Foamed composition, polyurethane foam, and method for producing the same

Abstract

This application relates to a foaming composition containing a hydrocarbon, a fluorine-containing compound (C n H 2n-m O z X m ), and water, wherein the mass fraction of the hydrocarbon is 20 to 90%, preferably 30 to 70%, and the mass fraction of the C n H 2n-m O z X m is 10 to 80%, preferably 30 to 60%, the mass fraction of the water is 0.1 to 15%, preferably 0.5 to 5%, n in C n H 2n-m O z X m is an integer from 3 to 10, z is 0 or 1, and a foaming composition where n ≤ m ≤ 2n is disclosed. Further, this application provides a polyurethane foam and a method for manufacturing the same. The GWP value of the hydrocarbon in the foaming composition provided by this application is less than 25, the GWP value of the fluorine-containing compound is less than 10, water is converted to CO2 during the process of manufacturing the polyurethane foam, and the GWP value of CO2 is 1.

Description

[Technical Field]

[0001] This application relates to the field of foamed thermal insulation materials, and more particularly to foamed compositions, polyurethane foams, and methods for producing the same. [Background technology]

[0002] Due to its excellent thermal insulation properties, rigid polyurethane foam is widely used in various fields, including cold storage warehouses, water heaters, and pipe insulation. As the international community demands that blowing agents used in the manufacture of rigid polyurethane foam have zero ozone depletion potential (ODP) and low global warming potential (GWP), conventional chlorofluorocarbon-based blowing agents have been phased out, and hydrocarbon-based blowing agent technology, represented by cyclopentane, has been gradually and actively promoted. Currently, the blowing agents used in the manufacture of polyurethane foam are mainly multi-component blowing agents consisting of mixtures of cyclopentane, isopentane, pentafluoropropane (HFC-245fa), pentafluorobutane (HFC-365mfc), and tetrafluoroethane (HFC-134a).

[0003] Currently, multi-component blowing agents, which are mixtures of cyclopentane, isopentane, pentafluoropropane (HFC-245fa), pentafluorobutane (HFC-365mfc), and tetrafluoroethane (HFC-134a), can meet environmental protection requirements because they have an ozone depletion potential (ODP) of zero. However, their global warming potential (GWP) is generally around 500 (when the pentane / fluorocarbon ratio is approximately 1:1), which is significantly higher than the GWP limit of 150, and therefore they cannot meet the GWP value requirements. Furthermore, when using this type of multi-component blowing agent, the density of the polyurethane foam must be 30 kg / m³ to meet the performance requirements such as compressive strength and dimensional stability of the polyurethane foam. 3 A higher density is needed. Because this density is relatively high, more materials (foaming agents, dry white materials, etc.) are required when manufacturing a unit volume of polyurethane foam, which increases raw material costs. [Overview of the project]

Problems to be Solved by the Invention

[0004] This application aims to solve the technical problems existing in the prior art. The objectives of the present invention are: 1) to provide an environmentally friendly foaming composition, that is, the GWP of the obtained foaming composition is 25 or less, which is significantly lower than the requirement of 150 stipulated by national laws and regulations; 2) to provide a method for manufacturing a polyurethane foam having characteristics of low molding density and low thermal conductivity using the obtained foaming composition.

Means for Solving the Problems

[0005] This application provides a foaming composition containing a hydrocarbon, a fluorine-containing compound (C n H 2n-m O z X m ) and water. In the foaming composition, the mass fraction of the hydrocarbon is 20 - 90%, the mass fraction of C n H 2n-m O z X m is 10 - 80%, the mass fraction of water is 0.1 - 15%, n in C n H 2n-m O z X m is an integer from 3 to 10, z is 0 or 1, n ≤ m ≤ 2n, and X is a halogen.

[0006] Furthermore, the X is at least one selected from F, Cl, Br, and I. When X contains two or more elements, the F element occupies 50 mol% or more of X.

[0007] Furthermore, the fluorine-containing compound is one or more selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, trans-1,1,1,3,3,3-hexafluoro-2-butene, cis-1,1,1,3,3,3-hexafluoro-2-butene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, perfluorobutyl ketone, perfluoropentanone, perfluorohexanone, methyl perfluoroheptyl ketone, cis-1-chloro-3,3,3-trifluoropropene and trans-1-chloro-3,3,3-trifluoropropene.

[0008] Furthermore, it consists of hydrocarbon, C n H 2n-m O z X m and water. In the foaming composition, the mass fraction of the hydrocarbon is 20 to 90%, the mass fraction of the C n H 2n-m O z X m is 10 to 80%, and the mass fraction of the water is 0.1 to 15%.

[0009] Furthermore, the GWP value of the foaming composition is less than 25.

[0010] Furthermore, the hydrocarbon contains a first hydrocarbon and a second hydrocarbon, and the boiling point of the first hydrocarbon is lower than that of the second hydrocarbon.

[0011] Furthermore, the mass ratio of the first hydrocarbon to the second hydrocarbon is (1 to 50):10.

[0012] Furthermore, the first hydrocarbon is n-butane, isobutane or neopentane, and the second hydrocarbon is any one selected from cyclopentane, n-pentane and isopentane.

[0013] Furthermore, the fluorine-containing compound comprises a first fluorine-containing compound and a second fluorine-containing compound, wherein the boiling point of the first fluorine-containing compound is lower than the boiling point of the second fluorine-containing compound.

[0014] Furthermore, the mass ratio of the first fluorine-containing compound to the second fluorine-containing compound is (1-50):10.

[0015] Furthermore, the first fluorine-containing compound is selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, perfluorobutyl ketone, 2-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, or trans-1,1,1,3,3,3-hexafluoro-2-butene. The second fluorine-containing compound is selected from perfluoropentanone, perfluorohexanone, methylperfluoroheptylketone, 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, cis-1,1,1,3,3,3-hexafluoro-2-butene, cis-1-chloro-3,3,3-trifluoropropene, or trans-1-chloro-3,3,3-trifluoropropene.

[0016] This application provides a polyurethane foam whose raw materials include the above-mentioned foam composition.

[0017] Furthermore, the raw materials for the polyurethane foam further include a polyol, an organic polyisocyanate, and an auxiliary agent.

[0018] Furthermore, the mass ratio of the auxiliary agent, the foaming composition, and the polyol is (0.01~0.2):(0.3~3):1, preferably (0.03~0.1):(0.5~2):1, or The mass ratio of the aforementioned auxiliary agent, the foaming composition, and the organic polyisocyanate is (0.01~0.3):(0.25~4):1, preferably (0.03~0.2):(0.5~2):1.

[0019] Furthermore, the density of the polyurethane foam is 30.0 kg / m³. 3 Less than, or The thermal conductivity of the polyurethane foam is less than 20.0 mW / m·k.

[0020] This application is, The steps include: preparing the foamed composition described above; The steps include: preparing a dry white material by mixing a polyol and an auxiliary agent; The process involves mixing a foaming composition, water, and a dry white material under sealed conditions at room temperature to obtain a white material liquid; The process involves mixing a white material liquid with an organic polyisocyanate and reacting them to obtain a polyurethane foam material liquid; The present invention provides a method for producing polyurethane foam, comprising the steps of subjecting a polyurethane foam material liquid to a molding reaction and forming a polyurethane foam of a desired shape by extrusion or spraying.

[0021] Furthermore, the foaming composition, water, and the dry white material are mixed at room temperature under sealed conditions for 0.5 to 24 hours, or The organic polyisocyanate and the white material solution are mixed and reacted for 0.1 to 4 hours. [Effects of the Invention]

[0022] In the foamed composition provided in this application, the GWP value of the hydrocarbons is less than 25, the GWP value of the fluorine-containing compounds is less than 10, and water is converted to CO2 during the polyurethane foam manufacturing process, with a GWP value of 1 for CO2. Therefore, the GWP value of the foamed composition provided in this application is less than 10, which is far below the 150 value required by policy to meet environmental protection requirements (environmental protection value), making it an ideal, environmentally friendly foamed composition.

[0023] Compared to existing polyurethane foams, polyurethane foam produced using the foam composition provided in this application has a significantly reduced molding density (more than 15% lower than the density of polyurethane foam produced using existing cyclopentane foam compositions, and more than 5% lower than the density of polyurethane foam plastics currently produced using ternary foam compositions). This reduces the amount of raw materials required (foam composition + dry white material) to produce the same volume of polyurethane foam, thereby lowering the manufacturing cost of the polyurethane foam. Polyurethane foam produced using the foam composition provided in this application has low thermal conductivity and excellent heat insulation properties, which is beneficial in reducing the energy consumption of refrigeration equipment. Furthermore, the polyurethane foam material liquid produced using the foam composition provided in this application has better fluidity, a more uniform density distribution, a smoother surface, and better compressive strength and dimensional stability of the foam, thus improving the overall performance of the resulting polyurethane foam. Therefore, polyurethane foam produced using the foam composition of this application has low molding density, low thermal conductivity, and high compressive strength and release properties; in other words, polyurethane foam produced using the foam composition provided in this application has excellent overall performance. [Modes for carrying out the invention]

[0024] The following is a description of exemplary embodiments of this application, including various details of the embodiments for the sake of ease of understanding, and should be construed as merely illustrative. Accordingly, it will be understood by those skilled in the art that the embodiments described herein can be modified in various ways without departing from the scope and spirit of the invention. Similarly, for clarity and brevity, descriptions of well-known functions and structures are omitted in the following description.

[0025] This application relates to hydrocarbons, fluorine-containing compounds (C n H 2n-m O z X mThe present invention provides a foaming composition comprising C and water, wherein the mass fraction of the hydrocarbon is 20 to 90%, preferably 30 to 70%, and C n H 2n-m O z X m The mass fraction of is 10-80%, preferably 30-60%, and the mass fraction of water is 0.1-15%, preferably 0.5-5%, C n H 2n-m O z X m In this equation, n is an integer between 3 and 10, z is 0 or 1, n ≤ m ≤ 2n, and X is a halogen.

[0026] Furthermore, X is at least one selected from F, Cl, Br, and I, and if X contains two or more elements, element F accounts for 50 mol% or more of X.

[0027] In some embodiments, X is F.

[0028] In some embodiments, X is Cl.

[0029] In some embodiments, X is Br.

[0030] In some embodiments, X is I.

[0031] In some embodiments, X is F and Cl.

[0032] In some embodiments, X is F and Br.

[0033] In some embodiments, X is F and I.

[0034] In some embodiments, X is F, Cl, and I.

[0035] In some embodiments, X is F, Br, and I.

[0036] In some embodiments, X is F, Cl, Br, and I.

[0037] In some embodiments, C n H 2n-m O z X m It is a fluoroolefin.

[0038] In some embodiments, C n H 2n-m O z X m It is a fluorinated ketone.

[0039] In some embodiments, the value of n may be 3, 4, 5, 6, 7, 8, 9, or 10, etc.

[0040] This application relates to hydrocarbons, fluorine-containing compounds (C n H 2n-m O z X m The present invention provides a foaming composition comprising a hydrocarbon and water, wherein the mass fraction of the hydrocarbon is 20-90%, preferably 30-70%, the mass fraction of the fluorine-containing compound is 10-80%, preferably 30-60%, and the mass fraction of water is 0.1-15%, preferably 0.5-5%.

[0041] In some embodiments, the mass fraction of the hydrocarbon is 20-90%.

[0042] In some embodiments, the mass fraction of the hydrocarbon is 30-70%.

[0043] In some embodiments, the mass fraction of the hydrocarbon is 30-80%.

[0044] In some embodiments, the mass fraction of the hydrocarbon is 30-90%.

[0045] Specifically, the mass fraction of the hydrocarbon may be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%.

[0046] In some embodiments, the mass fraction of the fluorine-containing compound is 10 to 80%.

[0047] In some embodiments, the mass fraction of the fluorine-containing compound is 30-60%.

[0048] In some embodiments, the mass fraction of the fluorine-containing compound is 30-70%.

[0049] In some embodiments, the mass fraction of the fluorine-containing compound is 30-80%.

[0050] Specifically, the mass fraction of the fluorine-containing compound may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%.

[0051] In some embodiments, the mass fraction of water is 0.1 to 15%.

[0052] In some embodiments, the mass fraction of water is 0.5 to 5%.

[0053] In some embodiments, the mass fraction of water is 0.5 to 10%.

[0054] In some embodiments, the mass fraction of water is 0.5 to 15%.

[0055] Specifically, the mass fraction of water may be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, or 15%.

[0056] In this application, the GWP value of the foamed composition is less than 10, and may be, for example, 9.

[0057] In this application, the hydrocarbon comprises a first hydrocarbon and a second hydrocarbon, wherein the boiling point of the first hydrocarbon is lower than the boiling point of the second hydrocarbon.

[0058] The first hydrocarbon is a low-boiling-point hydrocarbon, and its boiling point is 20°C or lower. For example, the boiling points may be 20°C, 19°C, 18°C, 17°C, 16°C, 15°C, 14°C, 13°C, 12°C, 11°C, 10°C, etc.

[0059] The second hydrocarbon is a high-boiling-point hydrocarbon, and its boiling point is above 20°C. For example, it may be 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, etc.

[0060] In this application, the mass ratio of the first hydrocarbon to the second hydrocarbon is (1-50):10, preferably (3-30):10.

[0061] Specifically, the mass ratio of the first hydrocarbon to the second hydrocarbon may be 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 11:10, 12:10, 13:10, 14:10, 15:10, 16:10, 17:10, 18:10, 19:10, 20:10, 21:10, 22:10, 23:10, 24:10, 25:10, 26:10, 27:10, 28:10, 29:10, or 30:10.

[0062] In this application, the first hydrocarbon is n-butane, isobutane, or neopentane, preferably n-butane; The second hydrocarbon is selected from cyclopentane, n-pentane, or isopentane, and is preferably cyclopentane.

[0063] Specifically, the boiling point of n-butane is -0.5°C.

[0064] Specifically, the boiling point of isobutane is -10.5°C.

[0065] Specifically, the boiling point of the cyclopentane is 49.2°C.

[0066] Specifically, the boiling point of n-pentane is 36°C.

[0067] Specifically, the boiling point of the neopentane is 9.5°C.

[0068] Specifically, the boiling point of the isopentane is 27.8°C.

[0069] In this application, the fluorine-containing compound is one or more selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, trans-1,1,1,3,3,3-hexafluoro-2-butene, 1-chloro-2,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, perfluorobutyl ketone, perfluoropentanone, perfluorohexanone, methyl perfluoroheptyl ketone, cis-1,1,1,3,3,3-hexafluoro-2-butene, cis-1-chloro-3,3,3-trifluoropropene, and trans-1-chloro-3,3,3-trifluoropropene.

[0070] In this application, the fluorine-containing compound comprises a first fluorine-containing compound and a second fluorine-containing compound, wherein the boiling point of the first fluorine-containing compound is lower than the boiling point of the second fluorine-containing compound.

[0071] The first fluorine-containing compound is a low-boiling-point fluorine-containing compound, and its boiling point is 15°C or lower. For example, its boiling point may be 15°C, 14°C, 13°C, 12°C, etc.

[0072] The second fluorine-containing compound is a high-boiling-point fluorine-containing compound, and its boiling point is above 15°C. For example, its boiling point may be 20°C, 25°C, 30°C, 40°C, etc.

[0073] In this application, the mass ratio of the first fluorine-containing compound to the second fluorine-containing compound is (1-50):10, preferably (3-30):10.

[0074] Specifically, the mass ratio of the first fluorine-containing compound to the second fluorine-containing compound may be 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 11:10, 12:10, 13:10, 14:10, 15:10, 16:10, 17:10, 18:10, 19:10, 20:10, 21:10, 22:10, 23:10, 24:10, 25:10, 26:10, 27:10, 28:10, 29:10, or 30:10.

[0075] In this application, the first fluorine-containing compound is one selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, perfluorobutyl ketone, 2-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, or trans-1,1,1,3,3,3-hexafluoro-2-butene, preferably trans-1,3,3,3-tetrafluoropropene; The second fluorine-containing compound is one selected from perfluoropentanone, perfluorohexanone, 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, methylperfluoroheptylketone, cis-1,1,1,3,3,3-hexafluoro-2-butene, cis-1-chloro-3,3,3-trifluoropropene, or trans-1-chloro-3,3,3-trifluoropropene, preferably perfluorohexanone or trans-1-chloro-3,3,3-trifluoropropene.

[0076] Specifically, the boiling point of 3,3,3-trifluoropropene is -17°C.

[0077] Specifically, the boiling point of the cis-1,3,3,3-tetrafluoropropene is 9.6°C.

[0078] Specifically, the boiling point of the trans-1,3,3,3-tetrafluoropropene is -19°C.

[0079] Specifically, the boiling point of the trans-1-chloro-3,3,3-trifluoropropene is 19°C.

[0080] Specifically, the boiling point of the cis-1-chloro-3,3,3-trifluoropropene is 39°C.

[0081] Specifically, the boiling point of 1-chloro-2,3,3-trifluoropropene is 54°C.

[0082] Specifically, the boiling point of 2-chloro-3,3,3-trifluoropropene is 15°C.

[0083] Specifically, the boiling point of the cis-1-chloro-2,3,3,3-tetrafluoropropene is 15°C.

[0084] Specifically, the boiling point of the trans-1-chloro-2,3,3,3-tetrafluoropropene is 19°C.

[0085] Specifically, the boiling point of the perfluorobutyl ketone is 0°C.

[0086] Specifically, the boiling point of the perfluoropentanone is 26.9°C.

[0087] Specifically, the boiling point of the perfluorohexanone is 49°C.

[0088] Specifically, the boiling point of the methyl perfluoroheptyl ketone is 57°C.

[0089] Specifically, the boiling point of the cis-1,1,1,3,3,3-hexafluoro-2-butene is 33.4°C.

[0090] Specifically, the boiling point of trans-1,1,1,3,3,3-hexafluoro-2-butene is 7.5°C.

[0091] In this application, the boiling point of the foamed composition is -19°C to 55°C, preferably -10°C to 40°C.

[0092] Specifically, the boiling point of the foaming composition may be -19°C, -18°C, -17°C, -16°C, -15°C, -14°C, -13°C, -12°C, -11°C, -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 40°C, 45°C, 50°C, or 55°C.

[0093] In some embodiments, the foamed composition is characterized in that the first hydrocarbon is n-butane, the second hydrocarbon is cyclopentane, the first fluorine-containing compound is trans-1-chloro-3,3,3-trifluoropropene, and the second fluorine-containing compound is perfluorohexanone.

[0094] This application provides a polyurethane foam whose raw materials include the above-mentioned foam composition.

[0095] The raw materials for polyurethane foam further include polyols, organic polyisocyanates, and auxiliary agents.

[0096] This application provides a polyurethane foam comprising the above-mentioned foaming composition, polyol, organic polyisocyanate, and auxiliary agents.

[0097] In some embodiments, the mass ratio of the above-mentioned auxiliary agent, foaming composition, and polyol is (0.01~0.2):(0.3~3):1, preferably (0.03~0.1):(0.5~2):1.

[0098] Specifically, when the polyol content is 1 part by weight, the auxiliary content is 0.01 to 0.2 parts by weight, preferably 0.03 to 0.1 parts by weight, and the foamed composition content is 0.3 to 3 parts by weight, preferably 0.5 to 2 parts by weight.

[0099] Specifically, if the polyol content is 1 part by weight, the auxiliary agent content may be 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.11 parts by weight, 0.12 parts by weight, 0.13 parts by weight, 0.14 parts by weight, 0.15 parts by weight, 0.16 parts by weight, 0.17 parts by weight, 0.18 parts by weight, 0.19 parts by weight, or 0.2 parts by weight.

[0100] Specifically, if the polyol content is 1 part by weight, the foam composition content may be 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, or 3 parts by weight.

[0101] In some embodiments, the mass ratio of the auxiliary agent, the foaming composition, and the organic polyisocyanate is (0.01~0.3):(0.25~4):1, preferably (0.03~0.2):(0.5~3):1.

[0102] Specifically, when the content of the organic polyisocyanate is 1 part by weight, the content of the auxiliary agent is 0.01 to 0.3 parts by weight, preferably 0.03 to 0.2 parts by weight, and the content of the foaming composition is 0.25 to 4 parts by weight, preferably 0.5 to 3 parts by weight.

[0103] Specifically, if the content of the organic polyisocyanate is 1 part by weight, the content of the auxiliary agent may be 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.11 parts by weight, 0.12 parts by weight, 0.13 parts by weight, 0.14 parts by weight, 0.15 parts by weight, 0.16 parts by weight, 0.17 parts by weight, 0.18 parts by weight, 0.19 parts by weight, 0.2 parts by weight, 0.21 parts by weight, 0.22 parts by weight, 0.23 parts by weight, 0.24 parts by weight, 0.25 parts by weight, 0.26 parts by weight, 0.27 parts by weight, 0.28 parts by weight, 0.29 parts by weight, or 0.3 parts by weight.

[0104] Specifically, if the content of the organic polyisocyanate is 1 part by weight, the content of the foamed composition may be 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.6 parts by weight, 0.65 parts by weight, 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight, 0.95 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, or 4 parts by weight.

[0105] In this application, the auxiliary agent is one or more selected from crosslinking agents, catalysts, foam stabilizers, antioxidants, flame retardants, and pigments.

[0106] In this application, the polyol is one or two selected from polyether polyols or polyester polyols.

[0107] In this application, the polyether polyol is one or more selected from polyetherdiol, polyethertriol, polyethertetraol, pentahydroxypolyether, polyethersorbitol, mannitol, and sucrose alcohol.

[0108] The aforementioned polyester polyol is selected from those obtained by condensing (or transesterifying) or polymerizing phthalic acid or phthalic anhydride or its ester, adipic acid, halogenated phthalic acid with polyols such as ethylene glycol, propylene glycol, diethylene glycol, trimethylolpropane, and pentaerythritol.

[0109] In this application, the organic polyisocyanate is one or more selected from hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate (TMHDI), methylcyclohexylene diisocyanate (TDI), dicyclohexylmethylene diisocyanate (MDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), meta- or para-1,4-methylxylylene diisocyanate (abbreviated as m- or p-TMXDI), vinyl isocyanate (TMI), and frangipane isocyanate.

[0110] In this application, the catalyst is an organoterite amine and a metal salt catalyst, specifically N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, triethylamine, N-ethylmorpholine, N-methylmorpholine, N,N-dimethylbenzylamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N'-diethylpiperazine, N,N'-diethyl-2-methylpiperazine, N,N-dimethylethanolamine, triethanolamine, organotin compounds, alkali metal and alkaline earth metal salt compounds, etc.

[0111] In some embodiments, the raw materials for the polyurethane foam include N,N-dimethylcyclohexylamine and a silicone surfactant, the polyol is a composite of a polyether polyol initiated by glycerol, a polyether polyol initiated by sorbitol, and a polyether polyol initiated by sucrose, and the organic polyisocyanate is MDI.

[0112] In this application, the density of the polyurethane foam is 30.0 kg / m³. 3 It is less than, for example, 28.0 kg / m³ 3 That's fine.

[0113] The thermal conductivity of the polyurethane foam is less than 20.0 mW / m·k, and may be, for example, 18.6 mW / m·k.

[0114] This application provides a method for manufacturing polyurethane foam, comprising the following steps. Step 1: Prepare the aforementioned foaming composition; Step 2: Mix the polyol and auxiliary agent to prepare a dry white material; Step 3: Mix the foaming composition, water, and dry white material at room temperature under sealed conditions to obtain a white material liquid; Step 4: Mix the white material liquid and the organic polyisocyanate and allow them to react to obtain a polyurethane foam material liquid; Step 5: The polyurethane foam material liquid is subjected to a molding reaction to form a polyurethane foam of the desired shape by extrusion or spraying.

[0115] In step 3, the foam composition, water, and the dry white material are mixed at room temperature under sealed conditions for 0.5 to 24 hours, for example, 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, or 24 hours.

[0116] The organic polyisocyanate and the white material liquid are mixed and reacted for 0.1 to 4 hours, for example, 0.1 hours, 0.2 hours, 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours, or 4 hours.

[0117] The GWP values ​​of all components in the foamed composition provided in this application are less than 10, which is far below the 150 value required by policy to meet environmental protection requirements, making it an ideal, environmentally friendly foamed composition. The foamed composition of this application employs a specific formulation so that the foamed composition has an appropriate boiling point and a low GWP. This is because if the boiling point of the foamed composition is too low, for example below -20°C, the foaming rate is too fast and it cannot be used normally at room temperature. On the other hand, if the boiling point of the foamed composition is too high, for example above 60°C, the foaming agent in the pores becomes liquid after foaming, the vapor pressure is low and it is difficult to ensure the dimensional stability of the foam, making it unsuitable for the manufacture of ultra-low density foam. Each component in the foamed composition provided in this application has a small relative molecular weight and a low boiling point, and the density of the manufactured polyurethane foam is 30.0 kg / m³. 3 It is less than 20.0 mW / m·k, and its thermal conductivity is less than 20.0 mW / m·k.

[0118] Polyurethane foam manufactured using the foam composition provided in this application has a significantly lower molding density (by 5% or more) compared to existing polyurethane foam plastics, resulting in less raw material required and reduced manufacturing costs when producing the same volume of polyurethane foam plastic. Furthermore, its low thermal conductivity and excellent insulation effect allow the same insulation effect to be achieved with a smaller amount of polyurethane foam, further reducing the total weight of the insulation product. In addition, the ODP of the foam composition provided in this application is zero or near zero, and the GWP is less than 25, fully meeting environmental protection requirements. Moreover, the polyurethane foam manufactured using the foam composition provided in this application has low thermal conductivity and good foam insulation performance, which helps reduce energy consumption in refrigeration equipment. Furthermore, the good fluidity of the polyurethane foam liquid makes it easy to achieve a polyurethane foam with a uniform density distribution during the construction process, a smooth surface, and excellent foam compressive strength and dimensional stability. [Examples]

[0119] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

[0120] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0121] Example 1 The manufacturing process for polyurethane foam is as follows: 1) A polyol (a polyol obtained by mixing 25g of 450L polyether polyol with a hydroxyl value of 500 mgKOH / g and 45g of polyester polyol PS-3152 with a hydroxyl value of 315 mgKOH / g) and an auxiliary agent (an auxiliary agent obtained by mixing 12g of flame retardant TCPP, 1g of catalyst PCS, and 2g of surfactant AK8803) was mixed to prepare a dry white material. 2) 15 g of n-butane, 25 g of cyclopentane, 30 g of trans-1,3,3,3-tetrafluoropropylene, 25 g of trans-1-chloro-3,3,3-trifluoropropylene, and 3 g of water were mixed at room temperature (15-25°C) under sealed conditions (1-3 atm) for 1 hour to obtain a foamed composition. 3) 150 g of polyisocyanate (polyisocyanate PM200) was added to the above foam composition and mixed uniformly to prepolymerize the polyisocyanate and the foam composition, thereby obtaining a polyurethane foam material liquid. 4) The manufactured polyurethane foam material liquid was pressed into a plate-shaped mold using a screw extruder, and foaming was continued at room temperature for 4 hours. The mold was disassembled to obtain a polyurethane foam profile with an appropriate shape and structure. Its various parameters are shown in Tables 1-1 to 1-3.

[0122] The only difference between Examples 2 to 5 and Example 1 is the mass ratio of the first hydrocarbon to the second hydrocarbon, and details are shown in Tables 1-1 to 1-3.

[0123] The only difference between Examples 6 to 9 and Example 1 is the mass ratio of the first fluorine-containing compound to the second fluorine-containing compound, which is shown in detail in Tables 1-1 to 1-3.

[0124] The only difference between Example 10 and Example 1 is the type of first hydrocarbon used, and details are shown in Tables 1-1 to 1-3.

[0125] The difference between Examples 11 to 13 and Example 1 lies in the differing content of the first hydrocarbon, the second hydrocarbon, the first fluorine-containing compound, and the second fluorine-containing compound. Details are shown in Tables 1-1 to 1-3.

[0126] The difference between Examples 14 and 15 and Example 1 is the water content, which is shown in detail in Tables 1-1 to 1-3.

[0127] The difference between Examples 16 to 18 and Example 1 lies in the types of the first hydrocarbon, the second hydrocarbon, the first fluorine-containing compound, and the second fluorine-containing compound. Details are shown in Tables 1-1 to 1-3.

[0128] The difference between Comparative Example 1 and Example 1 is that it does not contain a fluorine-containing compound. Details are shown in Tables 1-1 to 1-3.

[0129] The difference between Comparative Example 2 and Example 1 is that it does not contain hydrocarbons, and details are shown in Tables 1-1 to 1-3.

[0130] The difference between Comparative Example 3 and Example 1 is that it does not contain water. Details are shown in Tables 1-1 to 1-3.

[0131] The differences between Comparative Example 4 and Example 1 are the content of the first hydrocarbon, the second hydrocarbon, the first fluorine-containing compound, the second fluorine-containing compound, and water, which are shown in detail in Tables 1-1 to 1-3.

[0132] The difference between Comparative Example 5 and Example 1 is that it does not contain the second hydrocarbon, and details are shown in Tables 1-1 to 1-3.

[0133] The difference between Comparative Example 6 and Example 1 is that it does not contain the second fluorine-containing compound, and details are shown in Tables 1-1 to 1-3.

[0134] Tables 1-1 to 1-3 show the material conditions and various parameters for each example and comparative example.

[0135] [Table 1-1]

[0136] [Table 1-2]

[0137] [Table 1-3]

[0138] Summary: As can be seen from the table above, the foamed material produced using the foamed composition described in this application has low foam density and thermal conductivity, with a foam density of 26.1 to 28.0 kg / m³. 3 It falls within this range, with a thermal conductivity in the range of 16.8 to 18.2 mW / m·k, and the GWP value can be reduced to 25 or less, and even to 10 or less.

[0139] While embodiments of this application have been described above, this application is not limited to the specific embodiments and field of application described herein, and the specific embodiments described herein are merely illustrative and teaching examples, not limiting. Those skilled in the art can create many forms without departing from the scope of protection of the claims of this application by following the guidelines of this specification, and all such forms are included within the scope of protection of this application.

Claims

1. A foaming composition containing a hydrocarbon, a fluorine-containing compound (C ｎ H ２ｎ－ｍ O ｚ X ｍ ), and water, wherein in the foaming composition, the mass fraction of the hydrocarbon is 20 to 90%, and the C ｎ H ２ｎ－ｍ O ｚ X ｍ has a mass fraction of 10 to 80%, the mass fraction of the water is 0.1 to 15%, n in C ｎ H ２ｎ－ｍ O ｚ X ｍ is an integer from 3 to 10, z is 0 or 1, n ≤ m ≤ 2n, and X is a halogen. Foaming composition.

2. The foamed composition according to claim 1, wherein X is at least one selected from F, Cl, Br, and I, and if X contains two or more elements, element F accounts for 50 mol% or more of X.

3. The foaming composition according to claim 1, wherein the fluorine-containing compound is one or more selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, trans-1,1,1,3,3,3-hexafluoro-2-butene, perfluorohexanone, cis-1,1,1,3,3,3-hexafluoro-2-butene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, perfluorobutyl ketone, perfluoropentanone, perfluorohexanone, methylperfluoroheptyl ketone, cis-1-chloro-3,3,3-trifluoropropene, and trans-1-chloro-3,3,3-trifluoropropene.

4. Hydrocarbons, C ｎ H ２ｎ－ｍ O ｚ X ｍ and water, and in the foaming composition, the mass fraction of the hydrocarbon is 20 to 90%, and C ｎ H ２ｎ－ｍ O ｚ X ｍ The foaming composition according to any one of claims 1 to 3, wherein the mass fraction of is 10 to 80% and the mass fraction of water is 0.1 to 15%.

5. The foamed composition according to any one of claims 1 to 3, wherein the GWP value of the foamed composition is less than 25.

6. The foaming composition according to claim 1, wherein the hydrocarbon comprises a first hydrocarbon and a second hydrocarbon, and the boiling point of the first hydrocarbon is lower than the boiling point of the second hydrocarbon.

7. The foaming composition according to claim 6, wherein the mass ratio of the first hydrocarbon to the second hydrocarbon is (1 to 50):

10.

8. The first hydrocarbon is n-butane, isobutane, or neopentane. The foaming composition according to claim 6, wherein the second hydrocarbon is one selected from cyclopentane, n-pentane, and isopentane.

9. The foaming composition according to any one of claims 1 to 3, wherein the fluorine-containing compound comprises a first fluorine-containing compound and a second fluorine-containing compound, and the boiling point of the first fluorine-containing compound is lower than the boiling point of the second fluorine-containing compound.

10. The foamed composition according to claim 9, wherein the mass ratio of the first fluorine-containing compound to the second fluorine-containing compound is (1 to 50):

10.

11. The first fluorine-containing compound is one selected from 3,3,3-trifluoropropene, cis-1,3,3,3-tetrafluoropropene, perfluorobutyl ketone, 2-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, or trans-1,1,1,3,3,3-hexafluoro-2-butene. The foaming composition according to claim 9, wherein the second fluorine-containing compound is one selected from perfluoropentanone, perfluorohexanone, methylperfluoroheptylketone, 1-chloro-2,3,3-trifluoropropene, 1-chloro-2,3,3,3-tetrafluoropropene, cis-1,1,1,3,3,3-hexafluoro-2-butene, cis-1-chloro-3,3,3-trifluoropropene, or trans-1-chloro-3,3,3-trifluoropropene.

12. A polyurethane foam comprising a foam composition according to any one of claims 1 to 11 as a raw material.

13. The polyurethane foam according to claim 12, wherein the raw materials further comprise a polyol, an organic polyisocyanate, and an auxiliary agent.

14. The mass ratio of the aforementioned auxiliary agent, the foaming composition, and the polyol is (0.01 to 0.2):(0.3 to 3):1, or The polyurethane foam according to claim 13, wherein the mass ratio of the auxiliary agent, the foaming composition, and the organic polyisocyanate is (0.01 to 0.3):(0.25 to 4):

1.

15. The density of the aforementioned polyurethane foam is 30.0 kg / m³ ３ Less than, or The polyurethane foam according to claim 12, wherein the thermal conductivity of the polyurethane foam is less than 20.0 mW / m·k.

16. A step of preparing the foamed composition according to any one of claims 1 to 11; The steps include: preparing a dry white material by mixing a polyol and an auxiliary agent; The steps include: mixing the foaming composition, water, and the dry white material at room temperature under sealed conditions to obtain a white material liquid; The steps include: mixing the aforementioned white material liquid with an organic polyisocyanate and reacting them to obtain a polyurethane foam material liquid; A method for producing polyurethane foam, comprising the steps of subjecting the polyurethane foam material liquid to a molding reaction to form a polyurethane foam of a desired shape by extrusion or spraying, etc.

17. The foaming composition, water, and the dry white material are mixed at room temperature under sealed conditions for 0.5 to 24 hours, or The manufacturing method according to claim 16, comprising mixing the organic polyisocyanate with the white material liquid and reacting them for 0.1 to 4 hours.

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