Weather-resistant winding two-component polyurethane resin and preparation method thereof
By adopting a two-component polyurethane resin system for weather-resistant winding, the problem that traditional polyurethane resin systems cannot prepare large-sized composite materials is solved, and the preparation of composite materials with high weather resistance and wear resistance is achieved.
Patent Information
- Application Number
- CN202411809848.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-09
- Publication Date
- 2025-03-21
AI Technical Summary
The operation time and the casting body thermal deformation temperature of the traditional polyurethane resin system are low, resulting in the inability to prepare large-size composite products with a thickness of more than 10 meters and a thickness of more than 5 cm.
A two-component polyurethane resin system for weather-resistant winding is adopted, which includes white material components and black material components. Through specific raw material ratios and catalyst use, the operating time of the composite material and the thermal deformation temperature is increased.
While ensuring the basic mechanical properties of composite materials, excellent weather resistance and high surface hardness are achieved, large-size composite materials can be prepared, and excellent wear resistance is achieved.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of polyurethane resins, in particular to a two-component polyurethane resin for weather-resistant winding and a preparation method thereof. Background Art
[0002] Polyurethane resin is mainly used in aviation, railways, construction, sports and other fields; used for surface finishing of wooden furniture and metal; used for thermal insulation and cold preservation of storage tanks, pipelines, cold storage, beer, fermentation tanks, fresh-keeping barrels, thermal insulation and waterproofing of building construction, and can also be used for prefabricated polyurethane sheets; can be used to manufacture plastic products, wear-resistant synthetic rubber products, synthetic fibers, hard and soft foam plastic products, adhesives and coatings, etc.; used for surface finishing of various types of wooden products, chemical equipment, telecommunications equipment and instruments and various means of transportation.
[0003] The operable time of traditional polyurethane resin systems (the time it takes for the viscosity of 175g at 30°C to increase to 500mPa.s) cannot exceed 50 minutes, and the thermal deformation temperature of the casting body is generally lower than 60°C, making it impossible to prepare large-sized composite products with a length of more than 10 meters and a thickness of more than 5 cm. Summary of the invention
[0004] The purpose of the present invention is to provide a two-component polyurethane resin for weather-resistant winding and a preparation method thereof to solve the problems raised in the above background technology. A two-component polyurethane resin for weather-resistant winding, composed of a two-component polyurethane resin system, wherein the two-component polyurethane resin system includes a white material component and a black material component;
[0005] The white material components include: hydroxypropyl methacrylate HPMA, acrylate monomers (HPNDA, TPGDA, TCDDA, TMPTA, TMP(EO)3TA), castor oil, NJ6305, NJ8238 and catalyst;
[0006] The black material components include: HT-600, IPDI, and initiator TBPB.
[0007] Preferably, the weight ratio of each raw material in the white material component is: 1% to 30% hydroxypropyl methacrylate HPMA, 15% to 40% acrylate monomer, 20% to 40% castor oil, 10% to 40% NJ6305, 5% to 30% NJ8238 and 0.01% to 0.05% catalyst.
[0008] Preferably, the weight ratio of each raw material in the black material component is: 30% to 80% HT-600, 10% to 60% IPDI, and 1% to 5% initiator TBPB.
[0009] Preferably, the acrylate monomer in the white material is one or more of HPNDA, TPGDA, TCDDA, TMPTA, and TMP(EO)3TA; HPNDA is hydroxypivalic acid polyglycol diacrylate, with a molecular weight of 312, a viscosity of 15-30 cps measured at 25°C, and a Cas number of 30145-51-8; TPGDA is tripropylene glycol diacrylate, with a molecular weight of 300, a viscosity of 15-20 cps measured at 25°C, and a Cas number of 42978-66-5;
[0010] TCDDA is tricyclodecane dimethanol diacrylate, with a molecular weight of 304, a viscosity of 120-150 cps at 25°C, and a Cas number of 42594-17-2; TMPTA is trimethylolpropane triacrylate, with a molecular weight of 296, a viscosity of 80-120 cps at 25°C, and a Cas number of 15625-89-5; TMP(EO)3TA is 3(ethoxy)trimethylolpropane Alkane triacrylate, molecular weight is 428, viscosity measured at 25°C is 50-70cps, Cas number is 28961-43-5; NJ6305 has a functionality of 4-5, viscosity measured at 25°C is 5800mPa·s, and hydroxyl value is 500mgKOH / g; NJ8238 has a functionality of 5-6, viscosity measured at 25°C is 11250mPa·s, and hydroxyl value is 380mgKOH / g.
[0011] Preferably, the catalyst is an organotin catalyst, and the preparation method of the organotin catalyst comprises adding an organotin organic solution to a silica sol, and obtaining a supported organotin catalyst after gelling, drying and calcining.
[0012] A method for preparing a two-component polyurethane resin for weather-resistant winding comprises the following steps:
[0013] Step 1: Mix and stir the white material components of hydroxypropyl methacrylate HPMA, acrylate monomers (HPNDA, TPGDA, TCDDA, TMPTA, TMP(EO)3TA), NJ6305, NJ8238 and catalyst evenly and pack them;
[0014] Step 2: Mix the black material components HT-600, IPDI and TBPB evenly and package them separately.
[0015] Compared with the prior art, the present invention has the following beneficial effects:
[0016] The present invention provides a weather-resistant two-component polyurethane resin for winding, which mainly has excellent weather resistance and high surface hardness to meet the wear resistance requirement while ensuring the basic mechanical properties of the composite material.
[0017] Compared with the prior art, the present invention has the following beneficial effects:
[0018] (1) The system does not contain solvents or VOCs, making it more environmentally friendly.
[0019] (2) The addition of aliphatic isocyanate gives the system excellent weather resistance.
[0020] (3) The composite material of this system after curing has a high hardness and has excellent wear resistance when used as a surface weather-resistant material.
[0021] (4) Unlike other polyurethane resin systems, this system is not sensitive to moisture and can operate without a low humidity environment.
[0022] (5) It has excellent mechanical properties.
[0023] Other advantages and features of the present invention will be partially reflected in the following description, and partly will be understood by those skilled in the art through research and practice of the present invention. The above description is only an overview of the technical solution of the embodiment of the present application. In order to more clearly understand the technical means of the embodiment of the present application, it can be implemented according to the contents of the specification, and in order to make the above and other purposes, features and advantages of the embodiment of the present application more obvious and easy to understand, the specific implementation methods of the present application are specifically cited below. DETAILED DESCRIPTION
[0024] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.
[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used in the specification of the application are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and any variations thereof are intended to cover non-exclusive inclusions.
[0026] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase "embodiments" in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.
[0027] The two-component polyurethane prepreg molding resin stored at room temperature of the present invention comprises the following raw materials in the white material component: 1% to 30% hydroxypropyl methacrylate HPMA, 15% to 40% acrylate monomer, 20% to 40% castor oil, 10% to 40% NJ6305, 5% to 30% NJ8238 and 0.01% to 0.05% catalyst by weight;
[0028] The weight ratio of each raw material in the black material component is: 30% to 80% HT-600, 10% to 60% IPDI, and 1% to 5% initiator TBPB.
[0029] In a specific embodiment of the present invention, the white material component and the black material component are mixed at a mass ratio of 1:0.45-0.6 during use, and then cured to obtain a polyurethane resin.
[0030] The catalyst is an organotin catalyst, and the preparation method of the organotin catalyst includes adding an organotin organic solution to a silica sol, and preparing a supported organotin catalyst after gelling, drying and calcining. The weight content of silicon oxide in the silica sol is 10% to 40%.
[0031] Example 1
[0032] A weather-resistant two-component polyurethane resin for winding of this embodiment includes the following steps:
[0033] Step 1, weigh the white material component and the black material component by weight, wherein the white material component includes: 50 parts of hydroxypropyl methacrylate HPMA, 200 parts of NJ6305 (polyether polyol NJ6305), 50 parts of NJ8238 (polyether polyol NJ8238), 350 parts of TMP (EO) 3TA, 350 parts of castor oil, and 0.5 parts of organic bismuth catalyst, mixed and stirred evenly, and packaged; 490 parts of PM400, 490 parts of MDI50, and 20 parts of TBPB of the black material component are mixed and stirred evenly, and packaged; the reinforced glass fiber is the alkali-free glass fiber direct untwisted roving 308 for winding of Jushi Group; the above-mentioned white material component and black material component are stirred and mixed evenly according to 100:50, and the mixed viscosity and room temperature gel time are measured. The results are shown in Table 1. The viscosity was measured using a Brookfield DV-II+pro digital viscometer, the measurement standard was GB / T 22235, and the measurement temperature was 25° C. At the same time, a polyurethane resin casting was prepared, and the tensile properties of plastics were measured according to GB / T 1040.2, see Table 2.
[0034] Step 2: After the white material component and the black material component are fully mixed and stirred in a ratio of 100:50, they are made into composite material samples by winding molding, and the tensile properties and are tested according to the tensile properties test method of GB / T 1447-2005 fiber reinforced plastics. The bending properties and are tested according to the bending properties test method of GB / T 1449-2005 fiber reinforced plastics. The Barcol hardness is determined according to the Barcol hardness test method of GB / T 3854-2017 reinforced plastics. The results are shown in Table 3. The bending specimen is placed in a UV aging box, and the fluorescent ultraviolet lamp device for non-metallic material exposure is used according to the ASTM G154 standard practice. The light source is UVA-340, the irradiation intensity is 0.89W / ㎡*nm, and the contact cycle is 8 hours of ultraviolet light at a black panel temperature of 60±3℃, and 4 hours of ultraviolet condensation at a black panel temperature of 50±3℃. Weather resistance test is carried out, and the UV box weather resistance test data results are shown in Table 4.
[0035] Example 2
[0036] A weather-resistant two-component polyurethane resin for winding of this embodiment includes the following steps:
[0037] Step 1, weigh the white material component and the black material component by weight, wherein the white material component includes: 50 parts of hydroxypropyl methacrylate HPMA, 100 parts of NJ6305 (polyether polyol NJ6305), 150 parts of NJ8238 (polyether polyol NJ8238), 400 parts of TMP (EO) 3TA, 300 parts of castor oil, and 0.5 parts of organic bismuth catalyst, mix and stir evenly, and pack; 490 parts of PM400, 490 parts of MDI50, and 20 parts of TBPB of the black material component are mixed and stirred evenly, and then packaged; the reinforced glass fiber is the alkali-free glass fiber direct untwisted roving 308 for winding of Jushi Group; the above-mentioned white material component and black material component are stirred and mixed evenly according to 100:50, and the mixed viscosity and room temperature gel time are measured. The results are shown in Table 1. The viscosity was measured using a Brookfield DV-II+pro digital viscometer, the measurement standard was GB / T 22235, and the measurement temperature was 25° C. At the same time, a polyurethane resin casting was prepared, and the tensile properties of plastics were measured according to GB / T 1040.2, see Table 2.
[0038] Step 2: After the white material component and the black material component are fully mixed and stirred at a ratio of 100:47, they are made into composite material samples by winding molding, and the tensile properties and are tested according to the GB / T 1447-2005 fiber reinforced plastic tensile property test method. The bending properties and are tested according to the GB / T 1449-2005 fiber reinforced plastic bending property test method. The Barcol hardness is measured according to the GB / T 3854-2017 reinforced plastic Barcol hardness test method. The results are shown in Table 3.
[0039] Example 3
[0040] A weather-resistant two-component polyurethane resin for winding of this embodiment includes the following steps:
[0041] Step 1, weigh the white material component and the black material component by weight, wherein the white material component includes: 100 parts of hydroxypropyl methacrylate HPMA, 200 parts of NJ6305 (polyether polyol NJ6305), 150 parts of NJ8238 (polyether polyol NJ8238), 250 parts of TMP (EO) 3TA, 300 parts of castor oil, and 0.5 parts of organic bismuth catalyst, mix and stir evenly, and pack; 490 parts of PM400, 490 parts of MDI50, and 20 parts of TBPB of the black material component are mixed and stirred evenly, and then packed; the reinforcing glass fiber is the alkali-free glass fiber direct untwisted roving 308 for winding of Jushi Group; the above-mentioned white material component and black material component are stirred and mixed evenly according to 100:50, and the mixed viscosity and room temperature gel time are measured. The results are shown in Table 1. The viscosity was measured using a Brookfield DV-II+pro digital viscometer, the measurement standard was GB / T 22235, and the measurement temperature was 25° C. At the same time, a polyurethane resin casting was prepared, and the tensile properties of plastics were measured according to GB / T 1040.2, see Table 2.
[0042] Step 2: After the white material component and the black material component are fully mixed and stirred at a ratio of 100:50, they are made into composite material samples by winding molding, and the tensile properties and are tested according to the GB / T 1447-2005 fiber reinforced plastic tensile property test method. The bending properties and are tested according to the GB / T 1449-2005 fiber reinforced plastic bending property test method. The Barcol hardness is measured according to the GB / T 3854-2017 reinforced plastic Barcol hardness test method. The results are shown in Table 3.
[0043] Example 4
[0044] A weather-resistant two-component polyurethane resin for winding of this embodiment includes the following steps:
[0045] Step 1, weigh the white material component and the black material component by weight, wherein the white material component includes: 50 parts of hydroxypropyl methacrylate HPMA, 150 parts of NJ6305 (polyether polyol NJ6305), 200 parts of NJ8238 (polyether polyol NJ8238), 300 parts of TMP (EO) 3TA, 300 parts of castor oil, and 0.5 parts of organic bismuth catalyst, mix and stir evenly, and divide into packages; 490 parts of PM400, 490 parts of MDI50, and 20 parts of TBPB of the black material component are mixed and stirred evenly, and divided into packages; the reinforcing glass fiber is the alkali-free glass fiber direct untwisted roving 308 for winding of Jushi Group; the above-mentioned white material component and black material component are stirred and mixed evenly according to 100:50, and the mixed viscosity and room temperature gel time are measured. The results are shown in Table 1. The viscosity was measured using a Brookfield DV-II+pro digital viscometer, the measurement standard was GB / T 22235, and the measurement temperature was 25° C. At the same time, a polyurethane resin casting was prepared, and the tensile properties of plastics were measured according to GB / T 1040.2, see Table 2.
[0046] Step 2: After the white material component and the black material component are fully mixed and stirred at a ratio of 100:50, they are made into composite material samples by winding molding, and the tensile properties and are tested according to the GB / T 1447-2005 fiber reinforced plastic tensile property test method. The bending properties and are tested according to the GB / T 1449-2005 fiber reinforced plastic bending property test method. The Barcol hardness is measured according to the GB / T 3854-2017 reinforced plastic Barcol hardness test method. The results are shown in Table 3.
[0047] Mixed viscosity and gel time at room temperature (25°C)
[0048]
[0049]
[0050] Note: After mixing, take 150g of the mixture to test its viscosity change. The viscosity unit is cps
[0051] Table 1 Tensile properties test of pure resin casting
[0052]
[0053] Table 2 Tensile properties and bending properties of winding molding (along the fiber direction T0°)
[0054]
[0055] Table 3 (Implementation Case 1) UV Box Weathering Test Data
[0056]
[0057] Table 4
[0058] As described above, the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims
1. A two-component polyurethane resin for weather-resistant winding, characterized in that: It is composed of a two-component polyurethane resin system, wherein the two-component polyurethane resin system includes a white material component and a black material component; The white material components include: hydroxypropyl methacrylate HPMA, acrylate monomers (HPNDA, TPGDA, TCDDA, TMPTA, TMP(EO)3TA), castor oil, NJ6305, NJ8238 and a catalyst; The black material components include: HT-600, IPDI, and initiator TBPB.
2. A weather-resistant two-component polyurethane resin for winding according to claim 1, characterized in that: The weight ratio of each raw material in the white material component is: 1% to 30% of hydroxypropyl methacrylate HPMA, 15% to 40% of acrylate monomer, 20% to 40% of castor oil, 10% to 40% of NJ6305, 5% to 30% of NJ8238 and 0.01% to 0.05% of catalyst.
3. A weather-resistant two-component polyurethane resin for winding according to claim 1, characterized in that: The weight ratio of each raw material in the black material component is: 30% to 80% HT-600, 10% to 60% IPDI, and 1% to 5% initiator TBPB.
4. The weather-resistant two-component polyurethane resin for winding according to claim 1, characterized in that: The acrylate monomer in the white material is one or more of HPNDA, TPGDA, TCDDA, TMPTA, and TMP(EO)3TA; The HPNDA is hydroxypivalic acid polyglycol diacrylate, with a molecular weight of 312, a viscosity of 15-30 cps measured at 25°C, and a Cas number of 30145-51-8; The TPGDA is tripropylene glycol diacrylate, with a molecular weight of 300, a viscosity of 15-20 cps at 25°C, and a Cas number of 42978-66-5; The TCDDA is tricyclodecane dimethanol diacrylate, with a molecular weight of 304, a viscosity of 120-150 cps at 25°C, and a CAS number of 42594-17-2; The TMPTA is trimethylolpropane triacrylate, with a molecular weight of 296, a viscosity of 80-120 cps at 25°C, and a CAS number of 15625-89-5; The TMP(EO)3TA is 3(ethoxy)trimethylolpropane triacrylate, with a molecular weight of 428, a viscosity of 50-70 cps at 25°C, and a CAS number of 28961-43-5; The functionality of NJ6305 is 4-5, the viscosity is 5800 mPa·s at 25°C, and the hydroxyl value is 500 mgKOH / g; The functionality of NJ8238 is 5-6, the viscosity measured at 25° C. is 11250 mPa·s, and the hydroxyl value is 380 mgKOH / g.
5. A weather-resistant two-component polyurethane resin for winding according to claim 1, characterized in that: The catalyst is an organic tin catalyst. The preparation method of the organic tin catalyst comprises adding an organic tin organic solution into a silica sol, and preparing a supported organic tin catalyst after gelling, drying and calcining.
6. A method for preparing a weather-resistant two-component polyurethane resin for winding according to any one of claims 1 to 5, characterized in that: The following steps are involved: Step 1: Mix and stir the white material components of hydroxypropyl methacrylate HPMA, acrylate monomers (HPNDA, TPGDA, TCDDA, TMPTA, TMP(EO)3TA), NJ6305, NJ8238 and catalyst evenly and pack them; Step 2: Mix the black material components HT-600, IPDI, and TBPB evenly and package them.