CN117659490A - Reactive composition, polyurethane foam prepared from same and preparation method - Google Patents

Abstract

The invention discloses a reactive composition, polyurethane foam prepared from the reactive composition and a preparation method of the polyurethane foam. The reactive composition of the present invention comprises a polyol component, a physical blowing agent component, and an isocyanate component; the physical foaming agent comprises chlorofluoroolefin and fluoroolefin, wherein the boiling point of the chlorofluoroolefin is 10-20 ℃, and the boiling point of the fluoroolefin is < -10 ℃; based on the total weight of the physical foaming agent components, the total weight ratio of the chlorofluoroolefin and the fluoroolefin is more than or equal to 80wt percent, and the weight ratio of the chlorofluoroolefin is more than 60wt percent; the average hydroxyl number of the polyol component is > 300mgKOH/g, the average functionality is > 3, and the average functionality of the isocyanate component is > 2. The reactive composition provided by the invention can be used for obtaining rigid polyurethane foam with excellent heat insulation performance, and the heat conductivity coefficient of the rigid polyurethane foam can be less than or equal to 15 mW/m.K; the structure of the foam cells can be optimized, so that the anisotropy of the foam cells is low, and the comprehensive performance of the foam is optimized.

Description

Reactive composition, polyurethane foam prepared from same and preparation method

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to a reactive composition, polyurethane foam prepared from the reactive composition and a preparation method of the polyurethane foam.

Background

The heat insulating material is a key component of electric products such as a refrigerator, and the energy consumption level of the electric products is directly influenced by the heat insulating performance of the heat insulating material. With the advance of energy saving and consumption reduction policies, the market has put higher demands on the heat conductivity coefficient of the heat insulating material. At present, the heat-insulating material is a vacuum heat-insulating plate (VIP) with lower heat conductivity coefficient, which is formed by compounding a filling core material and a vacuum protection surface layer, wherein the heat conductivity coefficient is only 2-4 mW/m.K. However, VIP panels are expensive and difficult to fill in the corners of cavities and cavities of complex structures, and have limited application because of the cold leakage effect at their edges.

The most mainstream of the heat insulating materials is rigid polyurethane foam, which realizes better heat preservation and heat insulation effects by utilizing a closed cell structure and heat insulating gas in cells, and can realize complete filling of a cavity with a complex structure by using a reaction molding filling mode, but compared with a VIP plate, the heat conductivity coefficient of the rigid polyurethane foam is still higher.

CN113316599a discloses a thermoset foam with improved insulation value, which uses LBA as main foaming agent and matches with low-solubility polyester polyol to make rigid polyurethane foam with initial thermal conductivity as low as 17.62mW/m·k.

CN115073694A discloses a rigid polyurethane foam with low density and ultralow heat conductivity coefficient, a preparation method and application thereof, wherein a composite foaming system of LBA, butane and methyl formate is used, and the density of the prepared foam is 27.4-28.3 kg/m ³ The heat conductivity coefficient is 16.4-17.0 mW/mK.

In order to fully exert the heat insulation advantage of the rigid polyurethane foam, and simultaneously reduce the difference of the heat conductivity coefficient between the rigid polyurethane foam and the VIP plate, the heat conductivity coefficient of the rigid polyurethane foam still needs to be further reduced so as to enable the rigid polyurethane foam to meet the pursuit of low heat conductivity coefficient in the market, and finally, the low-energy-consumption operation of an application end is realized, and the carbon emission reduction of the polyurethane industry is promoted.

Disclosure of Invention

The invention aims to: the invention aims at overcoming the defects of the prior art and providing a reactive composition, polyurethane foam prepared from the reactive composition and a preparation method of the polyurethane foam.

The technical scheme is as follows: the aim of the invention is achieved by the following technical scheme:

the invention provides a reactive composition, which comprises a polyol component, a physical foaming agent component and an isocyanate component, wherein the physical foaming agent component comprises chlorofluoroolefin and fluoroolefin, the boiling point of the chlorofluoroolefin is 10-20 ℃, and the boiling point of the fluoroolefin is < -10 ℃; the total weight of the chlorofluoro-olefin and the fluoroolefin is more than or equal to 80wt percent based on the total weight of the physical foaming agent component, and the weight of the chlorofluoro-olefin is more than 60wt percent; the average hydroxyl number of the polyol component is > 300mgKOH/g, the average functionality is > 3, and the average functionality of the isocyanate component is > 2.

The invention adopts the complex of the chlorofluoro-olefin foaming agent with the boiling point of 10-20 ℃ and the fluoroolefin foaming agent with the boiling point of < -10 ℃, can cooperate in the polyurethane foaming reaction process, optimizes the nucleation process and the vaporization rate of the physical foaming agent component, and leads the physical foaming agent component to be matched with the polyurethane reaction process, thereby obtaining the uniform and finely distributed cell structure and being beneficial to reducing the heat conductivity coefficient of the rigid polyurethane foam.

As one embodiment, the chlorofluoroalkene may have a boiling point of 14 to 19℃and the fluoroalkene may have a boiling point of-30 to-14 ℃. The effect of improving the thermal conductivity is better when the total weight of the high boiling chlorofluoroolefin and the low boiling fluoroolefin is greater than or equal to 80wt% (e.g., 80 to 100 wt%) and the weight of the chlorofluoroolefin is greater than 60wt% (which may be 66 to 92 wt%), based on the total weight of the physical blowing agent component.

The chlorofluoroolefin according to the present invention is a compound containing both an unsaturated double bond, a carbon-chlorine bond and a carbon-fluorine bond, wherein the number of carbon atoms of the olefin is preferably 3 and the total number of carbon-halogen bonds is preferably 4 to 5 from the viewpoint of availability of raw materials.

In a preferred embodiment of the present invention, the chlorofluoroalkene having a boiling point of 10 to 20 ℃ is trans-1-chloro-3, 3-trifluoropropene and/or cis-1-chloro-2, 3-tetrafluoropropene.

The fluoroolefin disclosed by the invention is a compound containing both an unsaturated double bond and a carbon-fluorine bond and does not contain a carbon-chlorine bond, the carbon number of the olefin can be 3-4, and the fluoroolefin can be perfluoro olefin or fluoro olefin.

In a preferred embodiment of the present invention, the fluoroolefin having a boiling point of < -10deg.C is trifluoropropene (3, 3-trifluoropropene, CAS: 677-21-4), tetrafluoropropene (trans-1, 3-tetrafluoropropene, CAS:1645-83-6 or 2, 3-tetrafluoropropene, CAS: 754-12-1), pentafluoropropene (1, 2, 3-pentafluoropropene, CAS:2252-83-7 or 1, 3-pentafluoropropene, CAS: 690-27-7), pentafluorobutene (3, 4-pentafluorobutene, CAS: 374-27-6), hexafluoropropene (perfluoropropene, CAS: 116-15-4).

In a preferred embodiment of the present invention, the molar ratio of chlorofluoroolefin to fluoroolefin is (2-28): 1. Within this ratio range, a better cell structure is favored to achieve both low density and low thermal conductivity. Further, the molar ratio of the two is preferably (2 to 18): 1.

As a further preferred embodiment thereof, the physical blowing agent component may consist of 30 to 46 parts of chlorofluoroolefin and 1 to 15 parts of fluoroolefin.

As another embodiment, the physical foaming agent component can also contain a third foaming agent and/or foaming auxiliary agent besides the chlorofluoroolefin with the boiling point of 10-20 ℃ and the fluoroolefin with the boiling point of < -10 ℃ so as to realize the purposes of further optimizing the foam performance and the like. The weight of the third foaming agent is less than or equal to 10wt percent, and the weight of the foaming auxiliary agent is less than or equal to 10wt percent based on the total weight of the physical foaming agent components. The third foaming agent can be alkane compounds, chlorofluoroalkene with the boiling point less than 10 ℃ or with the boiling point more than 20 ℃, fluoroalkene with the boiling point more than-10 ℃, hydrofluorocarbon compounds, carbon dioxide, alcohols with 1-5 carbon atoms, aldehydes with 1-4 carbon atoms, ethers or diethers with 1-4 carbon atoms, organic acid or organic acid esters, and the like. Among them, alkanes having a boiling point of-45℃to 100℃are preferable, such as cyclopentane, isopentane, n-pentane, n-butane, isobutane, cyclohexane, propane, n-hexane and isomers thereof, n-heptane and isomers thereof, and the like. The fluoroolefin with the boiling point of > -10 ℃ can be selected from monofluoropropene, difluoropropene, monofluorobutene, difluorobutene, trifluorobutene, tetrafluorobutene, hexafluorobutene, heptafluorobutene, octafluorobutene, octafluoropentene or difluoroethylene, etc. The chlorofluoroalkene having a boiling point > 20℃may be selected from cis-1-chloro-3, 3-trifluoropropene and the like. The hydrofluorocarbon may be selected from the group consisting of pentafluoropropane, pentafluorobutane, difluoroethane, tetrafluoroethane, and the like, and the use of a hydrofluorocarbon as a blowing agent is not suggested in the present invention in view of the high global warming potential (GWP value) of the hydrofluorocarbon.

The foaming auxiliary agent can be at least one of perfluoroolefin, fluorine-containing ether and perfluoroalkyl amine with carbon number more than 3. Wherein the perfluoroolefin having more than 3 carbon atoms is selected from hexafluoropropylene dimer, hexafluoropropylene trimer, perfluoro-1-hexene, perfluoro-1-butene, perfluoro-2-butene, perfluorobutadiene, perfluoro-2-methyl-2-pentene, perfluoro-4-methyl-2-pentene, perfluorocyclopentene, perfluoro-1-heptene, perfluorobutylethylene, perfluorocyclohexane, octafluorocyclobutane or perfluoro-1, 2-dimethylcyclohexane. The fluorine-containing ether may be selected from nonafluoroisobutyl methyl ether, nonafluorobutyl ethyl ether, nonafluoroisobutyl ethyl ether, difluoroethyl tetrafluoroethyl ether, difluoromethyl trifluoroethyl ether, bis (trifluoroethyl) ether, tetrafluoroethyl ethyl ether, tetrafluoroethyl propyl ether, tetrafluoroethyl difluoromethyl ether, tetrafluoroethyl tetrafluoropropyl ether, octafluoropentyl tetrafluoroethyl ether heptafluoromethyl propyl ether, 1, 3-pentafluoro-2-trifluoromethyl propyl methyl ether, perfluorobutyl methyl ether, 2-difluoroethyl trifluoromethyl ether, trifluoromethyl trifluoro vinyl ether perfluoropropyl vinyl ether, 1, 3-hexafluoroisopropyl methyl ether 2, 3-pentafluoropropyl methyl ether, 2-trifluoroethyl methyl ether or a perfluoro-cyclic ether. The perfluoroalkyl amine is preferably perfluoro tributylamine or perfluoro triethylamine.

The third foaming agent and the foaming auxiliary agent are preferably used in an amount which does not increase the heat conductivity coefficient, for example, the physical foaming agent component can be composed of 30-46 parts of chlorofluoroolefin, 1-15 parts of fluoroolefin, 2.5-4 parts of the third foaming agent and 1-4 parts of the foaming auxiliary agent.

In a preferred embodiment of the present invention, the physical blowing agent component further comprises cyclopentane; further, the cyclopentane content is 10wt% or less based on the total weight of the physical blowing agent component, thereby avoiding adverse effects on heat insulating properties and low temperature dimensional stability. Preferably, the cyclopentane content of the physical blowing agent component is 8-10wt%, so that the total cost of the physical blowing agent component can be reduced, and better heat insulation performance and low-temperature dimensional stability can be achieved.

Polyol components commonly used in rigid polyurethane foams include polyether polyols, polyester polyols, bio-based polyols, catalysts, foam stabilizers, water, additives, and the like, which may be flame retardants, solubilizing agents, fillers, colorants, and the like. As one of the embodiments, the polyol component of the present invention may be composed of polyether polyol, polyester polyol, catalyst, foam stabilizer and water. For matching with the physical blowing agent component of the present invention, it is preferred that the polyol component of the present invention have an average hydroxyl number of > 300mgKOH/g, which may be 315 to 505mgKOH/g, or 370 to 429mgKOH/g, and an average functionality of > 3, which may be 3 to 6, or 3.3 to 4.6.

In order to balance the vaporization rate of the physical blowing agent component with the polyurethane reaction rate, it is preferred that the polyol component has a viscosity of > 5000 mPa.s at 25℃to reduce the escape loss of the physical blowing agent component and to obtain a better cell distribution. It is further preferred that the polyol component has a viscosity of 5014 to 9500 mPa.s at 25℃to obtain a uniform cell distribution.

The polyether polyol is prepared by using conventional polyether polyol in the field, namely a polyol compound prepared by ring-opening polymerization reaction by taking alkylene oxide as a polymerization monomer and taking polyhydroxy and amine compounds as an initiator. Examples of the common starter used in the art are trimethylolpropane, glycerol, mannitol, sorbitol, pentaerythritol, sucrose, xylitol, triethanolamine, aniline, etc. The invention can obtain better foam performance by using the conventional polyether.

In order to achieve a good foam strength, it is preferred that the conventional polyether polyols have a hydroxyl number of 350 to 650mgKOH/g and a functionality of > 3.

Further, in order to give a sufficient synergistic effect with a small total amount of the physical blowing agent component, it is preferable that the polyol component of the present invention contains a polyether polyol I prepared by using sucrose and glycerin as a mixed initiator, the polyether polyol I having a functionality of 4 to 7 and a hydroxyl value of 370 to 550mgKOH/g. The polyether polyol I can improve the inclusion of the physical foaming agent components, ensure the full play of the synergistic effect among the foaming agent components in the reaction process, and accounts for 28-61 wt% of the total weight of the polyol components.

The polyester polyols of the present invention may be prepared using conventional polyester polyols in the art, that is, typically by condensing an organic dicarboxylic acid (anhydride or ester) with a small molecule polyol (including a diol), or by polymerizing a lactone with a polyol. Wherein the dicarboxylic acid (anhydride or ester) may be selected from phthalic anhydride, terephthalic acid or dimethyl terephthalate, adipic acid, etc.; the small molecule polyol may be selected from ethylene glycol, propylene glycol, glycerin, butylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, etc. In order to achieve both the polyurethane reaction rate and the crosslinking density, the polyester polyol preferably has a functionality of 2 to 3 or 2 to 2.5 and a hydroxyl value of 200 to 440mgKOH/g.

In a preferred embodiment of the present invention, the polyol component contains an aromatic polyol; the weight ratio of the aromatic polyol is more than or equal to 32wt percent based on the total weight of the polyol component. Such as 32 to 67wt% to give consideration to specific strength.

The aromatic polyol may be an aromatic polyether polyol and/or an aromatic polyester polyol, i.e., a polyol containing a benzene ring, such as an aromatic polyether polyol obtained by reacting an aromatic dicarboxylic acid (or anhydride) with a polyol, preferably a phthalic anhydride polyester polyol, with an aniline compound as an initiator. The aromatic polyol can play a better synergistic effect with the physical foaming agent component of the invention so as to obtain a better nucleating process, and the bubble nuclei are uniformly grown, so that the anisotropy of the cells can be improved, and the foam performance can be optimized.

In a preferred embodiment of the present invention, the polyol component further comprises water; the water is present in a weight ratio of < 1.5wt% based on the total weight of the polyol component.

The water in the polyol component comprises added water and self-contained water in the raw material component, wherein the weight ratio of the added water is less than or equal to 1.1wt%, such as 0.8-1.1 wt%, based on the total weight of the polyol component, and the total amount of the water in the polyol component is less than or equal to 1.4wt%, such as 0.9-1.4 wt%, so as to achieve better material fluidity and foam performance.

The catalyst of the invention is a catalyst commonly used in the field, and the commonly selected catalyst has the functions of catalyzing foaming reaction and gel reaction, and can also optionally have the function of catalyzing trimerization reaction. Such as one or more selected from pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, tetramethylhexamethylenediamine, dibutyltin dilaurate, N-ethylmorpholine, N-dimethylcyclohexylamine, triethylenediamine, 1, 2-dimethylimidazole, dimethylbenzylamine, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2,4, 6-tris (dimethylaminomethyl) phenol, methylamine salt, potassium octoate, potassium 2-ethylhexanoate, potassium acetate, (2-hydroxypropyl) trimethylammonium formate, ethylquat salt and Xin Ji ammonium salt. When two or more catalysts are selected, a mixture of them in an arbitrary ratio may be employed. The catalyst is present in an amount of 1.9 to 5.3wt% based on the total weight of the polyol component.

In order to reduce the tendency of cell consolidation to obtain a fine cell structure, it is preferred in the present invention that the foam stabilizer is a polysiloxane-alkylene oxide block copolymer. Still further, to achieve a smaller cell size, it is preferred that the foam stabilizer be present in an amount of 1.9 to 4.6 weight percent based on the total weight of the polyol component. Can be selected from one or more of M-8815, M-8806, M-8860, M-8882, M-88308, M-88310, M-88312, winning B8465, B84725, B8486, B84204, B8404, B8407, B8409, B8110 of Maillard chemical, L5162, L6972, L6884, L6988, and L6889 of Michaelis. When two or more foam stabilizers are selected, any ratio of mixing may be employed.

As a particularly preferred embodiment, the polyol component of the present invention may comprise the following materials in weight percent: 92 to 96wt% of polyol (including polyether polyol and polyester polyol), 1.9 to 2.4wt% of catalyst, 1.9 to 4.6wt% of foam stabilizer, and 0.8 to 1.1wt% of water.

The isocyanate component is typically an isocyanate having an average functionality of > 2, as is well known in the art, and may be polymethylene polyphenyl polyisocyanates (abbreviated polymeric MDI), toluene diisocyanate (abbreviated TDI), modified isocyanates, and the like. When two or more isocyanates are selected, a mixture of them in any ratio may be employed. Among these, polymeric MDI preferably has an average functionality of 2.7 to 2.9 to give consideration to the thermal conductivity of polyurethane rigid foam. The polymeric MDI having an average functionality of 2.7 may be selected fromPM200、/>44v20L、/>M20s、/>Any of the PMs 2010. The polymeric MDI having an average functionality of 2.9 may be selected from +.>M50、/>PM400、/>44V40L、/>2085. The industrial TDI is usually a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate, and TDI-65, TDI-80, TDI-100, etc. can be used in the present invention depending on the mass ratio of 2, 4-toluene diisocyanate in the mixture. The modified isocyanate is a substance prepared by reacting polyol with isocyanate, wherein the polyol can be polyether polyol taking glycerol, glycol, diethylene glycol, pentaerythritol and the like as an initiator, or phthalic anhydride polyester polyol, or bio-based polyol. The bio-based polyol is a polyol compound prepared from soybean oil, castor oil, rapeseed oil, jatropha curcas oil, olive oil, palm oil or derivatives thereof, such as castor oil polyol, olive oil polyol, palm oil polyol, castor oil derivative polyol, etc.

The amount of isocyanate component is generally determined based on the isocyanate index, which refers to the ratio of the molar amount of NCO groups in the isocyanate component to the molar amount of OH groups in the polyol component, and is generally from 0.9 to 1.4. For matching the polyol component of the present application, the isocyanate index is preferably 1.05 to 1.2. The weight ratio of the polyol component to the physical foaming agent component to the isocyanate component=100:36-48:86-135.

The invention also provides a polyurethane foam prepared from the reactive composition, wherein the foam contains chlorofluoro-olefin and fluoroolefin.

In one specific embodiment of the invention, the polyurethane foam is prepared by foaming the polyol component, the physical foaming agent component and the isocyanate component, and the foam cells of the prepared polyurethane foam contain chlorofluoro-olefin and fluoroolefin, wherein the total amount of the chlorofluoro-olefin and the fluoroolefin is 86.2-94.5 wt% based on the total weight of the gas obtained in the polyurethane foam, and the chlorofluoro-olefin accounts for 70-92 wt%.

In order to achieve both low thermal conductivity and low density, it is preferred that the gas obtained in the polyurethane foam consists of the following substances in weight ratio: 62 to 92 weight percent of chlorofluoro-olefine, 2.5 to 31.1 weight percent of fluoro-olefine, 4.4 to 7.0 weight percent of carbon dioxide, 0 to 9.4 weight percent of cyclopentane, 0 to 9.4 weight percent of other foaming agents and foaming auxiliary agents, and the density of the prepared polyurethane hard foam is less than 30kg/m ³ Such as 24.6-29 kg/m ³ The heat conductivity coefficient at 10 ℃ is less than or equal to 15 mW/(m.K), such as 13.0-15.0 mW/(m.K).

The invention also provides a preparation method of the polyurethane foam, which uses the reactive composition as a raw material, mixes the raw materials, and then carries out polyurethane reaction to prepare the polyurethane foam.

The preparation method of the rigid polyurethane foam of the invention is achieved by adopting the known technology in the field, for example, after the physical foaming agent component, the polyol component and the isocyanate component are uniformly stirred and mixed at high speed, polyurethane reaction is carried out, wherein the mixing and adding of the chlorofluoroolefin foaming agent and the fluoroolefin foaming agent used in the invention can be carried out in three modes:

premixing fluoroolefin and isocyanate components to form a premix A, premixing the rest of the physical foaming agent and the polyol components to form a premix B, and uniformly stirring and mixing the premix A and the premix B at a high speed, wherein the mixing can be realized through a two-component gun head mixing device;

premixing fluoroolefin, part of chlorofluoroolefin and isocyanate components to form a premix A, premixing the rest of physical foaming agent and polyol components to form a premix B, and uniformly stirring and mixing the premix A and the premix B at a high speed to perform polyurethane reaction, wherein the mixing can be realized by a two-component gun head mixing device;

in a third mode, fluoroolefin is used as a first component, a premix of the rest of the physical foaming agent and the polyol component is used as a second component, the isocyanate component is used as a third component, and then the mixture is stirred at a high speed through a three-component gun head mixing device, and the polyurethane reaction is carried out after the three components are mixed.

All three modes can improve the stability of the reactive composition and prevent side reactions of fluoroolefins, catalysts and foam stabilizers during storage.

In a preferred embodiment of the invention, the pressure of the preparation environment after mixing is from 0.4 to 1.6bar.

The reactive composition can be injected into the cavity for reaction molding after being mixed at high speed, and the pressure in the cavity of the filler is the pressure of the preparation environment after mixing. The pressure range suitable for the physical foaming agent component of the invention is 0.4-1.6 bar, namely the pressure value can be in a normal pressure state, and the pressure value can be controlled to be changed within a preset pressure range, for example, when the reactive composition is injected into a cavity, the pressure can be regulated and controlled to be 1.0bar < P1 and less than or equal to 1.6bar, and after the injection is completed, the pressure is reduced to be 0.4bar and less than or equal to P2 and less than 1.0bar, wherein P1 and P2 are absolute pressures. When the pressure of the preparation environment is controlled by pressurizing and then depressurizing, the addition amount of the fluoroolefin foaming agent is also beneficial to be increased, so that the density of the rigid polyurethane foam is further reduced under the condition of the same material injection amount.

The beneficial effects are that:

(1) The reactive composition provided by the invention can be used for obtaining rigid polyurethane foam with excellent heat insulation performance, and the heat conductivity coefficient of the rigid polyurethane foam can be less than or equal to 15 mW/m.K.

(2) The reactive composition provided by the invention can also optimize the structure of the foam cells, so that the anisotropy of the foam cells is low, and the comprehensive performance of the foam is optimized.

(3) The invention has the advantages of low material injection quantity, excellent foam performance, excellent processability and the like while taking low heat conductivity into account, and the physical foaming agent used is safe and environment-friendly and has no inflammable risk.

Detailed Description

The technical scheme of the present invention is described in detail below through specific examples, but the scope of the present invention is not limited to the examples.

The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase through regular channels, with no manufacturer noted.

The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, are all commercially available products.

Unless otherwise indicated, the various terms in the present invention are defined as follows:

apparent core density: the average core density of foam prepared by injecting polyurethane raw materials into a mould for foaming is 1100mm multiplied by 300mm multiplied by 50mm;

the uniformity of the density distribution is represented by the extremely poor core density, namely the difference between the maximum core density and the minimum core density;

the water mass fraction, the average hydroxyl value and the viscosity are carried out by adopting a method in polyurethane rigid foam combined polyether for HG/T4961-2016 refrigerator and refrigerator, the apparent core density, the compressive strength, the heat conductivity coefficient and the dimensional stability are carried out by adopting a method in rigid polyurethane foam plastic for GB/T26689-2011 refrigerator and refrigerator, and the gas component in the rigid polyurethane foam is carried out by adopting a device and a method described in CN 204255913U.

The raw materials used in the examples and comparative examples of the present invention are as follows:

polyether polyol I, which takes sucrose and glycerol as composite initiator, is respectively: voranol 370 (hydroxyl value 370mgKOH/g, functionality 7.0), voranol 550 (hydroxyl value 550mgKOH/g, functionality 4.9), voranol 360 (hydroxyl value 360mgKOH/g, functionality 4.5), voranol 490 (hydroxyl value 490mgKOH/g, functionality 4.3);

glycerol polyether polyol: voranol 270 (hydroxyl value 238mgKOH/g, functionality 3.0);

sorbitol polyether polyol: red Baoli H5021 (hydroxyl value 370mgKOH/g, functionality 4.6);

phenylenediamine polyether polyol: new Hengfeng material HF406G (hydroxyl value 440mgKOH/G, functionality 4.0);

phthalic anhydride polyester polyol: terate HT5150 (hydroxyl value 295mgKOH/g, functionality 2.25), terate HT5360 (hydroxyl value 305mgKOH/g, functionality 2.45), terate HT5510 (hydroxyl value 257mgKOH/g, functionality 2.0), xuchuan chemical XCPA-195 (hydroxyl value 200mgKOH/g, functionality 2.0), stepanpol PS-4002 (hydroxyl value 400mgKOH/g, functionality 2.0).

The formulation compositions of the reactive compositions used in the examples and comparative examples of the present invention are shown in tables 1 to 4 (in parts by weight).

Table 11# to 10# polyol component composition

Composition of matter of polyol component # 2 to # d8

Physical blowing agent component and isocyanate component composition of tables 31 # to 10#

Physical blowing agent component and isocyanate component composition of tables 4# 11 through D8#

The formulations of tables 1 to 4 were used for the preparation of rigid polyurethane foams.

Example 1

The rigid polyurethane foam was prepared using a formulation # 1 and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 92wt% chlorofluoroolefin, 2.5wt% fluoroolefin, 5.5wt% carbon dioxide.

Example 2

The rigid polyurethane foam was prepared using a formulation # 2 and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 70.3wt% chlorofluoroolefin, 4.7wt% fluoroolefin, 6.3wt% carbon dioxide, 9.4wt% cyclopentane, 9.3wt% fluoroether.

Example 3

The rigid polyurethane foam was prepared using a 3# formulation and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 79.2wt% chlorofluoroolefin, 7.0wt% fluoroolefin, 5.7wt% carbon dioxide, 8.1wt% n-butane and perfluoroalkanes.

Example 4

The rigid polyurethane foam was prepared using a formulation # 4 and a three component gun head injection was used. Hexafluoropropylene is input into a three-component gun head through a first pipeline, meanwhile, a premix of a polyol component and the rest of a physical foaming agent component is input into the three-component gun head through a second pipeline, an isocyanate component is input into the three-component gun head through a third pipeline, a reactive composition is injected into a cavity of a mould after being mixed in the three-component gun head, the mould temperature is 38-42 ℃, the pressure P1 in the mould cavity is kept at 1.6bar absolute pressure, the pressure P1 is kept until the absolute pressure P2 is 0.40bar immediately and naturally reduced after the injection is finished, the pressure in the mould cavity is kept until the mixture is solidified and formed, and the gas composition in the foam is detected as follows: 72.5wt% chlorofluoroolefin, 21.7wt% fluoroolefin, 5.8wt% carbon dioxide.

Example 5

The rigid polyurethane foam was prepared using a formulation # 5 and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 77.6wt% chlorofluoroolefin, 10.2wt% fluoroolefin, 4.4wt% carbon dioxide, 7.8wt% cyclopentane.

Example 6

The rigid polyurethane foam was prepared using a 6# formulation and a two component gun head injection was used. Premixing 2, 3-tetrafluoropropene, 50wt% of cis-1-chloro-2, 3-tetrafluoropropene and an isocyanate component to form a premix A, premixing the rest of the physical foaming agent and a polyol component to form a premix B, uniformly stirring and mixing the premix A and the premix B at a high speed by a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes communicating the mold cavity with the atmospheric pressure on the mold are always in a natural open state, reacting and curing the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is: 86.5wt% chlorofluoroolefin, 7.5wt% fluoroolefin, 6.0wt% carbon dioxide.

Example 7

The rigid polyurethane foam was prepared using a formulation # 7 and a two-component gun head injection was used. Premixing hexafluoropropylene and isocyanate components to form a premix A, premixing the rest physical foaming agent and a polyol component to form a premix B, uniformly stirring and mixing the premix A and the premix B at a high speed by a two-component gun head, injecting the mixture into a cavity of a die, keeping the die temperature at 38-42 ℃, keeping the pressure P1 in the die cavity to be 1.6bar absolute pressure, keeping the pressure in the die cavity to be 0.40bar absolute pressure P2 after the injection is finished, and keeping the pressure in the die cavity until the mixture is cured and molded to obtain rigid polyurethane foam, wherein the gas composition in the foam is detected to be: 76.3wt% chlorofluoroolefin, 17.2wt% fluoroolefin, 6.5wt% carbon dioxide.

Example 8

The rigid polyurethane foam was prepared using a 8# formulation and a two component gun head injection was used. Premixing hexafluoropropylene, 30wt% of trans-1-chloro-3, 3-trifluoropropene and an isocyanate component to form a premix A, premixing the rest of physical foaming agent and a polyol component to form a premix B, uniformly stirring and mixing the premix A and the premix B at a high speed by a two-component gun head, injecting the mixture into a cavity of a die, wherein the die temperature is 38-42 ℃, the internal pressure of the die is normal pressure, holes communicating the die cavity with the atmospheric pressure on the die are always in a natural open state, reacting and curing the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is: 81.3wt% chlorofluoroolefin, 12.2wt% fluoroolefin, 6.5wt% carbon dioxide.

Example 9

The rigid polyurethane foam was prepared using a 9# formulation and injected using a three component gun head. 3, 4-pentafluorobutene is input into the three-component gun head through a first pipeline, meanwhile, a premix of a polyol component and the rest of a physical foaming agent component is input into the three-component gun head through a second pipeline, an isocyanate component is input into the three-component gun head through a third pipeline, a reactive composition is injected into a cavity of a mould after being mixed in the three-component gun head, the mould temperature is 38-42 ℃, the pressure P1 in the mould cavity is kept to be 1.6bar absolute pressure, the pressure in the mould cavity is kept to be naturally reduced to 0.40bar absolute pressure P2 immediately after the injection is completed, the pressure in the mould cavity is kept until the hard polyurethane foam is obtained through curing and forming, and the gas composition in the foam cavity is detected as follows: 62.3wt% chlorofluoroolefin, 31.1wt% fluoroolefin, 6.6wt% carbon dioxide.

Example 10

The rigid polyurethane foam was prepared using a formulation # 10 and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 81.4wt% chlorofluoroolefin, 12.9wt% fluoroolefin, 5.7wt% carbon dioxide.

Example 11

The rigid polyurethane foam was prepared using the 11# formulation and a two-component gun head injection was used. Premixing hexafluoropropylene and isocyanate components to form a premix A, premixing the rest of the physical foaming agent and the polyol components to form a premix B, uniformly stirring and mixing the premix A and the premix B at a high speed by a two-component gun head, injecting the mixture into a cavity of a die, wherein the die temperature is 38-42 ℃, the internal pressure of the die is normal pressure, holes communicated with the die cavity and the atmospheric pressure on the die are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is: 75.9wt% chlorofluoroolefin, 10.3wt% fluoroolefin, 7.0wt% carbon dioxide, 6.8wt% cis-1, 4-hexafluorobutene.

Comparative example 1

The rigid polyurethane foam was prepared using a d1# formulation and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 94.7wt% chlorofluoroolefin, 5.3wt% carbon dioxide.

Comparative example 2

The rigid polyurethane foam was prepared using a d2# formulation and injected using a three component gun head. Hexafluoropropylene is input into the three-component gun head through a first pipeline, meanwhile, a polyol component is input into the three-component gun head through a second pipeline, an isocyanate component is input into the three-component gun head through a third pipeline, the reactive composition is injected into a cavity of a mould after being mixed in the three-component gun head, the mould temperature is 38-42 ℃, the pressure P1 in the mould cavity is kept to be 1.6bar absolute pressure, the pressure P1 is kept to be naturally reduced to 0.40bar absolute pressure P2 immediately after the injection is completed, the pressure in the mould cavity is kept until solidification and molding are carried out, and the result shows that foam-like foaming is carried out, and foaming failure is caused.

Comparative example 3

The rigid polyurethane foam was prepared using a d3# formulation and injected using a three component gun head. Trans-1, 4-hexafluoro-2-butene is input into the three-component gun head through a first pipeline, meanwhile, a premix of a polyol component and the rest of a physical foaming agent component is input into the three-component gun head through a second pipeline, an isocyanate component is input into the three-component gun head through a third pipeline, a reactive composition is injected into a cavity of a mould after being mixed in the three-component gun head, the mould temperature is 38-42 ℃, the pressure P1 in the mould cavity is kept to be 1.6bar absolute pressure, the pressure P1 is kept to be naturally reduced to be 0.40bar absolute pressure P2 immediately after the injection is completed, the pressure in the mould cavity is kept until solidification and molding are carried out, and the rigid polyurethane foam is obtained through detection, wherein the gas composition in the foam cells is as follows: 61.8% by weight of chlorofluoroolefin, 6.3% by weight of carbon dioxide, 31.9% by weight of trans-1, 4-hexafluoro-2-butene.

Comparative example 4

The rigid polyurethane foam was prepared using a d4# formulation and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 84.1wt% chlorofluoroolefin, 6.0wt% carbon dioxide, 9.9wt% n-butane.

Comparative example 5

The rigid polyurethane foam was prepared using a d5# formulation and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 23.6wt% chlorofluoroolefin, 16.8wt% fluoroolefin, 9.1wt% carbon dioxide, 50.5wt% cyclopentane.

Comparative example 6

The rigid polyurethane foam was prepared using a d6# formulation and injected using a three component gun head. 3, 4-pentafluorobutene is input into the three-component gun head through a first pipeline, meanwhile, a premix of a polyol component and the rest of a physical foaming agent component is input into the three-component gun head through a second pipeline, an isocyanate component is input into the three-component gun head through a third pipeline, a reactive composition is injected into a cavity of a mould after being mixed in the three-component gun head, the mould temperature is 38-42 ℃, the pressure P1 in the mould cavity is kept to be 1.6bar absolute pressure, the pressure in the mould cavity is kept to be naturally reduced to 0.40bar absolute pressure P2 immediately after the injection is completed, the pressure in the mould cavity is kept until the hard polyurethane foam is obtained through curing and forming, and the gas composition in the foam cavity is detected as follows: 79.6wt% chlorofluoroolefin, 13.3wt% fluoroolefin, 7.1wt% carbon dioxide.

Comparative example 7

The rigid polyurethane foam was prepared using a d7# formulation and a two-component gun head injection was used. Premixing hexafluoropropylene and isocyanate components to form a premix A, premixing the rest of the physical foaming agent and the polyol components to form a premix B, uniformly stirring and mixing the premix A and the premix B at a high speed by a two-component gun head, injecting the mixture into a cavity of a die, wherein the die temperature is 38-42 ℃, the internal pressure of the die is normal pressure, holes communicated with the die cavity and the atmospheric pressure on the die are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is: 76.3wt% chlorofluoroolefin, 10.3wt% fluoroolefin, 6.6wt% carbon dioxide, 6.8wt% cis-1, 4-hexafluorobutene.

Comparative example 8

The rigid polyurethane foam was prepared using a d8# formulation and a two-component gun head injection was used. Premixing a physical foaming agent and a polyol component to form a premix, then uniformly stirring and mixing the premix and an isocyanate component at a high speed through a two-component gun head, injecting the mixture into a cavity of a mold, wherein the mold temperature is 38-42 ℃, the internal pressure of the mold is normal pressure, holes on the mold, which are communicated with the mold cavity and the atmospheric pressure, are always in a natural open state, reacting and curing and forming the reactive composition to obtain rigid polyurethane foam, and detecting that the gas composition in the foam is as follows: 86.7wt% chlorofluoroalkene, 2.6wt% fluoroalkene, 5.6wt% carbon dioxide, 5.1wt% n-butane and perfluoroalkanes.

The rigid polyurethane foams prepared in the examples and comparative examples of the present invention were subjected to performance characterization, and the results are shown in tables 5 and 6.

Table 51 # to 10# rigid polyurethane foam properties

Table 6# 11 to D8# rigid polyurethane foam Properties

As can be seen from the data in the table, the rigid polyurethane foam prepared using the reactive composition of the present invention has a small anisotropy (ratio of compressive strength in the parallel direction to compressive strength in the perpendicular direction), has an excellent cell structure, has a low thermal conductivity, and can achieve good properties at a low core density level. The vertical compressive strength refers to the compressive strength perpendicular to the rising direction of the foam, and the parallel compressive strength refers to the compressive strength parallel to the rising direction of the foam. While the comparative examples were all less effective.

Comparative example 1 all used high boiling trans-1-chloro-3, 3-trifluoropropene as the physical blowing agent component, the core density obtained was similar to that obtained in example 1, but the thermal conductivity was significantly increased, and the dimensional stability at low temperature was poor, the dimensional deformation rate was-1.5%, and the dimensional deformation rate data described in the present invention takes the maximum value among the dimensional deformation rates of length, width and thickness.

Comparative example 2 all used hexafluoropropylene of low boiling point as a physical blowing agent component, foam-like foaming phenomenon was generated even under pressure-regulated foaming conditions, resulting in foaming failure, and it was found that the maximum solubility of the polyurethane reaction material to hexafluoropropylene was limited, and that hexafluoropropylene of low boiling point was extremely liable to escape from the material system, resulting in a mismatch of bubble generation rate and polyurethane reaction rate, so that a simple hexafluoropropylene foaming system could not be realized, and if the amount of hexafluoropropylene was reduced until the foam-like foaming phenomenon disappeared, the physical blowing agent was less occupied, resulting in a hard polyurethane foam having a higher density (> 40 kg/m) ³ ) Not only increases the cost of the rigid foam, but also increases the thermal conductivity of the foam (> 17 mW/(mK)).

Comparative example 3 using high boiling chlorofluoroolefin and high boiling fluoroolefin as composite physical blowing agent components, the foam obtained had similar core densities but poor thermal conductivity and low temperature dimensional stability as compared to example 9.

Comparative example 4 using high boiling chlorofluoroalkene and low boiling alkane as composite physical blowing agent components, the obtained foam had a core density close to that of example 3, but had poor uniformity of density distribution and thermal conductivity.

Comparative example 5 reduced the duty cycle of the chlorofluorocarbon system, and the foam core obtained had similar density but very poor thermal conductivity compared to example 2.

Comparative example 6 uses a phthalic anhydride polyester polyol having a low viscosity (25 ℃,4500mpa·s) and a low functionality, resulting in poor uniformity of density distribution of the hard bubbles and poor performance.

Comparative example 7 uses polyether polyol I as the main component of the polyol component, and does not use an aromatic polyol, resulting in a higher core density and thermal conductivity, and lower compressive strength, and greater cell anisotropy.

Comparative example 8 uses an aromatic polyol as the main component of the polyol component, and does not use polyether polyol I, resulting in a higher core density and thermal conductivity.

As described above, although the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limiting the invention itself. Various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A reactive composition comprising a polyol component, a physical blowing agent component and an isocyanate component, wherein the physical blowing agent component comprises a chlorofluoroolefin and a fluoroolefin, the chlorofluoroolefin having a boiling point of 10-20 ℃ and the fluoroolefin having a boiling point of < -10 ℃; the total weight of the chlorofluoro-olefin and the fluoroolefin is more than or equal to 80wt percent based on the total weight of the physical foaming agent component, and the weight of the chlorofluoro-olefin is more than 60wt percent; the average hydroxyl number of the polyol component is > 300mgKOH/g, the average functionality is > 3, and the average functionality of the isocyanate component is > 2.

2. The reactive composition of claim 1, wherein the chlorofluoroalkene is trans-1-chloro-3, 3-trifluoropropene and/or cis-1-chloro-2, 3-tetrafluoropropene.

3. The reactive composition of claim 1, wherein the fluoroolefin is at least one of trifluoropropene, tetrafluoropropene, pentafluoropropene, pentafluorobutene, or hexafluoropropylene.

4. The reactive composition of claim 1, wherein the molar ratio of chlorofluoroolefin to fluoroolefin is (2-28): 1.

5. The reactive composition of claim 1, wherein said physical blowing agent component further comprises cyclopentane; the cyclopentane content is less than or equal to 10wt% based on the total weight of the physical blowing agent components.

6. The reactive composition of claim 1, wherein the polyol component comprises an aromatic polyol; the weight ratio of the aromatic polyol is more than or equal to 32wt percent based on the total weight of the polyol component.

7. The reactive composition of claim 1, wherein said polyol component further comprises water;

the water is present in a weight ratio of < 1.5wt% based on the total weight of the polyol component.

8. Polyurethane foam, characterized in that it is produced with the reactive composition according to any one of claims 1 to 7, said foam comprising chlorofluoroolefins and fluoroolefins.

9. A process for producing a polyurethane foam, comprising mixing the reactive composition according to any one of claims 1 to 7, and then reacting the mixture with a polyurethane.

10. The process according to claim 9, wherein the pressure of the environment after mixing is from 0.4 to 1.6bar.