An enhanced rigid polyurethane foam material and its preparation method

Abstract

This invention discloses an enhanced rigid polyurethane foam material and its preparation method, belonging to the field of polymer materials technology. It comprises: 5-10 parts glass fiber yarn, 40-60 parts aromatic polyether polyol, 30-50 parts aromatic polyester polyol, 30-50 parts toluene diisocyanate, 40-60 parts polymethylene polyphenyl polyisocyanate, 5-10 parts flame retardant, 5-15 parts foaming agent, 1-5 parts catalyst, and 1-5 parts surfactant. This invention enables uninterrupted production of enhanced rigid polyurethane foam materials, improves the tensile strength of the material by more than 20%, and increases the glass fiber utilization rate by more than 5%, making it widely applicable in the field of liquefied gas storage and transportation.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically to an enhanced polyurethane rigid foam material and its preparation method. Background Technology

[0002] Rigid polyurethane foam, or rigid polyurethane foam for short, is the second most widely used polyurethane product after flexible polyurethane foam. Rigid polyurethane foam materials are mostly closed-cell structures, possessing excellent properties such as good thermal insulation, light weight, high specific strength, and easy construction. They also feature sound insulation, shock absorption, electrical insulation, heat resistance, cold resistance, and solvent resistance. They are widely used in the insulation layers of refrigerators and freezers, cold storage facilities, refrigerated trucks, and other insulation materials, as well as in building, storage tank, and pipeline insulation materials. A smaller amount is used in non-insulation applications, such as wood-like materials and packaging materials. Generally speaking, lower-density rigid polyurethane foam is mainly used as a thermal insulation material, while higher-density rigid polyurethane foam can be used as a structural material (wood-like).

[0003] Ordinary rigid polyurethane foam materials possess excellent thermal insulation properties, but they suffer severe shrinkage and cracking in cryogenic environments, causing them to lose their mechanical strength and insulation performance. To address this issue, they are typically composited with continuous glass fiber mat to enhance the mechanical properties and dimensional stability of rigid polyurethane foam at low temperatures, and flame retardants are added to improve the flame retardancy rating of the polyurethane. For example, patent 2007101441393 (publication number CN101235128A) discloses a polyurethane foam material with a density of 400-800 kg / m³ reinforced with continuous fibers, but this material is suitable for "load-bearing structural materials" and cannot be used for thermal insulation in ultra-low temperature environments. Patent 200610058849X (publication number CN1834130A) discloses an insulation material with a density of 115-135 kg / m³ and a compressive strength of 1.4-1.7 MPa, but this application does not provide detailed information on the thermal conductivity of the material, and its mechanical properties at low temperatures are unknown.

[0004] Traditionally, continuous fiberglass mats used to enhance the strength of polyurethane foam materials are usually produced in rolls, with each roll being 100-150 meters long. Mass production can only be carried out intermittently, and a considerable proportion of scrap material is generated at the beginning and end of each batch, resulting in low production efficiency and significant environmental pollution.

[0005] Therefore, how to provide an environmentally friendly reinforced rigid polyurethane foam material that can be continuously produced is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0006] In view of this, the present invention provides an enhanced rigid polyurethane foam material and a method for preparing the same.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] An enhanced rigid polyurethane foam material comprises the following raw materials in parts by weight: 5-10 parts glass fiber yarn, 40-60 parts aromatic polyether polyol, 30-50 parts aromatic polyester polyol, 30-50 parts toluene diisocyanate, 40-60 parts polymethylene polyphenyl polyisocyanate, 5-10 parts flame retardant, 5-15 parts foaming agent, 1-5 parts catalyst, and 1-5 parts surfactant.

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

[0010] Furthermore, the glass fiber yarn has a single fiber diameter of 5-15 micrometers, preferably 5-10 micrometers, more preferably 9 micrometers; a linear density of 10-30 tex, preferably 10-15 tex, more preferably 15 tex; a moisture content of less than 0.1%; and a combustible content of 0.5%-1.5%.

[0011] The beneficial effects of adopting the above-mentioned further technical solution are that the present invention uses glass fiber yarn instead of the glass fiber continuous mat commonly used in traditional processes. On the one hand, glass fiber yarn has a larger specific surface area, which can increase the effective bonding area between glass fiber and resin, and further enhance the tensile strength of the material. On the other hand, glass fiber mat is a roll material with a certain length limitation, which can only be produced intermittently, while glass fiber yarn can be spliced ​​indefinitely, thereby realizing continuous production. While improving production efficiency, it can also effectively reduce the cutting loss at the beginning and end of batches, which is more environmentally friendly.

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

[0013] Furthermore, the aromatic polyether polyol is at least one of toluene diamine 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 increasing 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 400-600, preferably 450-550, more preferably 520; a hydroxyl value of 300-500 mgKOH / g, preferably 400-480, more preferably 430; a viscosity of 4000-6000 mPa·s, preferably 4500-5500 mPa·s, more preferably 4800 mPa·s; and a moisture 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 solution are as follows: the aromatic polyester polyol of the present invention has better compatibility with the polymethylene polyphenyl polyisocyanate component, which can increase the foam fineness of the rigid polyurethane foam material, thereby improving its thermal insulation performance. At the same time, 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 increased.

[0018] Furthermore, the isocyanate content of the polymethylene polyphenyl polyisocyanate is 25-35 wt%, preferably 25-30 wt%, more preferably 29 wt%; the viscosity is 100-300 mPa·s, preferably 150-250 mPa·s, more preferably 200 mPa·s; and the functionality is 2.5-3.5, preferably 2.0-2.5, more preferably 2.4.

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

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

[0021] The beneficial effects of adopting the above-mentioned further technical solution are as follows: the flame retardant selected in this invention has low viscosity, and its addition can effectively reduce the overall viscosity of the material, increase the fluidity of the material, thereby improving the wetting speed of the material on the glass fiber yarn, and making the distribution of the glass fiber yarn in the rigid foam more uniform.

[0022] Furthermore, the foaming agent has a boiling point of 5-25°C, preferably a boiling point of 10-20°C; and a moisture content of less than 0.05%.

[0023] Furthermore, the foaming agent is any one of pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, or a mixture of both.

[0024] The beneficial effect of adopting the above-mentioned further technical solution is that the ozone depletion potential (ODP) of the two foaming agents selected in this invention is 0, which can ensure the environmental friendliness of the production process.

[0025] Furthermore, the catalyst is a mixture of small molecule amine catalysts and organotin catalysts;

[0026] Furthermore, the small molecule amine catalyst is any one or a mixture of two of triethylenediamine, tetramethylhexanediamine, and triethylamine; the organotin catalyst is any one or a mixture of two of stannous octoate and dibutyltin diacetate.

[0027] Furthermore, the surfactant is a polysiloxane polymer with a viscosity of 200-600 mPa·s and a moisture content of less than 0.05%.

[0028] Furthermore, the surfactant is any one or a mixture of two of the following: polysiloxane-ethylene oxide AB type linear block polymer and polysiloxane-propylene oxide ABA type linear block polymer.

[0029] The beneficial effects of adopting the above-mentioned further technical solutions are that the flame retardant, foaming agent, catalyst and surfactant of the present invention can effectively improve the flame retardancy, thermal insulation performance, mechanical strength and dimensional stability of polyurethane rigid foam materials.

[0030] The present invention also provides a method for preparing the above-mentioned reinforced polyurethane rigid foam material, comprising the following steps:

[0031] (1) The glass fiber yarn is randomly laid on the conveyor belt by the throwing mechanism to form a glass fiber yarn random network; then each raw material is weighed according to the above weight proportions.

[0032] (2) Aromatic polyether polyol, aromatic polyester polyol, toluene diisocyanate, polymethylene polyphenyl polyisocyanate, flame retardant, foaming agent, catalyst and surfactant are mixed to obtain a mixture;

[0033] (3) The mixture is poured onto a random network structure formed by laying flat glass fiber yarn, and then foamed with a foaming machine to obtain a semi-finished product;

[0034] (4) After the semi-finished product is naturally cured, it is cut into sections and cured again to obtain reinforced polyurethane rigid foam material.

[0035] Furthermore, in step (1), the width of the fiber-spinning mechanism is 0.8-2.4m, preferably 1.2-2.0m; the traveling speed is 1-2m / s, preferably 1.4-1.8m / s; the thickness of the random fiberglass network is 40-180mm, preferably 80-120mm; and the density of the random fiberglass network is 0.5-5kg / m³. 2 The preferred value is 2-3 kg / m 2 .

[0036] 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℃, preferably 23℃; and a discharge rate of 50-100 kg / min, preferably 70 kg / min.

[0037] The beneficial effects of adopting the above-mentioned further technical solution are as follows: the high-pressure mixing head in this invention has a large mixing pressure, which can improve the mixing effect of hydroxyl components and isocyanate components, making the pores of polyurethane rigid foam material finer and improving the thermal insulation performance.

[0038] Furthermore, in step (3), kraft paper is used to isolate the glass fiber continuous mat from the chain plate; the apparent density of the kraft paper is 80-150 g / m³. 2 .

[0039] 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℃, preferably 20-30℃; and the temperature of the chain plate is 15-35℃, preferably 20-30℃.

[0040] Furthermore, the natural curing time in step (4) is 40-80 min; the second curing time is 72 h;

[0041] Furthermore, steps (2)-(4) are carried out in a constant temperature and humidity environment, wherein the temperature is 10-40℃ and the humidity is below 70%.

[0042] 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 evenly distributed, the foaming process speed is uniform, and the density distribution of the polyurethane foam is also more uniform.

[0043] The beneficial effects of this invention are as follows: This invention uses glass fiber yarn instead of the traditional continuous glass fiber mat. Glass fiber yarn has a larger specific surface area, which can increase the effective bonding area between glass fiber and resin and enhance the tensile strength of the material by more than 20%. Glass fiber mat is a roll material with a length limitation, which can only be produced intermittently, while glass fiber yarn can be spliced ​​indefinitely, thereby realizing continuous production. While improving production efficiency, it can also effectively reduce the cutting loss at the beginning and end of batches, making it more environmentally friendly. Under the premise of ensuring the low-temperature mechanical strength and thermal insulation performance of the material, the utilization rate of glass fiber is increased by more than 5%, which can be widely used in the field of cryogenic insulation. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the process flow for the preparation method of the polyurethane rigid foam material of the present invention. Detailed Implementation

[0045] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0046] Example 1

[0047] Reinforced polyurethane foam materials:

[0048] (1) Weigh out 5 kg of glass fiber yarn, 40 kg of toluene diamine 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-trifluoropropylene, 1 kg of tetramethylhexanediamine, and 2 kg of polysiloxane-propylene oxide ABA-type linear block polymer; wherein, the diameter of the glass fiber yarn is 10 micrometers and the linear density is 10 te x, moisture content 0.05%, combustible content 0.5%; toluene diamine polyether molecular weight 500, hydroxyl value 450 mgKOH / g, viscosity 5000 mPa·S, moisture content 0.1%; trimellitic anhydride polyester molecular weight 580, hydroxyl value 300 mgKOH / g, viscosity 4000 mPa·S, moisture content 0.07%; polymethylene polyphenyl polyisocyanate isocyanate content 29 wt%, viscosity 250 mPa·S, functionality 2.3;

[0049] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 1.2m wide, travels at a speed of 1.4m / s, and the random network of glass fiber yarn is 40mm thick with a density of 2kg / m³. 2 .

[0050] (2) The components were added to a high-pressure mixing head and mixed in a constant temperature and humidity environment of 20℃ and 60% humidity. The pressure was 80 bar, the temperature was 20℃, and the discharge rate was 50 kg / min to obtain a mixture.

[0051] (3) The mixture is evenly spread on the glass fiber yarn random network structure through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material. The chain plate temperature is 20℃.

[0052] (4) After the semi-finished product is naturally cured for 40 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0053] Example 2

[0054] Reinforced polyurethane foam materials:

[0055] (1) Weigh out 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-trifluoropropylene, 1 kg of triethylenediamine, 0.5 kg of tetramethylhexanediamine, and 5 kg of polysiloxane-ethylene oxide AB type linear block polymer. Among them, the glass fiber yarn has a diameter of 6 micrometers, a linear density of 15 tex, a moisture content of 0.06%, and a combustible content of 1.0%; the bisphenol A polyether has a molecular weight of 600, a hydroxyl value of 400 mg KOH / g, a viscosity of 7000 mPa·S, and a moisture content of 0.08%; the phthalic anhydride polyester has a molecular weight of 450, a hydroxyl value of 500 mg KOH / g, a viscosity of 6000 mPa·S, and a moisture content of 0.06%; and the polymethylene polyphenyl polyisocyanate has an isocyanate content of 32 wt%, a viscosity of 200 mPa·S, and a functionality of 3.5.

[0056] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 2.4m wide, travels at a speed of 2m / s, and the random network of glass fiber yarn is 80mm thick with a density of 2.5kg / m³. 2 .

[0057] (2) In a constant temperature and humidity environment of 25℃ and 40% humidity, each component is added to a high-pressure mixing head for mixing. The pressure is 100 bar, the temperature is 30℃, and the output rate is 70 kg / min to obtain a mixture.

[0058] (3) The mixture is evenly spread on the random network structure of glass fiber yarn through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material; the chain plate temperature is 25℃.

[0059] (4) After the semi-finished product is naturally cured for 65 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0060] Example 3

[0061] Reinforced polyurethane foam materials:

[0062] (1) Weigh out 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 tri(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. Among them, the glass fiber yarn has a diameter of 5 micrometers, a linear density of 20 tex, a moisture content of 0.05%, and a combustible content of 1.2%; the phthalic anhydride-formaldehyde polyether has a molecular weight of 550, a hydroxyl value of 450 mg KOH / g, a viscosity of 5500 mPa·S, and a moisture content of 0.09%; the phthalic anhydride polyester has a molecular weight of 550, a hydroxyl value of 350 mg KOH / g, a viscosity of 4200 mPa·S, and a moisture content of 0.08%; and the polymethylene polyphenyl polyisocyanate has an isocyanate content of 33 wt%, a viscosity of 190 mPa·S, and a functionality of 2.4.

[0063] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 1.6m wide, travels at a speed of 1.8m / s, and the random network of glass fiber yarn is 180mm thick with a density of 5kg / m³. 2 .

[0064] (2) In a constant temperature and humidity environment of 25℃ and 50% humidity, each component is added to a high-pressure mixing head for mixing. The pressure is 70 bar, the temperature is 28℃, and the output rate is 120 kg / min to obtain a mixture.

[0065] (3) The mixture is evenly spread on the glass fiber yarn random network structure through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material. The chain plate temperature is 30℃.

[0066] (4) After the semi-finished product is naturally cured for 60 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0067] Example 4

[0068] Reinforced polyurethane foam materials:

[0069] (1) Weigh out 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-trifluoropropylene, 1 kg of triethylamine, and 2.5 kg of polysiloxane-ethylene oxide AB type linear block polymer. The glass fiber yarn has a diameter of 15 micrometers, a linear density of 30 tex, a moisture content of 0.03%, and a combustible content of 0.9%; the phthalic anhydride-formaldehyde polyether has 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 has 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 has an isocyanate content of 30 wt%, a viscosity of 220 mPa·S, and a functionality of 2.0.

[0070] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 1.4m wide, travels at a speed of 1.6m / s, and the random network of glass fiber yarn is 100mm thick with a density of 3kg / m³. 2 .

[0071] (2) In a constant temperature and humidity environment of 30℃ and 67% humidity, each component is added to a high-pressure mixing head for mixing. The pressure is 60 bar, the temperature is 25℃, and the output rate is 80 kg / min to obtain a mixture.

[0072] (3) The mixture is evenly spread on the glass fiber yarn random network structure through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material; the chain plate temperature is 26℃.

[0073] (4) After the semi-finished product is naturally cured for 50 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0074] Example 5

[0075] Reinforced polyurethane foam materials:

[0076] (1) Weigh out 10 kg of glass fiber yarn, 45 kg of toluene diamine 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-trifluoropropylene, 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. The glass fiber yarn has a diameter of 8 micrometers, a linear density of 15 tex, a moisture content of 0.05%, and a combustible content of 0.5%; the toluene diamine polyether has a molecular weight of 500, a hydroxyl value of 500 mgKOH / g, a viscosity of 5000 mPa·S, and a moisture content of 0.08%; the aromatic-aliphatic copolyester has a molecular weight of 500, a hydroxyl value of 500 mgKOH / g, a viscosity of 5000 mPa·S, and a moisture content of 0.09%; and the polymethylene polyphenyl polyisocyanate has an isocyanate content of 25 wt%, a viscosity of 160 mPa·S, and a functionality of 2.5.

[0077] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 1.2m wide, travels at a speed of 1.4m / s, and the random network of glass fiber yarn has a thickness of 80mm and a density of 2.6kg / m³. 2 .

[0078] (2) In a constant temperature and humidity environment of 25℃ and 35% humidity, each component is added to a high-pressure mixing head for mixing, with a pressure of 80 bar, a temperature of 28℃, and a discharge rate of 75 kg / min to obtain a mixture;

[0079] (3) The mixture is evenly spread on the glass fiber yarn random network structure through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material; the chain plate temperature is 28℃.

[0080] (4) After the semi-finished product is naturally cured for 45 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0081] Example 6

[0082] Reinforced polyurethane foam materials:

[0083] (1) Weigh out 7 kg of glass fiber yarn, 45 kg of toluene diamine 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. The glass fiber yarn has a diameter of 6 micrometers, a linear density of 20 tex, a moisture content of 0.06%, and a combustible content of 0.8%; the toluene diamine polyether has a molecular weight of 500, a hydroxyl value of 550 mg KOH / g, a viscosity of 6500 mPa·S, and a moisture content of 0.08%; the phthalic anhydride polyester has a molecular weight of 500, a hydroxyl value of 550 mg KOH / g, a viscosity of 6000 mPa·S, and a moisture content of 0.09%; and the polymethylene polyphenyl polyisocyanate has an isocyanate content of 27 wt%, a viscosity of 210 mPa·S, and a functionality of 2.6.

[0084] Multiple sets of glass fiber spindles form a glass fiber yarn matrix, which is randomly laid out by a spinning mechanism to form a random network structure of glass fiber yarn with a certain thickness and density. The yarn then enters the foaming area via a chain plate. The spinning mechanism is 0.8m wide and travels at a speed of 1m / s. The thickness of the random network of glass fiber yarn is 60mm, and the density is 0.5kg / m³. 2 .

[0085] (2) In a constant temperature and humidity environment of 25℃ and 35% humidity, each component is added to a high-pressure mixing head for mixing, with a pressure of 40 bar, a temperature of 28℃, and a discharge rate of 30 kg / min to obtain a mixture;

[0086] (3) The mixture is evenly spread on the glass fiber yarn random network structure through the conveying pipe. After wetting the entire network structure, it begins to react and foam into a reinforced polyurethane rigid foam semi-finished material; the chain plate temperature is 15℃.

[0087] (4) After the semi-finished product is naturally cured for 45 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0088] Comparative Example 1

[0089] Reinforced polyurethane foam materials:

[0090] (1) Weigh out 9 kg of glass fiber continuous mat, 60 kg of toluene diamine 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-trifluoropropylene, 1.5 kg of triethylamine, and 1.5 kg of polysiloxane-ethylene oxide AB-type linear block polymer. The density of the glass fiber continuous mat is 1 kg / m³. 2The molecular weight of toluene diamine polyether is 550, the hydroxyl value is 500 mgKOH / g, the viscosity is 7500 mPa·S, and the moisture content is 0.1%; the molecular weight of phthalic anhydride polyester is 500, the hydroxyl value is 550 mgKOH / g, the viscosity is 6000 mPa·S, and the moisture content is 0.09%; the isocyanate content of polymethylene polyphenyl polyisocyanate is 31 wt%, the viscosity is 230 mPa·S, and the functionality is 2.9.

[0091] The components were added to a high-pressure mixing head and mixed at a pressure of 70 bar, a temperature of 28°C, and a discharge rate of 120 kg / min to obtain a mixture.

[0092] (2) In a constant temperature and humidity environment of 25℃ and 50% humidity, the mixture is poured onto a flat glass fiber continuous felt, then foamed and shaped to obtain a semi-finished product; the chain plate temperature is 30℃.

[0093] (3) After the semi-finished product is naturally cured for 45 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0094] Comparative Example 2

[0095] Reinforced polyurethane foam materials:

[0096] (1) Weigh out 10 kg of glass fiber continuous mat, 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-trifluoropropylene, 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. The density of the glass fiber continuous mat is 0.5 kg / m³. 2 The molecular weight of aniline-formaldehyde polyether is 580, the hydroxyl value is 480 mg KOH / g, the viscosity is 5800 mPa·S, and the moisture content is 0.1%; the molecular weight of phthalic anhydride polyester is 480, the hydroxyl value is 480 mg KOH / g, the viscosity is 4800 mPa·S, and the moisture content is 0.1%; the isocyanate content of polymethylene polyphenyl polyisocyanate is 30 wt%, the viscosity is 220 mPa·S, and the functionality is 2.8.

[0097] The components were added to a high-pressure mixing head and mixed at a pressure of 80 bar, a temperature of 28°C, and a discharge rate of 75 kg / min to obtain a mixture.

[0098] (2) In a constant temperature and humidity environment of 25℃ and 35% humidity, the mixture is poured onto a flat glass fiber continuous felt, then foamed and shaped to obtain a semi-finished product; the chain plate temperature is 28℃.

[0099] (3) After the semi-finished product is naturally cured for 45 minutes, it is cut into sections and cured again for 72 hours to obtain the reinforced polyurethane rigid foam material.

[0100] Performance testing

[0101] The polyurethane rigid foam materials prepared in Examples 1-6 and Comparative Examples 1-2 were tested for density, compressive strength, tensile strength, thermal conductivity, closed-cell ratio, surface smoothness and core material utilization rate. The test results are shown in Table 1.

[0102] The performance evaluation methods are as follows:

[0103] Density: The polyurethane rigid foam material is removed from its outer skin and cut into cubes, and tested according to GB / T 6343-2009.

[0104] Compressive strength: The rigid polyurethane foam material was cut into 50mm×50mm×50mm samples and tested at -160℃ according to GB / T 8813-2008.

[0105] Tensile strength: The rigid polyurethane foam material was cut into dumbbell-shaped samples and tested at -160°C in accordance with BS ISO 1926-2005.

[0106] Thermal conductivity: The rigid polyurethane foam material was cut into 300mm×300mm×30mm samples and tested at -160℃ according to ISO 8302.

[0107] Closed-cell rate: The rigid polyurethane foam material was cut into samples of 30mm×30mm×50mm and tested at 20℃ according to GB / T 10799-1989.

[0108] Surface flatness: Calculated by measuring the difference between the lowest and highest points on the surface of the rigid polyurethane foam material.

[0109] Core material utilization rate: Calculated by the ratio of the volume of the polyurethane rigid foam material after removing the top, bottom and side skins to the volume of the polyurethane rigid foam material blank.

[0110] Table 1. Performance test results of polyurethane rigid foam materials in Examples 1-6 and Comparative Examples 1-2.

[0111]

[0112]

[0113] As shown in Table 1, compared with Comparative Examples 1-2, the polyurethane rigid foam materials prepared in Examples 1-7 of the present invention have significantly improved properties such as density, compressive strength, tensile strength, thermal conductivity, and glass fiber utilization.

[0114] The above results show that the density of the polyurethane rigid foam material of the present invention is 80-150 kg / m3, which can realize the uninterrupted production of reinforced polyurethane rigid foam material, improve the tensile strength of the material by more than 20%, and improve the glass fiber utilization rate by more than 5%, and can be widely used in the field of liquefied gas storage and transportation.

[0115] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed 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 in that, The raw materials include the following parts by weight: 5-10 parts glass fiber yarn, 40-60 parts aromatic polyether polyol, 30-50 parts aromatic polyester polyol, 30-50 parts toluene diisocyanate, 40-60 parts polymethylene polyphenyl polyisocyanate, 5-10 parts flame retardant, 5-15 parts foaming agent, 1-5 parts catalyst, and 1-5 parts surfactant. The aromatic polyether polyol has a molecular weight of 400-600, a hydroxyl value of 400-600 mgKOH / g, and a viscosity of 5000-9000 mPa·S; the aromatic polyester polyol has a molecular weight of 400-600, a hydroxyl value of 300-500 mgKOH / g, and a viscosity of 4000-6000 mPa·S; the aromatic polyether polyol is at least one of toluene diamine polyether, bisphenol A polyether, and aniline-formaldehyde polyether; the aromatic polyester polyol is at least one of phthalic anhydride polyester polyol and trimellitic anhydride polyester polyol. The catalyst is a mixture of small molecule amine catalysts and organotin catalysts; the small molecule amine catalyst is any one or a mixture of two of triethylenediamine, tetramethylhexanediamine, and triethylamine; the organotin catalyst is any one or a mixture of two of stannous octoate and dibutyltin diacetate. The flame retardant is any one or a mixture of two of tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, and tris(dichloropropyl) phosphate; the foaming agent is any one or a mixture of two of pentafluoropropane and trans-1-chloro-3,3,3-trifluoropropene. The surfactant is a polysiloxane polymer with a viscosity of 200-600 mPa·S and a moisture content of less than 0.05%; the surfactant is any one or a mixture of two of the following: polysiloxane-ethylene oxide AB type linear block polymer and polysiloxane-propylene oxide ABA type linear block polymer.

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

3. A method for preparing an enhanced rigid polyurethane foam material, characterized in that, Includes the following steps: (1) The glass fiber yarn is randomly laid on the conveyor belt by the throwing mechanism to form a glass fiber yarn random network; then each raw material is weighed according to the weight proportions described in claim 1 or 2; (2) Mix aromatic polyether polyol, aromatic polyester polyol, toluene diisocyanate, polymethylene polyphenyl polyisocyanate, flame retardant, foaming agent, catalyst and surfactant to obtain a mixture; (3) The mixture is poured onto a random network structure formed by randomly laid glass fiber yarn, and then foamed using a foaming machine to obtain a semi-finished product; kraft paper is used to isolate the continuous glass fiber yarn from the chain plate; the apparent density of the kraft paper is 80-150 g / m³. 2 ; (4) After the semi-finished product is naturally cured, it is cut into sections and cured again to obtain reinforced polyurethane rigid foam material; Steps (2)-(4) are carried out in a constant temperature and humidity environment, wherein the temperature is 10-40℃ and the humidity is below 70%.

4. The method for preparing an enhanced polyurethane rigid foam material according to claim 3, characterized in that, In step (2), a high-pressure mixing head is used for mixing, with a pressure of 40-100 bar, a temperature of 5-25℃, and a discharge rate of 40-160 kg / min.

5. The method for preparing an enhanced rigid polyurethane foam material according to claim 3, characterized in that, The natural curing time in step (4) is 40-80 min; the second curing time is 72 h.

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