Low-boiling-point foaming material, application thereof and refrigerator

Abstract

The invention discloses a low-boiling-point foaming material, application thereof and a refrigerator, and belongs to the field of refrigerator materials. Comprising combined polyether polyol, a mixed foaming agent, a reaction catalyst, a silicone oil surfactant, water and isocyanate. The mixed foaming agent comprises a butane foaming agent, the content of n-butane r600 in the butane foaming agent is 75%-85%, and the content of iso-butane r600a in the butane foaming agent is 15%-25%. The foaming layer is applied to the aspect of the foaming layer of the refrigerator, solves the problems that the foaming layer is thick and occupies a large volume due to the pasting of a VIP plate, the usable volume of the refrigerator is small, the volume fraction is low, and the space utilization rate and the energy consumption reduction of the refrigerator cannot be optimized at the same time, and has the advantages that the strength, the dimensional stability, the expansion rate and the like are kept unchanged; the refrigerator has the advantages that raw material consumption is effectively reduced, production cost is reduced, cost is reduced, efficiency is improved, the space utilization rate of the refrigerator is increased, the refrigerator with the same size is larger in volume, and more articles can be stored.

Description

Technical Field

[0001] The invention belongs to the field of refrigerator materials, and in particular relates to a low-boiling point foaming material, application thereof and a refrigerator. Background Art

[0002] With the continuous improvement of residents' living standards, users now pay more and more attention to improving space utilization and green and low energy consumption. This requires refrigerator products to reduce the thickness of the foam layer of the refrigerator wall to increase the volume ratio and improve the insulation performance of the refrigerator under the premise of unchanged appearance size. At the same time, in order to remedy the loss of insulation performance caused by the thinning of the refrigerator, VIP panels (vacuum insulation panels) are added to the side panels of the refrigerator. Thermal conductivity is an important indicator to measure the insulation performance of materials. The thermal conductivity of VIP panels is 1.5mW / (mk), and that of general polyurethane insulation foam is 18.5mW / (mk). The difference between the two is more than ten times. The insulation performance of VIP panels is much better than that of polyurethane foam. Therefore, the more common measures in the refrigerator industry include posting VIP panels on the side panels and backs of refrigerators to improve the insulation performance of refrigerators, reduce the start-up rate of compressors, and thus reduce the energy consumption of refrigerators. However, since VIP panels will occupy the foam flow channel space, it will cause difficulty in the flow of foaming materials during refilling, which will cause poor filling problems. Therefore, the foam layer will be designed to be thicker, which will affect the volume ratio of the refrigerator.

[0003] Chinese patent CN110567222A discloses the use of pure LBA system to replace the VIP panels on both sides. The actual thermal conductivity of the pure LBA system foam is 16.8mW / (mk), which is an improvement compared with the 18.5mW / (mk) of the ordinary foam system. However, compared with the thermal conductivity of the VIP board of 1.5mW / (mk), the difference is obvious. It cannot meet the new European standard first-level energy efficiency machine, and still needs to rely on a large number of VIP boards to improve the thermal insulation performance. In addition, the density of the pure LBA system is 32kg / m 3 , the fluidity is poor and it is difficult to meet the flow channel filling requirements below 45mm. Summary of the invention

[0004] In view of the shortcomings of the prior art, the technical problem to be solved by the present invention is to solve the problem that the foam layer is thicker and occupies a larger volume due to the pasting of VIP boards, the usable volume of the refrigerator is small, the volume ratio is low, and the space utilization rate and energy consumption reduction of the refrigerator cannot be optimized at the same time. A low-boiling point foaming material, its application and refrigerator are proposed, which have the characteristics of maintaining the same strength, dimensional stability, expansion rate and other properties, effectively reducing the use of raw materials, reducing production costs, reducing costs and increasing efficiency, and at the same time, improving the space utilization rate of the refrigerator. The refrigerator volume of the same size is larger and more items can be stored.

[0005] In order to solve the technical problem, the technical solution adopted by the present invention is:

[0006] The present invention provides a low-boiling point foaming material, comprising: a combined polyether polyol, a mixed foaming agent, a reaction catalyst, a silicone oil surfactant, water, and an isocyanate;

[0007] The combined polyether polyol is composed of polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D, and phthalic anhydride polyester polyol E, wherein the hydroxyl value of the polyether polyol A is 380-480 mgKOH / g, the hydroxyl value of the polyether polyol B is 360-460 mgKOH / g, the hydroxyl value of the polyether polyol C is 400-500 mgKOH / g, the hydroxyl value of the polyether polyol D is 160-260 mgKOH / g, and the hydroxyl value of the phthalic anhydride polyester polyol E is 390-490 mgKOH / g;

[0008] The mixed foaming agent comprises a butane foaming agent, in which the content of normal butane R600 is 75%-85% and the content of isobutane R600a is 15%-25%.

[0009] Preferably, the mixed foaming agent consists of a cyclopentane foaming agent, an LBA foaming agent and the butane foaming agent, or consists of a cyclopentane foaming agent, a 245fa foaming agent and the butane foaming agent.

[0010] Preferably, by weight, it includes 100 parts of combined polyether polyol, 20-25 parts of mixed foaming agent, 1-4 parts of reaction catalyst, 1.5-3 parts of silicone oil surfactant, 1-3 parts of water, and 140-165 parts of isocyanate;

[0011] The weight portion of the butane foaming agent is selected from any value between 2 and 3 parts, the weight portion of the cyclopentane foaming agent is selected from any value between 11 and 14 parts, and the weight portion of the LBA foaming agent or the 245fa foaming agent is selected from any value between 4 and 9 parts.

[0012] Preferably, the polyether polyol A is prepared by reacting toluene diamine with propylene oxide, the polyether polyol B is prepared by reacting sucrose as an initiator with propylene oxide through an addition reaction, the polyether polyol C is prepared by reacting sorbitol as an initiator with propylene oxide through an addition reaction, and the polyether polyol D is prepared by reacting glycerol as an initiator with propylene oxide through an addition reaction;

[0013] The weight portion of the polyether polyol A is selected from any value between 0 and 30 parts, the weight portion of the polyether polyol B is selected from any value between 0 and 30 parts, the weight portion of the polyether polyol C is selected from any value between 0 and 20 parts, the weight portion of the polyether polyol D is selected from any value between 0 and 10 parts, and the weight portion of the phthalic anhydride polyester polyol E is selected from any value between 0 and 20 parts.

[0014] Preferably, the NCO content of the isocyanate is 30%-32%; the silicone oil surfactant is selected from at least one of silicone oil L6863, silicone oil L6988, silicone oil AK8830, silicone oil B8525, and silicone oil B8545.

[0015] Preferably, the reaction catalyst is a composite catalyst, including a foaming catalyst, a gel catalyst and a trimerization catalyst, and the mass ratio of the foaming catalyst to the gel catalyst and the trimerization catalyst is 2-4:3-8:1-3.

[0016] Preferably, the foaming catalyst is selected from at least one of pentamethyldiethylenetriamine, N-methyldicycloethylamine, tetramethylhexanediamine or bis-dimethylaminoethyl ether, the gel catalyst is selected from at least one of dimethylbenzylamine, dimethylcyclohexane or triethylenediamine, and the trimerization catalyst is selected from at least one of potassium acetate, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, (2-hydroxypropyl)trimethylammonium formate, ethyl quaternary ammonium salt or octyl quaternary ammonium salt.

[0017] Another aspect of the present invention provides the use of the low-boiling point foaming material described in any of the above technical solutions in a foaming layer of a refrigerator, using multiple single-gun foaming machines to simultaneously inject the low-boiling point foaming material into the refrigerator injection port.

[0018] Preferably, the mixing pressure of the gun head of the single-gun head foaming machine is any value between 120 and 140 MPa; and the injection method is vertical injection.

[0019] The present invention also provides a refrigerator, wherein the foaming layer of the refrigerator is prepared by using the low-boiling point foaming material described in any one of the above technical solutions.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The present invention provides a low-boiling point foaming material. By limiting the composition of a mixed foaming agent and further limiting the composition of a butane foaming agent, the foam fluidity is further enhanced and the foam density is reduced. Since the saturated vapor pressure is relatively large and the air pressure in the foam cells is large, after the foam density is reduced, the strength, dimensional stability, expansion rate and other properties remain unchanged, which is beneficial to reducing the amount of raw materials used, reducing production costs, and reducing costs and increasing efficiency. At the same time, for customers, the space utilization rate of refrigerators is effectively improved. The refrigerators of the same size have a larger volume and can store more items, thereby meeting the needs of consumers.

[0022] The present invention provides an application of the low-boiling point foaming material in a foaming layer of a refrigerator, and adopts an ultra-high fluidity and ultra-low density CP (cyclopentane foaming agent) + LBA (or 245FA) + R600 + R600a multi-component mixed foaming system in conjunction with a back multi-gun injection process. The fluidity of the foaming system is significantly improved, and the back multi-gun injection shortens the foam flow distance. The thickness of the refrigerator foaming layer can be reduced to 10 mm, thereby improving the refrigerator volume ratio and the design upper limit. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the anatomy diagram of an ultra-thin bubble layer refrigerator. DETAILED DESCRIPTION

[0024] The technical scheme in the specific embodiment of the present invention is described in detail and completely below. Obviously, the described embodiment is only a part of the specific implementation of the overall technical scheme of the present invention, rather than all implementations. Based on the overall concept of the present invention, all other embodiments obtained by ordinary technicians in this field fall within the scope of protection of the present invention.

[0025] The present invention provides a low-boiling point foaming material, comprising: a combined polyether polyol, a mixed foaming agent, a reaction catalyst, a silicone oil surfactant, water and an isocyanate; the combined polyether polyol consists of polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D and phthalic anhydride polyester polyol E, the polyether polyol A has a hydroxyl value of 380-480 mgKOH / g, the polyether polyol B has a hydroxyl value of 360-460 mgKOH / g, the polyether polyol C has a hydroxyl value of 400-500 mgKOH / g, the polyether polyol D has a hydroxyl value of 160-260 mgKOH / g, and the phthalic anhydride polyester polyol E has a hydroxyl value of 390-490 mgKOH / g; the mixed foaming agent comprises a butane foaming agent, the butane foaming agent contains 75%-85% of n-butane R600 and 15%-25% of isobutane R600A. The low-boiling point foaming material further enhances the foam fluidity and reduces the foam density by limiting the composition of the mixed foaming agent and further limiting the composition of the butane foaming agent. Due to the large saturated vapor pressure and the large air pressure in the foam pores, after the foam density is reduced, the strength, dimensional stability, expansion rate and other properties remain unchanged, which is conducive to reducing the amount of raw materials used, reducing production costs, reducing costs and increasing efficiency. At the same time, for customers, it effectively improves the space utilization rate of the refrigerator. The refrigerator volume of the same size is larger, and more items can be stored to meet the needs of consumers. The technical solution limits the composition of the combined polyether polyols, because polyether polyol A mainly provides the thermal insulation and heat preservation ability of the foam skeleton, polyether polyol B, polyether polyol C, polyether polyol D15, mainly provide cross-linking, polymerization, skeleton growth and foam strength of foam molecules, and polyester polyol E mainly provides strength and hardness, environmental resistance for the foam skeleton. The technical solution further defines that the content of n-butane R600 in the butane foaming agent is 75%-85%, and the content of isobutane R600a is 15%-25%, because the foaming agents in this ratio are mixed evenly and have uniform properties, which is conducive to rapid foaming during the foam growth process, and the foam structure is stable and the pores are fine, thereby improving various properties of the foam. It is understandable that the content of n-butane R600 in the butane foaming agent can also be 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84% and any point value within the range thereof, and the content of isobutane R600a can also be 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% and any point value within the range thereof.

[0026] In a preferred embodiment, the mixed foaming agent is composed of cyclopentane foaming agent, LBA foaming agent and the butane foaming agent, or is composed of cyclopentane foaming agent, 245fa foaming agent and the butane foaming agent. The technical solution specifically defines the composition of the mixed foaming agent because different types of foaming agents play different roles in the foaming stage and the reaction time stage. Cyclopentane is the main foaming agent with the highest boiling point and the latest participation in foaming, which plays a role in continuous foaming growth; LBA is the secondary main foaming agent, which plays a role in foaming and heat preservation in the second stage; butane foaming agent is an auxiliary foaming agent, which participates in the foaming reaction at the first time, which increases the foam flowability and shortens the start foaming time.

[0027] In a preferred embodiment, the composition comprises 100 parts of a combined polyether polyol, 20-25 parts of a mixed foaming agent, 1-4 parts of a reaction catalyst, 1.5-3 parts of a silicone oil surfactant, 1-3 parts of water, and 140-165 parts of an isocyanate, in parts by weight; the weight of the butane foaming agent is selected from any value between 2 and 3 parts, the weight of the cyclopentane foaming agent is selected from any value between 11 and 14 parts, and the weight of the LBA foaming agent or the 245fa foaming agent is selected from any value between 4 and 9 parts. The technical scheme specifically defines the amount of each component. It can be understood that the amount of the mixed foaming agent can also be 21, 22, 23, 24 parts and any point value within the range thereof, the amount of the reaction catalyst can also be 2, 3 parts and any point value within the range thereof, the amount of the silicone oil surfactant can also be 2.0, 2.5 parts and any point value within the range thereof, the amount of water can also be 1.5, 2.0, 2.5 parts and any point value within the range thereof, the amount of isocyanate can also be 145, 150, 155, 160 parts and any point value within the range thereof, the amount of butane foaming agent can also be 2.5 parts and any point value within the range thereof, the amount of cyclopentane foaming agent can also be 12, 13 parts and any point value within the range thereof, and the amount of LBA foaming agent or 245fa foaming agent can also be 5, 6, 7, 8 parts and any point value within the range thereof.

[0028] In a preferred embodiment, the polyether polyol A is prepared by reacting toluene diamine with propylene oxide, the polyether polyol B is prepared by an addition reaction between sucrose and propylene oxide, the polyether polyol C is prepared by an addition reaction between sorbitol and propylene oxide, and the polyether polyol D is prepared by an addition reaction between glycerol and propylene oxide; the weight of the polyether polyol A is selected from any value in the range of 0-30 parts, the weight of the polyether polyol B is selected from any value in the range of 0-30 parts, the weight of the polyether polyol C is selected from any value in the range of 0-20 parts, the weight of the polyether polyol D is selected from any value in the range of 0-10 parts, and the weight of the phthalic anhydride polyester polyol E is selected from any value in the range of 0-20 parts. The technical solution further limits the dosage of each polyether polyol. It can be understood that the dosage of polyether polyol A can also be 10, 20 and any point value within the range, the dosage of polyether polyol B can also be 10, 20 and any point value within the range, the dosage of polyether polyol C can also be 5, 10, 15 and any point value within the range, the dosage of polyether polyol D can also be 2, 4, 6, 8 and any point value within the range, and the dosage of phthalic anhydride polyester polyol E can also be 5, 10, 15 and any point value within the range.

[0029] In a preferred embodiment, the NCO content of the isocyanate is 30%-32%; the silicone oil surfactant is selected from at least one of silicone oil L6863, silicone oil L6988, silicone oil AK8830, silicone oil B8525, and silicone oil B8545. Among them, isocyanate is also called polymeric MDI, preferably at least one of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010, and polymeric MDI Wanhua PM-400. The above-mentioned silicone oil surfactant is at least one of an alkali metal salt of a fatty acid, an amine salt of a fatty acid, castor oil, ricinoleic acid, and a siloxane polymer. This technical solution further defines the types of silicone oil surfactants and isocyanates. It can be understood that the types of silicone oil surfactants and isocyanates can also be other substances reasonably selected in the field by those skilled in the art in combination with common knowledge in the field.

[0030] In a preferred embodiment, the reaction catalyst is a composite catalyst, including a foaming catalyst, a gel catalyst and a trimerization catalyst, and the mass ratio of the foaming catalyst to the gel catalyst and the trimerization catalyst is 2-4:3-8:1-3. Further, the foaming catalyst is selected from at least one of pentamethyldiethylenetriamine, N-methyldicycloethylamine, tetramethylhexanediamine or bis-dimethylaminoethyl ether, the gel catalyst is selected from at least one of dimethylbenzylamine, dimethylcyclohexane or triethylenediamine, and the trimerization catalyst is selected from at least one of potassium acetate, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, (2-hydroxypropyl)trimethylammonium formate, ethyl quaternary ammonium salt or octyl quaternary ammonium salt. It should be noted that the technical solution of the present invention limits the composition of the formula, and the polyurethane foam prepared is a hard foam material, and is used in the field of refrigerator and freezer solar pipe insulation to play a role in insulation support, with the characteristics of high strength and hard texture. Specifically, the present invention adopts a variety of physical foaming agents CP, 245fa / LBA, r600, r600a, and limits the black and white material ratio (1.20-1.25), monomer types (a variety of high-viscosity and high-functionality insulation performance, strength performance excellent monomers such as O-TDA, etc.), catalyst types (including foaming catalysts, gel catalysts, trimerization catalysts), gun head mixing pressure (gun head mixing pressure is 120-140MPa), so as to obtain a low-boiling point foaming material with the characteristics of maintaining strength, dimensional stability, expansion rate and other properties unchanged, effectively reducing the amount of raw materials used, reducing production costs, reducing costs and increasing efficiency, and at the same time, improving the utilization rate of refrigerator space, the refrigerator volume under the same size is larger, and more items can be stored.

[0031] Another aspect of the present invention provides the use of the low-boiling point foaming material described in any of the above technical solutions in a foaming layer of a refrigerator, using multiple single-gun foaming machines to simultaneously inject the low-boiling point foaming material into the refrigerator injection port. Among them, the use of multiple single-gun foaming machines to simultaneously inject the low-boiling point foaming material into the refrigerator injection port is also known as the back multi-gun injection technology in the field, which can be simply understood as several single-gun foaming machines injecting materials at the same time. The foaming machine is a polyurethane high-pressure foaming machine with operating parameters generally set in the industry. The gun heads are independent of each other and have independent circulation control systems. When injecting materials, the injection volume of the foaming machine gun head can be the same or different, and the injection starts at the same time. The gun heads are lifted out at the same time after the injection is completed. Different products will choose different positions on the back as the injection port. The position of the injection port is special. The position of the injection port is determined by the product structure and the results of the refrigerator body foaming experiment. This injection method can reduce the defects of bubbles in the inner tank, improve the level of product refinement, shorten the flow distance by about 50%, and the foam flow distance is short, so the bubbles are not over-stretched, and the bubbles are round and uniform in size. The material has significantly improved physical properties such as strength and thermal conductivity. Since the flow distance is shortened and combined with ultra-high fluidity foaming material, the flow channel can be thinned to 10mm, thereby improving the volume ratio of the refrigerator.

[0032] In a preferred embodiment, the mixing pressure of the gun head of the single-gun foaming machine is any value between 120-140MPa; the injection method is vertical injection. Specifically, the injection method is vertical injection, that is, the injection port is facing upward, the foaming machine gun head is located above and can be positioned and moved according to the actual position, the injection port is located at the four corners of the back plate, the distance between adjacent injection ports is greater than 800mm, and the minimum distance between the injection port and the top, bottom and side of the back plate is 5mm. Different models can be customized to select 1-4 injection ports, which can be moved up and down and left and right according to the structure of the refrigerator body. The optimal position is determined according to the foaming simulation; the design thickness of the side panel insulation layer is 20-35mm, the thickness of the VIP board is 8-20mm, and the actual foaming layer thickness after deducting the VIP board is 10-20mm. It should be noted that the gun heads corresponding to different injection port positions are independent of each other and have independent circulation control systems. When injecting, the injection volume of the foaming machine gun head can be set separately, and the injection starts at the same time, and the gun head is lifted out at the same time when the injection is completed. This injection method can reduce the bubble defects in the liner, improve the level of product refinement, shorten the flow distance, improve the various properties of the foaming material, reduce the thickness of the foaming layer at various locations, and improve the space utilization rate of the product. In the main material process, the black material (i.e., isocyanate) and the white material (i.e., combined polyether polyol, mixed foaming agent, silicone oil surfactant, reaction catalyst, and water) begin to react after passing through the high-pressure mixing gun head, and the system gradually expands. As the reaction heat accumulates, the foaming agent changes from liquid to gas, is wrapped by the high-viscosity liquid and is separated into closed bubbles of uniform size by the uniform foaming agent in the reaction system, and the expansion speed is rapidly accelerated. As the reaction proceeds, the foam changes from viscous to solid, and the bubbles are evenly locked inside the foam. The foaming system shortens the gasification time of the foaming agent by introducing r600 / r600a, increases the early expansion speed of the foam, shortens the gasification time of the foaming agent, accelerates the foam and improves the foam flow rate, and the 10mm width foam flow channel can also be filled well.

[0033] The present invention also provides a refrigerator, wherein the foaming layer of the refrigerator is prepared by using the low-boiling point foaming material described in any of the above technical solutions. The refrigerator has a higher space utilization rate, a larger refrigerator volume under the same size, and can store more items.

[0034] In order to more clearly and in detail introduce the low-boiling point foaming material, its application and refrigerator provided in the embodiments of the present invention, a description will be given below in conjunction with specific embodiments.

[0035] Example 1

[0036] Formula: 100 parts of dry white material, 12.5 parts of cyclopentane CP, 6.5 parts of LBA, 1.5 parts of low boiling point blowing agent n-butane R600, 3 parts of reaction catalyst, 2 parts of silicone oil surfactant, 2 parts of water, 153 parts of polymerized MDI;

[0037] The dry white material is a composite polyether polyol, which includes, by weight: 30 parts of polyether polyol A prepared from toluene diamine and propylene oxide, 20 parts of polyether polyol B prepared from propylene oxide via addition reaction with sucrose as an initiator, 20 parts of polyether polyol C prepared from propylene oxide via addition reaction with sorbitol as an initiator, 15 parts of polyether polyol D prepared from propylene oxide via addition reaction with glycerol as an initiator, and 15 parts of phthalic anhydride polyester polyol E; the reaction catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst.

[0038] Injection process: The injection method is vertical injection, that is, the injection port faces upward, the foaming machine gun head is located on the top and can be moved according to the actual position. The injection port is located at the four corners of the back panel, and the distance between adjacent injection ports is greater than 800mm. The minimum distance between the injection port and the top, bottom and side of the back panel is 5mm. Different models can be customized to select 1-4 injection ports, which can be moved up, down, left and right according to the structure of the refrigerator body. The best position is determined according to the foaming simulation; the design thickness of the side panel insulation layer is 20-35mm, the thickness of the VIP panel is 8-20mm, and the actual foaming layer thickness after deducting the VIP panel is 10-20mm.

[0039] Example 2

[0040] Formula: 100 parts of dry white material, 12.5 parts of cyclopentane CP, 6.5 parts of LBA, 2.5 parts of low boiling point blowing agent n-butane R600, 3 parts of reaction catalyst, 2 parts of silicone oil surfactant, 2 parts of water, 155 parts of polymerized MDI;

[0041] The dry white material is a composite polyether polyol, which includes, by weight: 30 parts of polyether polyol A prepared from toluene diamine and propylene oxide, 20 parts of polyether polyol B prepared from propylene oxide via addition reaction with sucrose as an initiator, 20 parts of polyether polyol C prepared from propylene oxide via addition reaction with sorbitol as an initiator, 15 parts of polyether polyol D prepared from propylene oxide via addition reaction with glycerol as an initiator, and 15 parts of phthalic anhydride polyester polyol E; the reaction catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst.

[0042] Injection process: The injection method is vertical injection, that is, the injection port faces upward, the foaming machine gun head is located on the top and can be moved according to the actual position. The injection port is located at the four corners of the back panel, and the distance between adjacent injection ports is greater than 800mm. The minimum distance between the injection port and the top, bottom and side of the back panel is 5mm. Different models can be customized to select 1-4 injection ports, which can be moved up, down, left and right according to the structure of the refrigerator body. The best position is determined according to the foaming simulation; the design thickness of the side panel insulation layer is 20-35mm, the thickness of the VIP panel is 8-20mm, and the actual foaming layer thickness after deducting the VIP panel is 10-20mm.

[0043] Example 3

[0044] Formula: 100 parts of dry white material, 12.5 parts of cyclopentane CP, 6.5 parts of LBA, 1.25 parts of low boiling point blowing agent n-butane R600, 1.25 parts of isobutane R600A, 3 parts of reaction catalyst, 2 parts of silicone oil surfactant, 2 parts of water, 155 parts of polymerized MDI;

[0045] The dry white material is a composite polyether polyol, which includes, by weight: 30 parts of polyether polyol A prepared from toluene diamine and propylene oxide, 20 parts of polyether polyol B prepared from propylene oxide via addition reaction with sucrose as an initiator, 20 parts of polyether polyol C prepared from propylene oxide via addition reaction with sorbitol as an initiator, 15 parts of polyether polyol D prepared from propylene oxide via addition reaction with glycerol as an initiator, and 15 parts of phthalic anhydride polyester polyol E; the reaction catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst.

[0046] Injection process: The injection method is vertical injection, that is, the injection port faces upward, the foaming machine gun head is located on the top and can be moved according to the actual position. The injection port is located at the four corners of the back panel, and the distance between adjacent injection ports is greater than 800mm. The minimum distance between the injection port and the top, bottom and side of the back panel is 5mm. Different models can be customized to select 1-4 injection ports, which can be moved up, down, left and right according to the structure of the refrigerator body. The best position is determined according to the foaming simulation; the design thickness of the side panel insulation layer is 20-35mm, the thickness of the VIP panel is 8-20mm, and the actual foaming layer thickness after deducting the VIP panel is 10-20mm.

[0047] Example 4

[0048] Formula: 100 parts of dry white material, 12.5 parts of cyclopentane CP, LBA, 2 parts of low boiling point blowing agent n-butane R600, 0.5 parts of isobutane R600A, 3 parts of reaction catalyst, 2 parts of silicone oil surfactant, 2 parts of water, 155 parts of polymerized MDI;

[0049] The dry white material is a composite polyether polyol, which includes, by weight: 30 parts of polyether polyol A prepared from toluene diamine and propylene oxide, 20 parts of polyether polyol B prepared from propylene oxide via addition reaction with sucrose as an initiator, 20 parts of polyether polyol C prepared from propylene oxide via addition reaction with sorbitol as an initiator, 15 parts of polyether polyol D prepared from propylene oxide via addition reaction with glycerol as an initiator, and 15 parts of phthalic anhydride polyester polyol E; the reaction catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst.

[0050] Injection process: The injection method is vertical injection, that is, the injection port faces upward, the foaming machine gun head is located on the top and can be moved according to the actual position. The injection port is located at the four corners of the back panel, and the distance between adjacent injection ports is greater than 800mm. The minimum distance between the injection port and the top, bottom and side of the back panel is 5mm. Different models can be customized to select 1-4 injection ports, which can be moved up, down, left and right according to the structure of the refrigerator body. The best position is determined according to the foaming simulation; the design thickness of the side panel insulation layer is 20-35mm, the thickness of the VIP panel is 8-20mm, and the actual foaming layer thickness after deducting the VIP panel is 10-20mm.

[0051] Comparative Example 1

[0052] The formula is the same as that of Example 4, as follows: 100 parts of dry white material, 12.5 parts of cyclopentane CP, 6.5 parts of LBA, 2 parts of low boiling point blowing agent n-butane R600, 0.5 parts of isobutane R600A, 3 parts of reaction catalyst, 2 parts of silicone oil surfactant, 2 parts of water, and 155 parts of polymeric MDI;

[0053] The dry white material is a composite polyether polyol, which includes, by weight: 30 parts of polyether polyol A prepared from toluene diamine and propylene oxide, 20 parts of polyether polyol B prepared from propylene oxide via addition reaction with sucrose as an initiator, 20 parts of polyether polyol C prepared from propylene oxide via addition reaction with sorbitol as an initiator, 15 parts of polyether polyol D prepared from propylene oxide via addition reaction with glycerol as an initiator, and 15 parts of phthalic anhydride polyester polyol E; the reaction catalyst includes a foaming catalyst, a gel catalyst and a trimerization catalyst.

[0054] Injection process: The existing injection process is to inject material with one gun on the upper part of the compressor compartment. This method has a long flow distance, poor foam state, and is prone to problems such as foam shrinkage and delamination.

[0055] Performance Testing

[0056] The foam properties of the above embodiments and comparative examples were tested, and the results are shown in Table 1.

[0057] Table 1 Foam properties

[0058]

[0059]

[0060] From the foam test results in Table 1, compared with Example 1, Examples 2-4 have basically maintained the same compressive strength and dimensional stability, but the density is significantly reduced and the fluidity is significantly increased. Among them, Example 4 has the best thermal conductivity. Figure 1This is the anatomical diagram of the ultra-thin bubble layer refrigerator. As shown in the figure, excluding the thickness of the VIP panel, the thinnest bubble layer of the side panel is 10mm and it is still well filled.

Claims

1. A low boiling point foaming material, characterized in that: include: Combine polyether polyol, mixed foaming agent, reaction catalyst, silicone oil surfactant, water and isocyanate; The combined polyether polyol is composed of polyether polyol A, polyether polyol B, polyether polyol C, polyether polyol D, and phthalic anhydride polyester polyol E, wherein the hydroxyl value of the polyether polyol A is 380-480 mgKOH / g, the hydroxyl value of the polyether polyol B is 360-460 mgKOH / g, the hydroxyl value of the polyether polyol C is 400-500 mgKOH / g, the hydroxyl value of the polyether polyol D is 160-260 mgKOH / g, and the hydroxyl value of the phthalic anhydride polyester polyol E is 390-490 mgKOH / g; The mixed foaming agent comprises a butane foaming agent, in which the content of normal butane R600 is 75%-85% and the content of isobutane R600a is 15%-25%.

2. The low boiling point foaming material according to claim 1, characterized in that: The mixed foaming agent consists of a cyclopentane foaming agent, an LBA foaming agent and the butane foaming agent, or consists of a cyclopentane foaming agent, a 245fa foaming agent and the butane foaming agent.

3. The low boiling point foaming material according to claim 2, characterized in that: In parts by weight, it includes 100 parts of combined polyether polyol, 20-25 parts of mixed foaming agent, 1-4 parts of reaction catalyst, 1.5-3 parts of silicone oil surfactant, 1-3 parts of water, and 140-165 parts of isocyanate; The weight portion of the butane foaming agent is selected from any value between 2 and 3 parts, the weight portion of the cyclopentane foaming agent is selected from any value between 11 and 14 parts, and the weight portion of the LBA foaming agent or the 245fa foaming agent is selected from any value between 4 and 9 parts.

4. The low boiling point foaming material according to claim 1, characterized in that: The polyether polyol A is prepared by reacting toluene diamine with propylene oxide, the polyether polyol B is prepared by reacting sucrose as an initiator with propylene oxide through an addition reaction, the polyether polyol C is prepared by reacting sorbitol as an initiator with propylene oxide through an addition reaction, and the polyether polyol D is prepared by reacting glycerol as an initiator with propylene oxide through an addition reaction; The weight portion of the polyether polyol A is selected from any value between 0 and 30 parts, the weight portion of the polyether polyol B is selected from any value between 0 and 30 parts, the weight portion of the polyether polyol C is selected from any value between 0 and 20 parts, the weight portion of the polyether polyol D is selected from any value between 0 and 10 parts, and the weight portion of the phthalic anhydride polyester polyol E is selected from any value between 0 and 20 parts.

5. The low boiling point foaming material according to claim 1, characterized in that: The NCO content of the isocyanate is 30%-32%; the silicone oil surfactant is selected from at least one of silicone oil L6863, silicone oil L6988, silicone oil AK8830, silicone oil B8525 and silicone oil B8545.

6. The low boiling point foaming material according to claim 1, characterized in that: The reaction catalyst is a composite catalyst, including a foaming catalyst, a gel catalyst and a trimerization catalyst. The mass ratio of the foaming catalyst to the gel catalyst and the trimerization catalyst is 2-4:3-8:1-3.

7. The low boiling point foaming material according to claim 6, characterized in that: The foaming catalyst is selected from at least one of pentamethyldiethylenetriamine, N-methyldicycloethylamine, tetramethylhexanediamine or bis-dimethylaminoethyl ether, the gelling catalyst is selected from at least one of dimethylbenzylamine, dimethylcyclohexane or triethylenediamine, and the trimerization catalyst is selected from at least one of potassium acetate, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, (2-hydroxypropyl)trimethylammonium formate, ethyl quaternary ammonium salt or octyl quaternary ammonium salt.

8. Use of the low boiling point foaming material according to any one of claims 1 to 7 in a foaming layer of a refrigerator, characterized in that: A plurality of single-gun head foaming machines are used to simultaneously inject the low-boiling point foaming material into the refrigerator injection port.

9. The use of the low boiling point foaming material according to claim 8 in a foaming layer of a refrigerator, characterized in that: The mixing pressure of the gun head of the single-gun head foaming machine is any value between 120 MPa and 140 MPa; the injection method is vertical injection.

10. A refrigerator, characterized in that: The foaming layer of the refrigerator is prepared by using the low-boiling point foaming material according to any one of claims 1 to 8.

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