Reinforced rigid polyurethane foam material and method for manufacturing the same

Abstract

This invention discloses a reinforced rigid polyurethane foam material and a method for producing the same, and belongs to the field of polymer materials. The material comprises 5 to 10 parts glass fiber yarn, 40 to 60 parts aromatic polyether polyol, 30 to 50 parts aromatic polyester polyol, 30 to 50 parts toluene diisocyanate, 40 to 60 parts polymethylene polyphenyl polyisocyanate, 5 to 10 parts flame retardant, 5 to 15 parts blowing agent, 1 to 5 parts catalyst, and 1 to 5 parts surfactant. This invention enables continuous production of reinforced rigid polyurethane foam material, improves the tensile properties of the material by more than 20%, improves the utilization rate of glass fibers by more than 5%, and can be widely used in the field of liquefied gas storage and transportation.

Description

[Technical Field]

[0001] This invention relates to the technical field of polymer materials, and more specifically to reinforced rigid polyurethane foam material and a method for producing the same. [Background technology]

[0002] Rigid polyurethane foam plastic, also simply called rigid polyurethane foam, is the second most widely used polyurethane product after flexible polyurethane foam. Rigid polyurethane foam material has an almost closed-cell structure and possesses excellent properties such as good thermal insulation, light weight, high specific strength, and ease of handling. It also has properties such as sound insulation, shock absorption, electrical insulation, heat resistance, cold resistance, and solvent resistance. It is widely used as insulation for refrigerator and freezer boxes, refrigerated warehouses and refrigerated trucks, buildings, storage tanks and pipelines, and, in smaller quantities, for applications other than insulation, such as imitation wood and packaging materials. Generally, low-density rigid polyurethane foam is mainly used as thermal insulation, while high-density rigid polyurethane foam is used as structural material (imitation wood).

[0003] While conventional rigid polyurethane foam materials all have excellent heat retention properties, they suffer from severe shrinkage and cracking in extremely cold environments, resulting in a loss of mechanical strength and heat retention. To solve this problem, rigid polyurethane foam is typically compounded with glass fiber continuous felt to improve its mechanical properties and dimensional stability at low temperatures, and the flame retardancy level of the polyurethane is improved by adding a predetermined flame retardant. For example, in patent 2007101441393 (publication number CN101235128A), a density of 400-800 kg / m³ reinforced with continuous fibers is described. 3 Although a polyurethane foam material is disclosed, this material is suitable for "load-bearing structural materials" and cannot be used for heat retention in cryogenic environments. Patent 200610058849X (Publication No. CN1834130A) describes a material with a density of 115-135 kg / m³. 3The patent application discloses a thermal insulation material with a compressive strength of 1.4 to 1.7 MPa. However, this application does not provide detailed thermal conductivity information regarding the thermal insulation properties of the material, nor does it provide information on the material's mechanical properties at low temperatures.

[0004] Traditionally, continuous fiberglass felt, used to increase the strength of polyurethane foam materials, typically comes in rolls of 100-150 meters in length. Mass production can only be carried out intermittently, resulting in significant scrap at the beginning and end of each batch, reducing production efficiency and causing serious environmental pollution.

[0005] Therefore, the urgent challenge for those skilled in the art is how to provide an environmentally friendly, reinforced rigid polyurethane foam material that can be produced in continuous production. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In view of the foregoing, the present invention provides a reinforced rigid polyurethane foam material and a method for producing the same. [Means for solving the problem]

[0007] To achieve the above objectives, the present invention employs the following technical solutions.

[0008] The reinforced rigid polyurethane foam material contains 5 to 10 parts by weight of glass fiber yarn, 40 to 60 parts by weight of aromatic polyether polyol, 30 to 50 parts by weight of aromatic polyester polyol, 30 to 50 parts by weight of toluene diisocyanate, 40 to 60 parts by weight of polymethylene polyphenyl polyisocyanate, 5 to 10 parts by weight of flame retardant, 5 to 15 parts by weight of blowing agent, 1 to 5 parts by weight of catalyst, and 1 to 5 parts by weight of surfactant.

[0009] Preferably, the raw materials include 6 parts by weight of glass fiber yarn, 50 parts by weight of aromatic polyether polyol, 40 parts by weight of aromatic polyester polyol, 50 parts by weight of toluene diisocyanate, 60 parts by weight of polymethylene polyphenyl polyisocyanate, 5 parts by weight of flame retardant, 9 parts by weight of blowing agent, 2 parts by weight of catalyst, and 2 parts by weight of surfactant.

[0010] Furthermore, the glass fiber yarn has a single fiber diameter of 5 to 15 μm, preferably 5 to 10 μm, more preferably 9 μm, a yarn density of 10 to 30 tex, preferably 10 to 15 tex, more preferably 15 tex, a water content of less than 0.1%, and a flammable content of 0.5% to 1.5%.

[0011] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: In this invention, by using glass fiber yarn instead of the glass fiber continuous felt commonly used in conventional processes, the glass fiber yarn has a larger specific surface area, which increases the effective bonding area between the glass fibers and the resin, thereby further increasing the tensile strength of the material. Furthermore, while glass fiber felt is a roll material with a limited length and can only be produced intermittently, glass fiber yarn can be continuously produced because it can be spliced ​​indefinitely. This not only improves production efficiency but also effectively reduces cutting losses at the beginning and end of batches, resulting in a more environmentally friendly product.

[0012] Furthermore, the aromatic polyether polyol has a molecular weight of 400 to 600, preferably 500 to 600, more preferably 550; a hydroxyl value of 400 to 600 mgKOH / g, preferably 450 to 550 mgKOH / g, more preferably 480 mgKOH / g; a viscosity of 5000 to 9000 mPa·S, preferably 5000 to 7000 mPa·S, more preferably 6000 mPa·S; and a water content of less than 0.15%.

[0013] Furthermore, the aromatic polyether polyol is at least one of toluenediamine polyether, bisphenol A polyether, and aniline formaldehyde polyether.

[0014] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: The aromatic polyether polyol of the present invention can introduce an aromatic ring structure into the rigid polyurethane foam skeleton, thereby improving the dimensional stability, heat resistance, and flame retardancy of the rigid polyurethane foam material.

[0015] Furthermore, the aromatic polyester polyol has a molecular weight of 400 to 600, preferably 450 to 550, more preferably 520; a hydroxyl value of 300 to 500 mgKOH / g, preferably 400 to 480, more preferably 430; a viscosity of 4000 to 6000 mPa·S, preferably 4500 to 5500 mPa·S, more preferably 4800 mPa·S; and a water content of less than 0.10%.

[0016] Furthermore, the aromatic polyester polyol is at least one of phthalic anhydride polyester polyol, trimellitic anhydride polyester polyol, and aromatic-aliphatic copolyester.

[0017] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: The aromatic polyester polyol of the present invention has improved compatibility with the polymethylene polyphenyl polyisocyanate component, which can increase the fineness of the rigid polyurethane foam material, thereby improving its heat retention properties. Furthermore, by introducing more aromatic ring structures into the rigid polyurethane foam skeleton, the dimensional stability, heat resistance, and flame retardancy of the rigid polyurethane foam material can also be improved.

[0018] Furthermore, the polymethylene polyphenyl polyisocyanate has an isocyanate content of 25 to 35 wt%, preferably 25 to 30 wt%, more preferably 29 wt%, a viscosity of 100 to 300 mPa·S, preferably 150 to 250 mPa·S, more preferably 200 mPa·S, and a functionality of 2.5 to 3.5, preferably 2.0 to 2.5, more preferably 2.4.

[0019] Furthermore, the flame retardant has a phosphorus content of 5 to 15%, preferably 5 to 10%, more preferably 9%, a viscosity of 50 to 200 mPa·S, preferably 50 to 90 mPa·S, more preferably 60 mPa·S, and a water content of less than 0.10%.

[0020] In addition, the flame retardant is any one or a mixture of two of tris(2-chloroethyl) phosphate, tris(2-chloropropyl phosphate), and tris(dichloropropyl) phosphate. <​​​​​​​​​​​​​​​

[0025] Furthermore, the catalyst is a mixture of a small molecule amine-based catalyst and an organotin-based catalyst, and further, the small molecule amine-based catalyst is any one or a mixture of two of triethylenediamine, tetramethylhexanediamine, and triethylamine, and the organotin-based catalyst is any one or a mixture of two of stannous octoate and dibutyltin diacetate.

[0026] Furthermore, the surfactant is a polysiloxane-based polymer having a viscosity of 200 to 600 mPa·S and a water content of less than 0.05%.

[0027] Also, further, the surfactant is any one or a mixture of two of a polysiloxane-ethylene oxide AB-type linear block polymer and a polysiloxane-propylene oxide ABA-type linear block polymer.

[0028] The beneficial effects obtained by adopting the above further technical solutions are as follows. The flame retardant, foaming agent, catalyst, and surfactant of the present invention can effectively improve the flame retardancy, heat insulation properties, mechanical strength, and dimensional stability of the rigid polyurethane foam material.

[0029] The present invention randomly laminates glass fiber yarns on a conveyor belt by a throwing mechanism to form a glass fiber yarn random web, and then step (1) of weighing each raw material in the above parts by weight, step (2) of mixing aromatic polyether polyol, aromatic polyester polyol, toluene diisocyanate, polymethylene polyphenyl polyisocyanate, flame retardant, foaming agent, catalyst, and surfactant to obtain a mixture, pouring the mixture onto a random web structure formed by randomly laminating flatly spread glass fiber yarns, and then foaming by a foaming machine to obtain a semi-finished product, step (3), The present invention further provides a method for producing the above-described reinforced rigid polyurethane foam material, which includes the step (4) of allowing a semi-finished product to naturally harden, cutting it into multiple parts, and hardening it again to obtain a reinforced rigid polyurethane foam material.

[0030] Furthermore, in step (1), the thread throwing mechanism has a width of 0.8 to 2.4 m, preferably 1.2 to 2.0 m, a travel speed of 1 to 2 m / s, preferably 1.4 to 1.8 m / s, the glass fiber random web has a thickness of 40 to 180 mm, preferably 80 to 120 mm, and the glass fiber random web has a density of 0.5 to 5 kg / m³. 2 Preferably 2-3 kg / m 2 That was the case.

[0031] Furthermore, in step (2), a high-pressure mixing head is used for mixing, with a mixing pressure of 40-100 bar, preferably 80 bar, a mixing temperature of 20-30°C, preferably 23°C, and a discharge rate of 50-100 kg / min, preferably 70 kg / min.

[0032] The advantageous effects of adopting the above-mentioned further technical solutions are as follows: The high-pressure mixing head of the present invention, due to its high mixing pressure, improves the mixing effect of the hydroxyl component and the isocyanate component, making the foam of the rigid polyurethane foam material finer and improving its heat retention properties.

[0033] Furthermore, in step (3), the glass fiber continuous felt is separated from the chain plate using kraft paper, and the apparent density of the kraft paper is 80-150 g / m². 2 That is the case.

[0034] Furthermore, in step (3), the discharge rate of the mixture is 30-120 kg / min, preferably 50-70 kg / min, the discharge temperature is 15-35°C, preferably 20-30°C, and the chain plate temperature is 15-35°C, preferably 20-30°C.

[0035] Furthermore, in step (4), the natural hardening time is 40-80 minutes, and the re-hardening time is 72 hours.

[0036] Furthermore, steps (2) to (4) are carried out in a constant temperature and humidity environment with a temperature of 10 to 40°C and a humidity of 70% or less.

[0037] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: The polyurethane foam foaming process of the present invention is carried out in a controlled temperature and humidity environment, the material is uniformly dispersed, the foaming process rate is uniform, and the density distribution of the polyurethane foam is more uniform. [Effects of the Invention]

[0038] The beneficial effects of this invention are as follows: In this invention, glass fiber yarn is used instead of continuous glass fiber felt in conventional processes. Because glass fiber yarn has a larger specific surface area, it increases the effective bonding area between glass fibers and resin, and can increase the tensile strength of the material by more than 20%. Glass fiber felt is a roll material with a limited length and can only be produced intermittently, but glass fiber yarn can be spliced ​​indefinitely, making continuous production possible. This not only improves production efficiency but also effectively reduces cutting losses at the beginning and end of batches, resulting in a more environmentally friendly product. Furthermore, it can improve the utilization rate of glass fibers by more than 5% while ensuring the mechanical strength and heat retention properties of the material at low temperatures, making it widely applicable in extremely low heat retention fields. [Brief explanation of the drawing]

[0039] [Figure 1] This is a schematic diagram of the process for manufacturing the rigid polyurethane foam material of the present invention. [Modes for carrying out the invention]

[0040] The technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the accompanying drawings of the embodiments of the present invention, but it is clear that the embodiments described are only a part of the embodiments of the present invention and not all embodiments. All other embodiments that a person skilled in the art could obtain without creative work based on the embodiments of the present invention are within the scope of the protection of the present invention. Example 1

[0041] Reinforced rigid polyurethane foam material: (1) Weigh 5 kg of glass fiber yarn, 40 kg of toluenediamine polyether, 50 kg of trimellitic anhydride polyester, 50 kg of toluene diisocyanate, 40 kg of polymethylene polyphenyl polyisocyanate, 5 kg of tris(2-chloroethyl) phosphate, 15 kg of trans-1-chloro-3,3,3-trifluoropropene, 1 kg of tetramethylhexanediamine, and 2 kg of polysiloxane-propylene oxide ABA type linear block polymer. Here, the glass fiber yarn has a diameter of 10 μm. The toluenediamine polyether had a molecular weight of 500, a hydroxyl value of 450 mgKOH / g, a viscosity of 5000 mPa·S, and a water content of 0.1%. The trimellitic anhydride polyester had a molecular weight of 580, a hydroxyl value of 300 mgKOH / g, a viscosity of 4000 mPa·S, and a water content of 0.07%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 29 wt%, a viscosity of 250 mPa·S, and a functionality of 2.3. A glass fiber matrix was constructed using multiple sets of glass fiber spindles, and randomly stacked using a yarn throwing mechanism to form a glass fiber random web structure with a predetermined thickness and density. This web was then introduced into a foaming region via a chain plate. The yarn throwing mechanism had a width of 1.2 m and a travel speed of 1.4 m / s. The glass fiber random web had a thickness of 40 mm and a density of 2 kg / m³. 2 That was the case. (2) In a constant temperature and humidity environment of 20°C and 60% humidity, each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 80 bar, a temperature of 20°C, and a discharge rate of 50 kg / min. (3) The mixture was uniformly spread onto a random web structure of glass fiber yarn via a conveyor pipe to wet the entire web structure, after which the reaction was initiated and foamed into a reinforced rigid polyurethane foam semi-finished material. The temperature of the chain plate was 20°C. (4) The semi-finished product was allowed to cure naturally for 40 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Example 2

[0042] Reinforced rigid polyurethane foam material: (1) 7 kg of glass fiber yarn, 50 kg of bisphenol A polyether, 40 kg of phthalic anhydride polyester, 30 kg of toluene diisocyanate, 60 kg of polymethylene polyphenyl polyisocyanate, 9 kg of tris(2-chloropropyl phosphate), 10 kg of trans-1-chloro-3,3,3-trifluoropropene, 1 kg of triethylenediamine, 0.5 kg of tetramethylhexanediamine, and 5 kg of polysiloxane-ethylene oxide type AB linear block polymer were weighed. Here, the glass fiber yarn had a diameter of 6 μm, a yarn density of 15 tex, a water content of 0.06%, and a flammability content of 1.0%. The bisphenol A polyether had a molecular weight of 600, a hydroxyl value of 400 mg KOH / g, a viscosity of 7000 mPa·S, and a water content of 0.08%. The phthalic anhydride polyester had a molecular weight of 450, a hydroxyl value of 500 mg KOH / g, a viscosity of 6000 mPa·S, and a water content of 0.06%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 32 wt%, a viscosity of 200 mPa·S, and a functionality of 3.5. A glass fiber matrix was constructed using multiple sets of glass fiber spindles, and randomly stacked using a yarn throwing mechanism to form a glass fiber random web structure with a predetermined thickness and density. This web was then introduced into a foaming region via a chain plate. The yarn throwing mechanism had a width of 2.4 m and a travel speed of 2 m / s. The glass fiber random web had a thickness of 80 mm and a density of 2.5 kg / m³. 2 That was the case. (2) In a constant temperature and humidity environment of 25°C and 40% humidity, each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 100 bar, a temperature of 30°C, and a discharge rate of 70 kg / min. (3) The mixture was uniformly sprayed onto a random web structure of glass fiber yarn via a conveyor pipe to wet the entire web structure, after which the reaction was initiated and foamed into a reinforced rigid polyurethane foam semi-finished material. The temperature of the chain plate was 25°C. (4) The semi-finished product was allowed to cure naturally for 65 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Example 3

[0043] Reinforced rigid polyurethane foam material: (1) 9 kg of glass fiber yarn, 60 kg of phthalic anhydride-formaldehyde polyether, 40 kg of phthalic anhydride polyester, 40 kg of toluene diisocyanate, 55 kg of polymethylene polyphenyl polyisocyanate, 5 kg of tris(dichloropropyl) phosphate, 5 kg of pentafluoropropane, 1 kg of trans-1-chloro-3,3,3-trifluoropropene, 1 kg of tetramethylhexanediamine, 0.5 kg of triethylamine, 1 kg of polysiloxane-ethylene oxide AB type linear block polymer, and 0.5 kg of polysiloxane-propylene oxide ABA type linear block polymer were weighed. Here, the glass fiber yarn had a diameter of 5 μm, a yarn density of 20 tex, a water content of 0.05%, and a flammability content of 1.2%. The phthalic anhydride-formaldehyde polyether had a molecular weight of 550, a hydroxyl value of 450 mg KOH / g, a viscosity of 5500 mPa·S, and a water content of 0.09%. The phthalic anhydride polyester had a molecular weight of 550, a hydroxyl value of 350 mg KOH / g, a viscosity of 4200 mPa·S, and a water content of 0.08%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 33 wt%, a viscosity of 190 mPa·S, and a functionality of 2.4. A glass fiber matrix was constructed using multiple sets of glass fiber spindles, and the fibers were randomly stacked using a fiber throwing mechanism to form a glass fiber random web structure with a predetermined thickness and density. This web was then introduced into a foaming region via a chain plate. The fiber throwing mechanism had a width of 1.6 m and a travel speed of 1.8 m / s. The glass fiber random web had a thickness of 180 mm and a density of 5 kg / m³. 2 That was the case. (2) In a constant temperature and humidity environment of 25°C and 50% humidity, each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 70 bar, a temperature of 28°C, and a discharge rate of 120 kg / min. (3) The mixture was uniformly spread onto a random web structure of glass fiber yarn via a conveyor pipe to wet the entire web structure, after which the reaction was initiated and foamed into a reinforced rigid polyurethane foam semi-finished material. The temperature of the chain plate was 30°C. (4) The semi-finished product was allowed to cure naturally for 60 minutes, then cut into multiple pieces and allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Example 4

[0044] Reinforced rigid polyurethane foam material: (1) 8 kg of glass fiber yarn, 55 kg of phthalic anhydride-formaldehyde polyether, 45 kg of aromatic-aliphatic copolyester, 45 kg of toluene diisocyanate, 50 kg of polymethylene polyphenyl polyisocyanate, 2 kg of tris(2-chloroethyl) phosphate, 3 kg of tris(dichloropropyl) phosphate, 1 kg of pentafluoropropane, 7 kg of trans-1-chloro-3,3,3-trifluoropropene, 1 kg of triethylamine, and 2.5 kg of polysiloxane-ethylene oxide AB-type linear block polymer were weighed. The glass fiber yarn had a diameter of 15 μm, a yarn density of 30 tex, a moisture content of 0.03%, and a combustible content of 0.9%. The phthalic anhydride-formaldehyde polyether had a molecular weight of 600, a hydroxyl value of 400 mgKOH / g, a viscosity of 9000 mPa·S, and a moisture content of 0.07%. The aromatic-aliphatic copolyester had a molecular weight of 400, a hydroxyl value of 600 mgKOH / g, a viscosity of 8000 mPa·S, and a moisture content of 0.07%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 30 wt%, a viscosity of 220 mPa·S, and a functionality of 2.0. A glass fiber yarn matrix was formed using a plurality of sets of glass fiber yarn spindles, randomly laminated by a yarn throwing mechanism to form a glass fiber yarn random web structure having a predetermined thickness and density, and then placed into the foaming region through a chain plate. The yarn throwing mechanism had a width of 1.4 m and a running speed of 1.6 m / s, and the glass fiber yarn random web had a thickness of 100 mm and a density of 3 kg / m 2 . (2) In a constant temperature and humidity environment of 30 °C and 67% humidity, each component was put into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 60 bar, a temperature of 25 °C, and a discharge rate of 80 kg / min. (3) The mixture was uniformly sprayed onto the glass fiber yarn random web structure through a conveyor pipe to wet the entire web structure, and then the reaction was started to foam into a semi-finished product material of reinforced rigid polyurethane foam. The temperature of the chain plate was 26 °C. (4) The semi-finished product was naturally cured for 50 min, cut into a plurality of parts, and then cured again for 72 h to obtain a reinforced rigid polyurethane foam material. Example 5

[0045] Reinforced rigid polyurethane foam material: (1) 10 kg of glass fiber yarn, 45 kg of toluenediamine polyether, 50 kg of aromatic-aliphatic copolyester, 35 kg of toluene diisocyanate, 55 kg of polymethylene polyphenyl polyisocyanate, 6 kg of tris(2-chloroethyl) phosphate, 2 kg of pentafluoropropane, 7 kg of trans-1-chloro-3,3,3-trifluoropropene, 0.5 kg of triethylenediamine, 1 kg of triethylamine, 1.5 kg of polysiloxane-ethylene oxide AB type linear block polymer, and 0.5 kg of polysiloxane-propylene oxide ABA type linear block polymer were weighed. The glass fiber yarn had a diameter of 8 μm, a yarn density of 15 tex, a water content of 0.05%, and a flammability content of 0.5%. The toluenediamine polyether had a molecular weight of 500, a hydroxyl value of 500 mg KOH / g, a viscosity of 5000 mPa·S, and a water content of 0.08%. The aromatic-aliphatic copolyester had a molecular weight of 500, a hydroxyl value of 500 mg KOH / g, a viscosity of 5000 mPa·S, and a water content of 0.09%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 25 wt%, a viscosity of 160 mPa·S, and a functionality of 2.5. A glass fiber matrix was constructed using multiple sets of glass fiber spindles, and randomly stacked using a yarn throwing mechanism to form a glass fiber random web structure with a predetermined thickness and density. This web was then introduced into a foaming region via a chain plate. The yarn throwing mechanism had a width of 1.2 m and a travel speed of 1.4 m / s. The glass fiber random web had a thickness of 80 mm and a density of 2.6 kg / m³. 2 That was the case. (2) In a constant temperature and humidity environment of 25°C and 35% humidity, each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 80 bar, a temperature of 28°C, and a discharge rate of 75 kg / min. (3) The mixture was uniformly sprayed onto a random web structure of glass fiber yarn via a conveyor pipe to wet the entire web structure, after which the reaction was initiated and foamed into a reinforced rigid polyurethane foam semi-finished material. The temperature of the chain plate was 28°C. (4) The semi-finished product was allowed to cure naturally for 45 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Example 6

[0046] Reinforced rigid polyurethane foam material: (1) 7 kg of glass fiber yarn, 45 kg of toluenediamine polyether, 55 kg of phthalic anhydride polyester, 45 kg of toluene diisocyanate, 60 kg of polymethylene polyphenyl polyisocyanate, 10 kg of tris(2-chloropropyl phosphate), 8 kg of pentafluoropropane, 1 kg of triethylenediamine, 1 kg of triethylamine, 1 kg of polysiloxane-ethylene oxide AB type linear block polymer, and 1.5 kg of polysiloxane-propylene oxide ABA type linear block polymer were weighed. The glass fiber yarn had a diameter of 6 μm, a yarn density of 20 tex, a water content of 0.06%, and a flammability content of 0.8%. The toluenediamine polyether had a molecular weight of 500, a hydroxyl value of 550 mg KOH / g, a viscosity of 6500 mPa·S, and a water content of 0.08%. The phthalic anhydride polyester had a molecular weight of 500, a hydroxyl value of 550 mg KOH / g, a viscosity of 6000 mPa·S, and a water content of 0.09%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 27 wt%, a viscosity of 210 mPa·S, and a functionality of 2.6. A glass fiber matrix was constructed using multiple sets of glass fiber spindles, and randomly stacked using a yarn throwing mechanism to form a glass fiber random web structure with a predetermined thickness and density. This web was then introduced into a foaming region via a chain plate. The yarn throwing mechanism had a width of 0.8 m and a travel speed of 1 m / s. The glass fiber random web had a thickness of 60 mm and a density of 0.5 kg / m³. 2 That was the case. (2) In a constant temperature and humidity environment of 25°C and 35% humidity, each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 40 bar, a temperature of 28°C, and a discharge rate of 30 kg / min. (3) The mixture was uniformly spread onto a random web structure of glass fiber yarn via a conveyor pipe to wet the entire web structure, after which the reaction was initiated and foamed into a reinforced rigid polyurethane foam semi-finished material. The temperature of the chain plate was 15°C. (4) The semi-finished product was allowed to cure naturally for 45 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Comparative Example 1

[0047] Reinforced rigid polyurethane foam material: (1) Weighing was performed the following: 9 kg of glass fiber continuous felt, 60 kg of toluenediamine polyether, 40 kg of trimellitic anhydride polyester, 40 kg of toluene diisocyanate, 55 kg of polymethylene polyphenyl polyisocyanate, 5 kg of tris(2-chloropropyl phosphate), 4 kg of pentafluoropropane, 2 kg of trans-1-chloro-3,3,3-trifluoropropene, 1.5 kg of triethylamine, and 1.5 kg of polysiloxane-ethylene oxide type AB linear block polymer. The glass fiber continuous felt had a density of 1 kg / m³. 2 Toluene diamine polyether had a molecular weight of 550, a hydroxyl value of 500 mgKOH / g, a viscosity of 7500 mPa·S, and a water content of 0.1%. Phthalic anhydride polyester had a molecular weight of 500, a hydroxyl value of 550 mgKOH / g, a viscosity of 6000 mPa·S, and a water content of 0.09%. Polymethylene polyphenyl polyisocyanate had an isocyanate content of 31 wt%, a viscosity of 230 mPa·S, and a functionality of 2.9. Each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 70 bar, a temperature of 28°C, and a discharge rate of 120 kg / min. (2) The mixture was poured onto a flat sheet of continuous glass fiber felt in a constant temperature and humidity environment of 25°C and 50% humidity, and then foamed and molded to obtain a semi-finished product. The temperature of the chain plate was 30°C. (3) The semi-finished product was allowed to cure naturally for 45 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Comparative Example 2

[0048] Reinforced rigid polyurethane foam material: (1) 10 kg of glass fiber continuous felt, 45 kg of aniline-formaldehyde polyether, 50 kg of aromatic-aliphatic copolyester, 35 kg of toluene diisocyanate, 55 kg of polymethylene polyphenyl polyisocyanate, 6 kg of tris(2-chloropropyl phosphate), 3 parts of pentafluoropropane, 6 parts of trans-1-chloro-3,3,3-trifluoropropene, 1 part of tetramethylhexanediamine, 2 parts of polysiloxane-ethylene oxide AB type linear block polymer, and 1.5 parts of polysiloxane-propylene oxide ABA type linear block polymer were weighed. Here, the glass fiber continuous felt had a density of 0.5 kg / m³. 2 The aniline-formaldehyde polyether had a molecular weight of 580, a hydroxyl value of 480 mgKOH / g, a viscosity of 5800 mPa·S, and a water content of 0.1%. The phthalic anhydride polyester had a molecular weight of 480, a hydroxyl value of 480 mgKOH / g, a viscosity of 4800 mPa·S, and a water content of 0.1%. The polymethylene polyphenyl polyisocyanate had an isocyanate content of 30 wt%, a viscosity of 220 mPa·S, and a functionality of 2.8. Each component was introduced into a high-pressure mixing head and mixed to obtain a mixture at a pressure of 80 bar, a temperature of 28°C, and a discharge rate of 75 kg / min. (2) The mixture was poured onto a flat sheet of continuous glass fiber felt in a constant temperature and humidity environment of 25°C and 35% humidity, and then foamed and molded to obtain a semi-finished product. The temperature of the chain plate was 28°C. (3) The semi-finished product was allowed to cure naturally for 45 minutes, cut into multiple parts, and then allowed to cure again for 72 hours to obtain a reinforced rigid polyurethane foam material. Characteristic testing

[0049] The rigid polyurethane foam materials produced in Examples 1-6 and Comparative Examples 1-2 were tested for density, compressive strength, tensile strength, thermal conductivity, closed-cell ratio, surface flatness, and core material utilization rate. The test results are shown in Table 1.

[0050] The evaluation methods for each characteristic are as follows: Density: Remove the skin from the rigid polyurethane foam material, cut it into cubes, and test it according to GB / T 6343-2009. Compressive strength: Rigid polyurethane foam material is cut into 50mm x 50mm x 50mm samples and tested at -160°C according to GB / T 8813-2008. Tensile strength: Rigid polyurethane foam material is cut into dumbbell-shaped samples and tested at -160°C according to BS ISO 1926-2005. Thermal conductivity: Rigid polyurethane foam material is cut into 300mm x 300mm x 30mm samples and tested at -160°C according to ISO 8302. Closed-cell ratio: Rigid polyurethane foam material is cut into 30mm x 30mm x 50mm samples and tested at 20°C according to GB / T 10799-1989. Surface flatness: Calculated by measuring the difference between the lowest and highest points on the surface of a rigid polyurethane foam material. Core material utilization rate: Calculated as the ratio of the volume of rigid polyurethane foam material after removing the top, bottom, and side layers to the volume of the rigid polyurethane foam material blank.

[0051] Table 1 Test results of the properties of rigid polyurethane foam materials in Examples 1-6 and Comparative Examples 1-2. [Table 1]

[0052] As can be seen from Table 1, the rigid polyurethane foam materials produced in Examples 1 to 7 of the present invention exhibit significantly improved properties such as density, compressive strength, tensile strength, thermal conductivity, and glass fiber utilization compared to Comparative Examples 1 to 2.

[0053] Based on the above results, the rigid polyurethane foam material of the present invention has a density of 80-150 kg / m³. 3This enabled the continuous production of reinforced rigid polyurethane foam material, improving the tensile properties of the material by more than 20% and the utilization rate of glass fibers by more than 5%, making it widely applicable in the field of liquefied gas storage and transportation.

[0054] Although embodiments of the present invention have been shown and described above, these embodiments are illustrative and should not be understood as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present invention.

Claims

1. A reinforced rigid polyurethane foam material characterized by comprising 5 to 10 parts by weight of glass fiber yarn, 40 to 60 parts by weight of aromatic polyether polyol, 30 to 50 parts by weight of aromatic polyester polyol, 30 to 50 parts by weight of toluene diisocyanate, 40 to 60 parts by weight of polymethylene polyphenyl polyisocyanate, 5 to 10 parts by weight of flame retardant, 5 to 15 parts by weight of blowing agent, 1 to 5 parts by weight of catalyst, and 1 to 5 parts by weight of surfactant.

2. The reinforced rigid polyurethane foam material according to claim 1, characterized in that the glass fiber yarn has a single fiber diameter of 5 to 15 μm, a yarn density of 10 to 30 tex, a water content of less than 0.1%, and a flammable content of 0.5% to 1.5%.

3. The aforementioned aromatic polyether polyol has a molecular weight of 400 to 600, a hydroxyl value of 400 to 600 mgKOH / g, and a viscosity of 5000 to 9000 mPa·S. The reinforced rigid polyurethane foam material according to claim 1, characterized in that the aromatic polyester polyol has a molecular weight of 400 to 600, a hydroxyl value of 300 to 500 mgKOH / g, and a viscosity of 4000 to 6000 mPa·S.

4. The aforementioned flame retardant has a phosphorus content of 5 to 15%, a viscosity of 50 to 200 mPa·s, and a moisture content of less than 0.10%. The reinforced rigid polyurethane foam material according to claim 1, characterized in that the foaming agent has a boiling point of 5 to 25°C and a water content of less than 0.05%.

5. The catalyst is a mixture of a small molecule amine-based catalyst and an organotin-based catalyst. The reinforced rigid polyurethane foam material according to claim 1, characterized in that the surfactant is a polysiloxane-based polymer with a viscosity of 200 to 600 mPa·s and a water content of less than 0.05%.

6. A method for manufacturing a reinforced rigid polyurethane foam material, Step (1) involves randomly stacking glass fiber yarns on a conveyor belt using a throwing mechanism to form a random web of glass fiber yarns, and then weighing each raw material in the weight quantities specified in any one of claims 1 to 5. Step (2) involves mixing aromatic polyether polyol, aromatic polyester polyol, toluene diisocyanate, polymethylene polyphenyl polyisocyanate, flame retardant, blowing agent, catalyst, and surfactant to obtain a mixture. Step (3) involves pouring a mixture onto a random web structure formed by randomly layering flattened glass fiber threads, and then foaming it using a foaming machine to obtain a semi-finished product. A method for producing a reinforced rigid polyurethane foam material, characterized by comprising the step (4) of allowing a semi-finished product to naturally harden, cutting it into multiple parts, and hardening it again to obtain a reinforced rigid polyurethane foam material.

7. The method for producing a reinforced rigid polyurethane foam material according to claim 6, characterized in that in step (2), a high-pressure mixing head is used for mixing, with a pressure of 40 to 100 bar, a temperature of 5 to 25°C, and a discharge rate of 40 to 160 kg / min.

8. In step (3), the glass fiber continuous felt is separated from the chain plate using kraft paper, and the apparent density of the kraft paper is 80 to 150 g / m². ２ The method for producing a reinforced rigid polyurethane foam material according to claim 6, characterized in that it is the same.

9. The method for producing a reinforced rigid polyurethane foam material according to claim 6, characterized in that in step (4), the time for natural curing is 40 to 80 minutes, and the time for re-curing is 72 hours.

10. The method for producing a reinforced rigid polyurethane foam material according to claim 6, characterized in that steps (2) to (4) are carried out in a constant temperature and humidity environment with a temperature of 10 to 40°C and a humidity of 70% or less.

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