to the method for preparing hard polyurethane foam of the embodiment of the invention, and the advantages such as foam has, and thermal conductivity is low, dimensional stabilizing, intensity are high, lightweight, environmental protection, thereby further make foam can be widely used in domain of control temperature.
Aspect another, the present invention proposes a kind of hard polyurethane foam of the present invention.According to one embodiment of present invention, described hard polyurethane foam is prepared from by the above-described method for preparing hard polyurethane foam.Thus, hard polyurethane foam according to the embodiment of the invention, can make that foam has that thermal conductivity is low, the advantage such as dimensional stabilizing, intensity are high, lightweight, environmental protection, thereby further make foam can be widely used in domain of control temperature, such as refrigeration equipment, heat insulation module etc.
According to still a further embodiment, the density of described hard polyurethane foam is 25～35 kilograms per cubic meter.Thus, according to the hard polyurethane foam of the embodiment of the invention, can effectively reduce the density of foam, alleviate the weight of utilizing the obtained product of foam.
According to one embodiment of present invention, the thermal conductivity λ of described hard polyurethane foam (10 ℃) is that 17.00～19.50 milliwatt/rice are opened.Thus, according to the preparation hard polyurethane foam of the embodiment of the invention, can effectively reduce the thermal conductivity of foam, thereby be conducive to reduce the energy consumption of utilizing the obtained product of foam.
In one aspect of the invention, the present invention proposes a kind of refrigeration equipment.According to one embodiment of present invention, described refrigeration equipment comprises above-described hard polyurethane foam.Thus, according to the refrigeration equipment of the embodiment of the invention, refrigeration equipment has the advantages such as good refrigeration effect, less energy consumption, cost are low, environmental protection.
According to one embodiment of present invention, described refrigeration equipment is refrigerator.Thus, according to the refrigeration equipment of the embodiment of the invention, refrigerator has the advantages such as good refrigeration effect, less energy consumption, cost are low, environmental protection.
Aspect another, the present invention proposes a kind of heat insulation module of the present invention.According to one embodiment of present invention, described heat insulation module comprises above-described hard polyurethane foam.Thus, according to the heat insulation module of the embodiment of the invention, heat insulation module has the advantages such as good heat insulating, less energy consumption, cost are low, environmental protection, can be widely used in domain of control temperature.
The method for preparing according to an embodiment of the invention hard polyurethane foam can realize that following advantages is one of at least:
1, according to the method for preparing hard polyurethane foam of the embodiment of the invention, employing pentane/245fa/134a is whipping agent, the ODP(ODP) be zero, harmless to ozone, be a kind of desirable environmental protection whipping agent;
2, according to the method for preparing hard polyurethane foam of the embodiment of the invention, pentane/245fa/134a type whipping agent and polyethers consistency are good, can reduce the addition of water, reduce CO in the foam
2Ratio reduces the foam thermal conductivity, is conducive to reduce the energy consumption of utilizing the obtained product of foam;
3, according to the method for preparing hard polyurethane foam of the embodiment of the invention, can significantly reduce foam density (reducing more than 16% than existing density), can alleviate the gross weight of utilizing the obtained product of foam, reduce manufacturing cost;
4, according to the method for preparing hard polyurethane foam of the embodiment of the invention, the cohesiveness between foam and the base material is good, and it is even that foam also has density distribution, surfacing, the advantage such as intensity is large, dimensional stabilizing is good.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the schematic flow sheet for preparing according to an embodiment of the invention the method for hard polyurethane foam.
Embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, only be used for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, it will be appreciated that, term " thickness ", " on ", orientation or the position relationship of the indication such as D score be based on orientation shown in the drawings or position relationship, only be for convenience of description the present invention and simplified characterization, rather than indication or the hint device of indication or element must have specific orientation, with specific orientation structure and operation, therefore can not be interpreted as limitation of the present invention.
In the present invention, unless stated otherwise, the various term definitions in the literary composition of the present invention are as follows:
Polyalcohol formulation: polyhydric alcohol composition adds additive, such as catalyzer, tensio-active agent, water, does not comprise pneumatogen;
Premixture: polyalcohol formulation adds all pneumatogens;
Minimum filling weight (MFW): the complete required minimum weight of mold filling, unit gram;
Overpacking: inject weight * 100/MFW, the % of unit;
Molded density: by the definite density of volume of in mould, injecting weight and this mould, the i.e. global density of foam;
Packing factor: molded density/freely steep density;
Demould time: foam is injected into the time of die sinking.
In one aspect of the invention, the present invention proposes a kind of foaming agent composotion.According to embodiments of the invention, foaming agent composotion comprises pentane, 245fa and 134a.The contriver finds, the consistency of this foaming agent composotion and polyether glycol is better, can freely regulate itself and the ratio of water, reduce combination expect in the ratio of water, thereby in the minimizing foam as the CO of whipping agent
2Content reduces the thermal conductivity of foam, is conducive to reduce the energy consumption of product.In addition, the minimizing of water-content can make the consumption of organic multiple isocyanate be reduced in the combination material, thereby is conducive to reduce the production cost of product.The contriver also finds, employing pentane/245fa/134a is whipping agent, the ODP(ODP) be zero, harmless to ozone, be a kind of desirable environmental protection whipping agent, have huge market popularization value.
According to embodiments of the invention, the content of the combined composition of foaming composition is not particularly limited.According to embodiments of the invention, foaming composition comprises: the pentane of 5～20 weight parts, the 134a of the 245fa of 1～25 weight part and 0～5 weight part.Thus, utilization can be used for preparing foam effectively according to the foaming composition of the embodiment of the invention, foam can be widely used in domain of control temperature, for example refrigeration equipment, heat insulation module, thus further can effectively obtain to reduce energy consumption, reduce the actively effects such as cost, environmental protection.
According to embodiments of the invention, the kind of pentane is not particularly limited, can be selected from pentamethylene, Skellysolve A and iso-pentane one of at least.Thus, pentane can form foaming composition, further can effectively be used for preparing foam.
According to one embodiment of present invention, described foaming agent composotion comprises: the pentane of 8～15 weight parts; The 245fa of 5～20 weight parts; And the 134a of 0～4 weight part.According to one embodiment of present invention, described foaming agent composotion comprises: the pentane of 8～12 weight parts; The 245fa of 10～15 weight parts; And the 134a of 0～3 weight part.Thus, utilize the foaming composition according to the embodiment of the invention can effectively be used for preparing foam, can make effectively that foam has that thermal conductivity is low, dimensional stabilizing, intensity is high, lightweight and the advantage such as environmental protection.
According to embodiments of the invention, the kind of preparation foam is not particularly limited, for example according to one embodiment of present invention, and the preparation hard polyurethane foam.Thus, this hard polyurethane foam can be widely used in domain of control temperature, for example refrigeration equipment, heat insulation module, thus further can effectively obtain to reduce energy consumption, reduce the actively effects such as cost, environmental protection.
In the prior art, whipping agent then more adopts pentamethylene, but the solubleness of pentamethylene in polyvalent alcohol is very limited, and the foam thermal conductivity of preparation is higher, causes utilizing the energy consumption of the obtained product of foam to rise.In addition, in the prior art, whipping agent also has the thermal conductivity that adopts pure 245fa, pure 365mfc, pentamethylene and 245fa mixing, pentamethylene and 245fa and 365mfc ternary mixture etc. to reduce foam as whipping agent, but because 245fa, 365mfc raw materials cost are higher, if it is less that foam-filled amount does not reduce or reduces, will inevitably cause manufacturing cost to rise.
In another aspect of the present invention, the present invention proposes a kind of method for preparing hard polyurethane foam.With reference to figure 1, according to embodiments of the invention, the method for preparing hard polyurethane foam can may further comprise the steps:
S100: foaming agent composotion, polyhydric alcohol composition, catalyzer, water, suds-stabilizing agent and organic multiple isocyanate are mixed, in order to obtain reaction mixture
In this step, foaming agent composotion, polyhydric alcohol composition, catalyzer, water, suds-stabilizing agent and organic multiple isocyanate are mixed.Thus, obtain reaction mixture.According to embodiments of the invention, the kind of polyhydric alcohol composition is not particularly limited.The contriver finds, in polyhydric alcohol composition, select to contain the solubleness that uncle's nitrogen polyvalent alcohol is conducive to improve fluorinated hydrocarbons or pentane foaming agent, making in the polyhydric alcohol composition can to organize the agent compound compatible preferably with foaming, for example contain amine-initiated dose of tolylene diamine in the embodiment of the invention, it can play self-catalysis in combined polyether, reduce the demould time of foam, and reduce the consumption of catalyzer in the combination material, thereby be conducive to reduce cost.On the other hand, owing to contain aromatic ring structure in the tolylene diamine, can reinforced foam intensity, also be conducive to reduce simultaneously the thermal conductivity of foam.In this research, also selected aromatic polyester polyol in the polyhydric alcohol composition, this is because its nontoxic, non-corrosiveness, is non-inflammable explosive article, its dissolving properties better, can mix with foaming composition preferably, in addition, owing to containing the phenyl ring rigid radical in its molecule, can play the effect of gaining in strength, and its price being more cheap, thereby be conducive to increase foamy body, reinforced foam dimensional stabilizing, raising foam wear resistance and thermotolerance and the production cost that reduces product.
According to embodiments of the invention, described polyhydric alcohol composition comprise at least a functionality at least 3, hydroxyl value is 300～800 polyvalent alcohol.According to embodiments of the invention, polyhydric alcohol composition can be selected from polyether glycol and polyester polyol one of at least.According to embodiments of the invention, described polyvalent alcohol comprise following one of at least: take sucrose and glycerine as mix initiator by with the resulting polyether glycol of olefin oxide addition reaction (molecular weight 400～1200) 15～60 weight parts; With tolylene diamine as initiator by with the resulting polyether glycol of olefin oxide addition reaction (molecular weight 400～800) 5～40 weight parts; With glycerine as initiator by with the resulting polyether glycol of olefin oxide addition reaction (molecular weight 600～1200) 5～20 weight parts; And take sorbyl alcohol and glycerine as mixing initiator and the resulting polyether glycol of olefin oxide addition reaction (molecular weight 600～1000) 10～25 weight parts.According to one embodiment of present invention, preferably with tolylene diamine as initiator by with the resulting polyether glycol of olefin oxide addition reaction (molecular weight 400～800) 5～40 weight parts; With glycerine as initiator by with the resulting polyether glycol of olefin oxide addition reaction (molecular weight 600～1200) 5～20 weight parts.According to one embodiment of present invention, described polyhydric alcohol composition comprises the aromatic polyester polyol (molecular weight 200～600) of 5～30 % by weight.Thus, utilization prepares hard polyurethane foam according to the method for preparing hard polyurethane foam of the embodiment of the invention, can effectively reduce the thermal conductivity of foam, intensity and the dimensional stabilizing of reinforced foam, the effect that improves foam wear resistance and thermotolerance and reduction products production cost.
According to embodiments of the invention, described catalyzer comprises kicker, gel catalyst and catalyst for trimerization.The contriver finds, catalyzer can very effective acceleration contain active hydrogen atom (particularly hydroxyl) compound and the compound that organically-modified or unmodified polyisocyanates reacts, and can further effectively reduce density, thermal conductivity and the rate of expansion of foam.According to one embodiment of present invention, described kicker is for being selected from pentamethyl-diethylenetriamine, two-the dimethyl amine benzyl ethyl ether, N, N, N, N ', N "-Tetramethyl Ethylene Diamine and 4-methyl hexamethylene diamine at least a; According to one embodiment of present invention, described gel catalyst is be selected from dimethyl cyclohexane and dimethyl benzylamine at least a; According to one embodiment of present invention, described catalyst for trimerization is be selected from first quaternary amine, second quaternary amine, hot quaternary amine and hexahydrotriazine at least a.Thus, utilization prepares hard polyurethane foam according to the method for preparing hard polyurethane foam of the embodiment of the invention, can effectively reduce foam density, reduce the gross weight of insulating product, and the manufacturing cost that can effectively reduce thermal conductivity and rate of expansion and reduce product.According to embodiments of the invention, described suds-stabilizing agent is silicone oil.The contriver finds, the effect that this suds-stabilizing agent has effectively to be had the reduction surface tension, improve the big or small of Combination, the even bubble that produces and regulate foam structure.
According to embodiments of the invention, described organic multiple isocyanate is polymethine polyphenyl polyisocyanate (MDI).According to one embodiment of present invention, described organic multiple isocyanate index is 100～120.Thus, polymethine polyphenyl polyisocyanate (MDI) can react with polyhydric alcohol composition, water and foaming agent composotion effectively, the foam generated by chainpropagation, gas generation and interlinkage effect, can effectively make the cohesiveness between foam and the base material good, in addition, it is even that foam also has density distribution, surfacing, the advantage such as intensity is large, dimensional stabilizing is good.
According to embodiments of the invention, described reaction mixture comprises: at first 134a is mixed with 245fa; And then, mix with pentane, polyvalent alcohol again.According to one embodiment of present invention, the viscosity of described reaction mixture under 20 ℃ is 300～800mpas.Thus, utilization can be used for preparing hard polyurethane foam effectively according to the reaction mixture of the embodiment of the invention, and the advantages such as foam has, and thermal conductivity is low, dimensional stabilizing, intensity are high, lightweight, environmental protection, thereby further make foam can be widely used in domain of control temperature.
S200: described reaction mixture is reacted, in order to obtain described polyurethane foam
In this step, resulting reaction mixture among the step S100 is reacted.Thus, can obtain hard polyurethane foam.According to embodiments of the invention, the means that are used for reaction mixture is reacted are not particularly limited, and can utilize any any means known that reaction mixture is reacted.According to embodiments of the invention, the reaction of described reaction mixture is carried out in die cavity, and wherein, the stacking factor of described reaction mixture in die cavity is 1.2 to 2.0.According to one embodiment of present invention, described stacking factor is 1.3～1.7.According to one embodiment of present invention, demould time is no more than 4 minutes.Thus, utilization can prepare hard polyurethane foam effectively according to the embodiment of the invention reaction mixture is reacted, and the advantages such as foam has, and thermal conductivity is low, dimensional stabilizing, intensity are high, lightweight, environmental protection, thereby further make foam can be widely used in domain of control temperature, such as refrigeration equipment, heat insulation module etc.
In one aspect of the invention, the present invention proposes a kind of hard polyurethane foam.According to embodiments of the invention, this hard polyurethane foam is prepared from by the above-described method for preparing hard polyurethane foam.Thus; the advantages such as hard polyurethane foam has that thermal conductivity is low, dimensional stabilizing, intensity are high, lightweight, environmental protection; thereby further make hard polyurethane foam can be widely used in domain of control temperature; such as refrigeration equipment, heat insulation module etc.; person skilled can certainly be extended to it other its Application Areas; do not repeat them here, these are all within the scope of the present invention.In addition, the front for foaming agent composotion, prepare the described feature and advantage of method of hard polyurethane foam, also applicable this hard polyurethane foam natch repeats no more.About the actual conditions that hard polyurethane foam uses, those skilled in the art can adopt any currently known methods and equipment, do not repeat them here.
According to one embodiment of present invention, the density of described hard polyurethane foam is 25～35 kilograms per cubic meter.Thus, according to the hard polyurethane foam of the embodiment of the invention, can reduce the density of foam, alleviate the weight of utilizing the obtained product of foam.
According to one embodiment of present invention, the thermal conductivity λ of described hard polyurethane foam (10 ℃) is that 17.00～19.50 milliwatt/rice are opened.Thus, according to the preparation hard polyurethane foam of the embodiment of the invention, can reduce the thermal conductivity of foam, reduce the energy consumption of utilizing the obtained product of foam.
In one aspect of the invention, the present invention proposes a kind of refrigeration equipment.According to embodiments of the invention, this refrigeration equipment comprises above-described hard polyurethane foam.Thus, according to the refrigeration equipment of the embodiment of the invention, refrigeration equipment has the advantages such as good refrigeration effect, less energy consumption, cost are low, environmental protection.In addition, the front also is suitable for this refrigeration equipment natch for foaming agent composotion, the method for preparing hard polyurethane foam and the described feature and advantage of hard polyurethane foam, repeats no more.About the miscellaneous part of refrigeration equipment, can adopt any known parts in any art of refrigeration units, do not repeat them here.
According to one embodiment of present invention, described refrigeration equipment is refrigerator.Thus, according to the refrigeration equipment of the embodiment of the invention, refrigerator has the advantages such as good refrigeration effect, less energy consumption, cost are low, environmental protection.
In one aspect of the invention, the present invention proposes a kind of heat insulation module.According to embodiments of the invention, this heat insulation module comprises above-described hard polyurethane foam.Thus, according to the heat insulation module of the embodiment of the invention, heat insulation module has the advantages such as good heat insulating, less energy consumption, cost are low, environmental protection.In addition, the front also is suitable for this refrigeration equipment natch for foaming agent composotion, the method for preparing hard polyurethane foam and the described feature and advantage of hard polyurethane foam, repeats no more.About the actual conditions that hard polyurethane foam is used as heat insulation module, those skilled in the art can adopt any currently known methods and equipment, do not repeat them here.
Below by specific embodiment, the present invention will be described, need to prove that these embodiment only are for illustration purpose, and can not be construed to by any way limitation of the present invention.In addition, if not otherwise specified, the equipment that then adopts and material are commercially available in the following example.
General method:
1 material and reagent:
1) polyethers A: the sucrose polyethers, 15 ~ 60 weight parts are available from Shanghai Gaoqiao;
2) polyethers B: the tolylene diamine polyethers, 5 ~ 40 weight parts are available from Shanghai Gaoqiao;
3) polyethers C: glycerin polyether, 5 ~ 20 weight parts are available from the Ningwu chemical industry;
4) polyethers D: mix the initiator polyethers, 10 ~ 25 weight parts are available from the Ningwu chemical industry;
5) polyester E: aromatic polyester polyols, 5 ~ 30 weight parts are available from Nanjing Si Taipan;
6) amine catalyst: PC-5 is available from Air Products ﹠amp; Chemicals Inc;
7) amine catalyst: PC-8 is available from Air Products ﹠amp; Chemicals Inc;
8) catalyzer: Dabco TMR-2, available from Air Products ﹠amp; Chemicals Inc;
9) silicone oil A: the rigid foam tensio-active agent, available from Evonik Degussa;
10) silicone oil B: the rigid foam tensio-active agent, available from Momentive;
11) combined polyether: BJ2-3879B is purchased from Nanjing Bayer urethane company limited;
12) organic multiple isocyanate: PM2010 is purchased from Yantai ten thousand China;
13) catalyzer: PC-41 is available from Air Products ﹠amp; Chemicals Inc.
2. equipment:
1) high pressure foaming machine: model: A SYS 100PTW, available from Italian Cannon Kang Long Far East company limited;
2) mixing kettle: model: T-100L-SUS is available from Taiwan Tongyoushun Pneumatic Motor Mfg. Co., Ltd.;
3) multistage static premixing device: model: PX50-4C, available from Singapore profit English polymerization Industrial Co., Ltd;
3. in the following example, the key step for preparing the method for hard polyurethane foam is:
1. reaction mixture comprises:
1) foaming agent composotion comprises: the pentane of 5～20 weight parts, the 134a of the 245fa of 1～25 weight part and 0～5 weight part;
2) polyhydric alcohol composition comprises at least wherein that a kind of functionality is 3, hydroxyl value is 300 ~ 800 polyvalent alcohol;
3) catalyzer;
4) water: content is total polyalcohol formulation 0.5～3.0 % by weight;
5) suds-stabilizing agent;
6) organic multiple isocyanate.
2. the method for preparing pentane/245fa/134a type premixture:
1) load weighted polyether glycol, polyester polyol are packed into mixing kettle adds load weighted linking agent, suds-stabilizing agent, catalyzer etc., and the at normal temperatures physical mixed of pressurizeing stirred 0.5 ~ 1.5 hour;
2) use multistage static premixing device, 134a and 245fa under 0.7 ~ 2.0MPa pressure in proportion one-level mix, mix with a certain proportion of pentane, polyalcohol formulation secondary again.
3. the method that foams:
Organic multiple isocyanate mixes in 1.0 ~ 1.2 ratios with premixture, and premixture and organic isocyanate are injected die cavity under the pressure of 130 ± 10bar.The I-Mould mould is made of aluminum, is of a size of 1100x300x 50mm, and venting hole is arranged at the top, and the gas that can will produce in mould in foaming process is in time got rid of.During foaming, adopt the Cannon high pressure foaming machine of being furnished with the mixing head that is connected with the mould filling orifice, by high-pressure foam machine gun head, can make the hard polyurethane foam of the low heat conduction of extremely-low density.
4. mensuration correlation parameter:
1) I-Mould(is of a size of 1100x 300x 50mm) foam that makes in the mould can be used for heat conducting coefficient measuring, compressive strength, molding density and density distribution.
2) adopt and will steep in a like fashion liquid and inject and to be of a size of 700x 500x 100mm H-Mould, the foam of acquisition is used for measuring the release property of different demould time foams, its objective is the mensuration rate of expansion, measures thus the foam curing rate, approximately 40 ℃ of die temperatures;
3) according to ISO12939-01/DIN 52612, at 10 ℃ (medial temperatures) the lower foam thermal conductivity of measuring, prepared rear 24 hours at foam, from the heart cutting foam sample of molding part, and after cutting, immediately these samples are measured;
4) measure the density of molded foam and free foaming foam according to ASTM1622-88;
5) measure foam compression intensity according to DIN53421-06-84, in kPa.
Embodiment 1,2:
Prepare hard polyurethane foam according to the program described in the general method.
Comparative example 2 used BJ2-3879B in comparative example 1 in the table 1 and the table 3 be at present for the combined polyether of the pure pentamethylene system of industry.
All adopt the foaming agent composotion of the 134a of the 245fa of pentane, 12 weight parts of 10 weight parts and 0.6 weight part at embodiment 1 and embodiment 2, and the foaming agent composotion of the pentane of the BJ2-3879B of comparative example 1 employing 100 weight parts and 12.5 weight parts, but the aromatic-polyether polyvalent alcohol that the three is used different with the content of aromatic polyester polyols (seeing Table 1), then prepare respectively hard polyurethane foam, detect at last correlation parameter, detected result sees Table 1.
As shown in table 1, embodiment 1 compares with comparative example 1 foam, can find out that the former obviously improves bubble mobility, and moulding core density reduces by 18.3%, and thermal conductivity has reduced by 8%.
As shown in table 1, embodiment 2 has increased the consumption of composite catalyst, compares with comparative example 1 foam, and embodiment 2 bubble mobility obviously improve, and moulding core density reduces by 17.8%, and thermal conductivity has reduced by 13%.When demould time is 4min, compare with comparative example 1 foam, embodiment 1,2 foam rate of expansion have all obtained obvious reduction, and embodiment 2 compares with embodiment 1, and rate of expansion is all lower.
As shown in Table 1, adopting pentane, 245fa and 134a is the combination material of mixed foaming agent, and density and the rate of expansion of prepared foam significantly reduce, the dimensional stability of foam and compressive strength be improved significantly.In addition, also reduced the consumption of organic multiple isocyanate, thus favourable attenuating production cost.
Table 1
Embodiment 3-5:
Adopt component shown in the table 2, prepare hard polyurethane foam according to the program described in the general method.
In embodiment 3,4 and 5, all adopt the foaming agent composotion of pentane, 245fa and 134a, but the ratio of the used whipping agent pentane of three, 245fa, 134a is different, and the design's purpose is to verify whipping agent to the impact of foaming properties with this, and relevant information sees Table 2.In an embodiment, taking by weighing whipping agent according to the upper limit, lower limit and the intermediate value of weight part ratio all can implement.
As can be seen from Table 2, by changing the ratio of whipping agent pentane, 245fa and 134a, can effect change significantly the density of foam, and affect less on thermal conductivity, rate of expansion and the compressive strength of foam.
Table 2
Embodiment 6
Prepare hard polyurethane foam according to the program described in the general method.The prepared refrigerator of foam that embodiment 6 adopts by embodiment 1 preparation, the prepared refrigerator of foam that comparative example 2 adopts by comparative example 1 preparation, the relevant information of used foam sees Table 3.Experimental selection is made same model of refrigerator at same equipment, and refrigerator is 3 refrigerators, has the thick 90mm of the reaching refrigeration chamber of foam, 65mm refrigerating chamber and 65mm temperature-changing chamber, and the normal demould time of this refrigerator is 6min.After the refrigerator demoulding, measure the rate of expansion (in mm) of casing left and right sides side top, middle part, bottom, the maximin difference at every place should be less than 2mm, and detected result sees Table 3.As shown in Table 3, compare with comparative example 2, embodiment 6 has preferably bubble mobility and a density distribution, the refrigerator of same model, foam-filled amount has reduced by 17.4%, and density has reduced by 17.7%, and thermal conductivity has reduced by 8.4%, rate of expansion is less, thereby makes foam have advantages of that dimensional stabilizing, weight saving, thermal conductivity reduce.
Table 3
Although the above has illustrated and has described embodiments of the invention; be understandable that; above-described embodiment is exemplary; can not be interpreted as limitation of the present invention; those of ordinary skill in the art is not in the situation that break away from principle of the present invention and aim can change above-described embodiment within the scope of the invention, modification, replacement and modification, and these all drop within the scope of the present invention.
Claims (24)
1. a foaming agent composotion is characterized in that, comprises:
The pentane of 5～20 weight parts;
The 245fa of 1～25 weight part; And
The 134a of 0～5 weight part.
2. foaming agent composotion according to claim 1 is characterized in that, described pentane be selected from pentamethylene, Skellysolve A and iso-pentane one of at least.
3. foaming agent composotion according to claim 1 is characterized in that, comprises:
The pentane of 8～15 weight parts;
The 245fa of 5～20 weight parts; And
The 134a of 0～4 weight part.
4. foaming agent composotion according to claim 3 is characterized in that, comprises:
The pentane of 8～12 weight parts;
The 245fa of 10～15 weight parts; And
The 134a of 0～3 weight part.
5. a method for preparing hard polyurethane foam is characterized in that, comprising:
Foaming agent composotion, polyhydric alcohol composition, catalyzer, water, suds-stabilizing agent and organic multiple isocyanate are mixed, in order to obtain reaction mixture; And
Described reaction mixture is reacted, in order to obtain described polyurethane foam,
Wherein,
Described polyhydric alcohol composition comprise at least a functionality at least 3, hydroxyl value is 300～800 polyvalent alcohol.
6. method according to claim 5 is characterized in that, described polyhydric alcohol composition comprise be selected from polyether glycol and polyester polyol one of at least.
7. method according to claim 6 is characterized in that, described polyvalent alcohol comprises:
With tolylene diamine as initiator by with resulting polyether glycol 5～40 weight parts of olefin oxide addition reaction.
8. method according to claim 6 is characterized in that, described polyhydric alcohol composition comprises the aromatic polyester polyol of 5～30 % by weight.
9. method according to claim 5 is characterized in that, described catalyzer comprises kicker, gel catalyst and catalyst for trimerization.
10. method according to claim 9 is characterized in that, described kicker is for being selected from pentamethyl-diethylenetriamine, two-the dimethyl amine benzyl ethyl ether, N, N, N, N ', N "-Tetramethyl Ethylene Diamine and 4-methyl hexamethylene diamine at least a;
Described gel catalyst is be selected from dimethyl cyclohexane and dimethyl benzylamine at least a;
Described catalyst for trimerization is be selected from first quaternary amine, second quaternary amine, hot quaternary amine and hexahydrotriazine at least a.
11. method according to claim 5 is characterized in that, described suds-stabilizing agent is silicone oil.
12. method according to claim 5 is characterized in that, described organic multiple isocyanate is polymethine polyphenyl polyisocyanate (MDI).
13. method according to claim 5 is characterized in that, described organic multiple isocyanate index is 100～120.
14. method according to claim 5 is characterized in that, described reaction mixes and comprises:
At first 134a is mixed with 245fa; And
Then, mix with pentane, polyvalent alcohol again.
15. method according to claim 5 is characterized in that, the viscosity of described reaction mixture under 20 ℃ is 300～800mpas.
16. method according to claim 5 is characterized in that, described reaction mixture reacts in die cavity, and wherein, the stacking factor of described reaction mixture in die cavity is 1.2 to 2.0.
17. method according to claim 16 is characterized in that, described stacking factor is 1.3 to 1.7.
18. method according to claim 16 is characterized in that, demould time is no more than 4 minutes.
19. a hard polyurethane foam, it is that each described method prepares according to claim 5～18.
20. hard polyurethane foam according to claim 19 is characterized in that, the density of described hard polyurethane foam is 25～35 kilograms per cubic meter.
21. hard polyurethane foam according to claim 19 is characterized in that, the thermal conductivity λ of described hard polyurethane foam (10 ℃) is that 17.00～19.50 milliwatt/rice are opened.
22. a refrigeration equipment is characterized in that, comprises each described hard polyurethane foam of claim 19～21.
23. refrigeration equipment according to claim 22 is characterized in that, described refrigeration equipment is refrigerator.
24. a heat insulation module is characterized in that, comprises each described hard polyurethane foam of claim 19～21.
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