A high-strength polyethylene modified TPU high and low temperature film and its preparation method

Abstract

The present invention relates to the field of TPU technology, and in particular to a high-strength polyethylene modified TPU high and low temperature film and a preparation method thereof. The high-strength polyethylene modified TPU high and low temperature film comprises a first TPU film layer, a yarn layer, and a second TPU film layer arranged in sequence from top to bottom, and a PU composite film layer is provided between the first TPU film layer and the yarn layer, and between the second TPU film layer and the yarn layer. The high-strength polyethylene modified TPU high and low temperature film of the present invention has the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile performance, and can be used as a shoe upper skeleton, shoe upper, and other. The preparation method of the high-strength polyethylene modified TPU high and low temperature film has a simple process and is easy to control in operation, which is conducive to large-scale industrial production. The obtained high-strength polyethylene modified TPU high and low temperature film has stable quality and excellent comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of TPU, and in particular to a high-strength polyethylene modified TPU high and low temperature film and a preparation method thereof. Background Art

[0002] At present, many shoes use mesh uppers in pursuit of lightness, but mesh uppers have many problems. They have a simple structure, are easily broken, have poor impact resistance, and poor aging resistance. After long-term use, the uppers are prone to delamination, which causes the uppers to be damaged due to excessive impact absorption during running or competition. Many athletes' toes protrude from the uppers, causing toe injuries. The protection for athletes' feet is poor. At the same time, the uppers are relatively light and thin, lack water resistance, and are easily damaged after washing. Therefore, the performance of sports shoe uppers made of TPU high and low temperature films needs to be further improved. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a high-strength polyethylene modified TPU high and low temperature film, which has the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile properties. It can be used as a shoe upper skeleton, shoe upper, and other parts, and has a protective effect on athletes' feet and is easy to use.

[0004] The preparation method of the high-strength polyethylene modified TPU high-low temperature film of the present invention has a simple process, easy operation and control, and is conducive to large-scale industrial production. The prepared high-strength polyethylene modified TPU high-low temperature film has stable quality, strong aging resistance, strong water resistance, strong impact resistance and strong tensile performance, and has excellent comprehensive performance.

[0005] The purpose of the present invention is achieved through the following technical scheme: a high-strength polyethylene modified TPU high and low temperature film, comprising a first TPU film layer, a yarn layer and a second TPU film layer arranged in sequence from top to bottom, and a PU composite film layer is provided between the first TPU film layer and the yarn layer and between the second TPU film layer and the yarn layer.

[0006] The high-strength polyethylene modified TPU high and low temperature film of the present invention includes a first TPU film layer, a yarn layer and a second TPU film layer arranged in sequence from top to bottom, the yarn layer having the characteristics of low density, high strength, good toughness, tear resistance, and not easy to deform, the PU composite film layer is used to firmly bond the lower surface of the first TPU film layer to the upper surface of the yarn layer, and the upper surface of the second TPU film layer to the lower surface of the yarn layer, the first TPU film layer and the second TPU film layer are both made of TPU high and low temperature film, and the two sides of the TPU high and low temperature film have different melting points, mainly including a high-temperature layer with a higher melting point and a low-temperature layer with a lower melting point, the low-temperature layer is mainly used for bonding with other materials, the high-temperature layer can be used as a carrier or surface layer, applied to the surface of the product, improving the performance of the product, such as corrosion resistance, impact resistance, wear resistance, etc., and can protect the product, and the upper and lower surfaces of the yarn layer are both connected to the low-temperature layer of the TPU high and low temperature film. The high-strength polyethylene modified TPU high and low temperature film of the present invention has the advantages of aging resistance, strong water resistance, strong tensile performance, etc., its structure is simple and easy to use.

[0007] In the above technical solution, the yarn layer is woven from modified aramid fiber or polyethylene fiber. Preferably, the yarn layer is woven from modified aramid fiber

[0008] In the above technical solution, the preparation method of the modified aramid fiber comprises the following steps:

[0009] (1) Aramid fiber cleaning: Soak the aramid fiber in anhydrous ethanol and clean it with ultrasound for 1.5-2.5 hours, then wash it with deionized water for 4-5 times, and then dry it at 80-90℃;

[0010] (2) Modification treatment with CaCl2 ethanol solution: The cleaned aramid fiber is placed in a CaCl2 ethanol solution with a CaCl2 mass fraction of 10-15%, and the temperature is raised to 85-95°C. After reacting for 4-5 hours, the fiber is taken out and rinsed with deionized water 4-5 times, and then dried at 80-90°C to obtain pretreated aramid fiber;

[0011] (3) Preparation of dopamine aqueous solution: Add tris(hydroxymethyl)aminomethane to a 4-6 g / L dopamine aqueous solution to adjust the pH value of the solution to 8.3-8.7 to obtain a dopamine pretreatment solution;

[0012] (4) Dopamine modification: The pretreated aramid fiber was immersed in a dopamine pretreatment solution for 25-30 hours, then washed with deionized water for 4-5 times, and then dried at 80-90°C to obtain modified aramid fiber.

[0013] In the above technical solution, the aramid fiber is aramid 1414 with a specification of 23S / 2, the yarn layer is woven from aramid fiber, and the density of the yarn layer is 60g / m2 , thickness is 0.5mm.

[0014] The present invention prepares modified aramid fiber by adopting the above-mentioned preparation method, and the raw materials are well matched, so that the interaction between dopamine water, aramid fiber and other raw materials makes the high-strength polyethylene modified TPU high and low temperature film have the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile performance.

[0015] In the above technical solution, the PU composite film includes a PU composite adhesive; the PU composite adhesive includes the following raw materials in parts by weight: 45-55 parts of polyurethane emulsion, 22-28 parts of polyethylene, 16-19 parts of hydantoin epoxy resin, 8-10 parts of modified coupling agent and 3-4 parts of accelerator.

[0016] In the above technical solution, the polyethylene is polyethylene with model number 2426H produced by Shenhua Chemical; the hydantoin epoxy resin is hydantoin epoxy resin with CAS number 15336-81-9 produced by Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0017] In the above technical solution, the accelerator is at least one of dibutyltin diacetate, bis(acetoxy)dibutylstannane, dibutyltin diacetate or dibutylstannane diacetate. Preferably, the accelerator is dibutyltin diacetate.

[0018] In the above technical solution, the preparation method of the modified coupling agent comprises the following steps:

[0019] (1) adding vinyl tris(2-methoxyethoxy)silane and maleic anhydride into a reaction tube, then adding anhydrous dichloromethane and stirring to dissolve, and finally adding a metal compound catalyst to obtain a pre-reaction solution;

[0020] (2) The pre-reaction solution is heated to 40-50° C. and reacted for 15-18 hours. After the reaction is completed, the modified coupling agent is separated by column chromatography.

[0021] In the above technical solution, the molar ratio of vinyltris(2-methoxyethoxy)silane to maleic anhydride is 1.8-2.2:1, and the molar content of the metal compound catalyst is 5-10 mol%. Preferably, the molar ratio of vinyltris(2-methoxyethoxy)silane to maleic anhydride is 2:1, and the molar content of the metal compound catalyst is 8 mol%.

[0022] In the above technical solution, the metal compound catalyst is Grubbs 2 nd Catalysts and Hoveyda-Grubbs 2 ndThe catalyst is compounded in a molar ratio of 1.2-1.5:1. Preferably, the metal compound catalyst is Grubbs 2 nd Catalysts and Hoveyda-Grubbs 2 nd The catalyst is compounded in a molar ratio of 1.3:1.

[0023] The present invention prepares the modified coupling agent by adopting the above-mentioned preparation method, achieves good coordination of the raw materials, and the interaction between vinyl tris (2-methoxyethoxy) silane, maleic anhydride and other raw materials makes the high-strength polyethylene modified TPU high and low temperature film have the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile performance.

[0024] In the above technical solution, the preparation method of the polyurethane emulsion comprises the following steps:

[0025] (1) placing polyether diol and phthalic anhydride polyester polyol in a reaction vessel, stirring and heating to 115-130° C., controlling the pressure in the reaction vessel to -0.02 to -0.06 MPa, and dehydrating; then filling with nitrogen, cooling to 60-70° C., adding toluene diisocyanate and a catalyst, and catalytically reacting for 1-3 hours, cooling to 64-70° C., adding dimethylolpropionic acid, and continuing the reaction for 1-2 hours, and completing the reaction to obtain mixture A;

[0026] (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

[0027] In the above technical solution, the molar ratio of the polyether diol, phthalic anhydride polyester polyol and toluene diisocyanate is 0.25-0.5:(0.25-0.5):1. Preferably, the molar ratio of the polyether diol, phthalic anhydride polyester polyol and toluene diisocyanate is 0.5:0.3:1.

[0028] In the above technical solution, the molar content of the deionized water is 8-12 mol%.

[0029] In the above technical solution, the catalyst is at least one of dibutyltin dilaurate or stannous octoate.

[0030] In the above technical solution, the polyether diol is Arkema 330HP, France; the phthalic anhydride polyester polyol is phthalic anhydride polyester polyol 20-32-56, Shandong New Kinetic Energy Chemical Co., Ltd.

[0031] The present invention prepares the polyurethane emulsion by adopting the above-mentioned preparation method, achieves good coordination of various raw materials, and the interaction of polyether diol, phthalic anhydride polyester polyol and toluene diisocyanate and other raw materials makes the high-strength polyethylene modified TPU high and low temperature film have the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile performance.

[0032] In the above technical solution, the preparation method of the PU composite adhesive includes the following steps:

[0033] (1) placing polyethylene in a reaction vessel, stirring and heating to 110-115° C. to melt, introducing nitrogen, adding a polyurethane emulsion and a modified coupling agent into the reactor, reacting for 1-1.5 hours, then adding an accelerator and continuing the reaction for 1-1.5 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture;

[0034] (2) The system temperature is cooled to 75-85°C, and then hydantoin epoxy resin is added to the polyurethane / polyethylene mixture for reaction for 1-1.5 hours to obtain a PU composite adhesive.

[0035] The present invention prepares the PU composite adhesive by adopting the above-mentioned preparation method, and the raw materials are well matched. The interaction between polyethylene, hydantoin epoxy resin, polyurethane emulsion, modified coupling agent and other raw materials makes the high-strength polyethylene modified TPU high and low temperature film have the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile performance.

[0036] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0037] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0038] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0039] Preferably, the thickness of the first TPU film layer and the second TPU film layer is 0.7 mm, and the coating thickness of the PU composite adhesive is 0.05 mm.

[0040] The preparation method of the high-strength polyethylene modified TPU high and low temperature film of the present invention has simple process, easy operation and control, is conducive to large-scale industrial production, and the prepared TPU high and low temperature film has stable quality, strong aging resistance, water resistance, impact resistance and tensile properties, and has excellent comprehensive performance.

[0041] The beneficial effects of the present invention are that the high-strength polyethylene modified TPU high and low temperature film of the present invention is sequentially provided with a first TPU film layer, a yarn layer and a second TPU film layer from top to bottom, and the yarn layer has the characteristics of low density, high strength, good toughness, tear resistance, and not easy to deform. The PU composite film layer is used to firmly bond the lower surface of the first TPU film layer to the upper surface of the yarn layer, and to firmly bond the upper surface of the second TPU film layer to the lower surface of the yarn layer.

[0042] The high-strength polyethylene modified TPU high-low temperature film of the present invention has the advantages of aging resistance, strong water resistance, strong tensile properties, etc., and its structure is simple and easy to use. The interaction of polyethylene, hydantoin epoxy resin, polyurethane emulsion, modified coupling agent and other raw materials in the high-strength polyethylene modified TPU high-low temperature film makes the high-strength polyethylene modified TPU high-low temperature film have the characteristics of aging resistance, strong water resistance, strong impact resistance and strong tensile properties, and can be used as a shoe upper skeleton, shoe upper, and other products.

[0043] At the same time, the preparation method of high-strength polyethylene modified TPU high and low temperature film is simple in process and easy to control in operation, which is conducive to large-scale industrial production. The prepared high-strength polyethylene modified TPU high and low temperature film has stable quality, strong aging resistance, water resistance, impact resistance and tensile properties, and has excellent comprehensive performance. DETAILED DESCRIPTION

[0044] In order to facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the embodiments. The contents mentioned in the embodiments are not intended to limit the present invention.

[0045] Example 1

[0046] In this embodiment, a high-strength polyethylene modified TPU high and low temperature film includes a first TPU film layer, a yarn layer and a second TPU film layer arranged in sequence from top to bottom, and a PU composite film layer is provided between the first TPU film layer and the yarn layer and between the second TPU film layer and the yarn layer.

[0047] In this embodiment, the first TPU film layer and the second TPU film layer are both made of a transparent TPU film with a model number of ZD-135CM*85A produced by Guangdong Zhongding Technology Development Co., Ltd., and have a thickness of 0.7 mm.

[0048] Furthermore, the yarn layer is woven from modified aramid fibers.

[0049] It should be further explained that the aramid fiber is aramid 1414 with a specification of 23S / 2, the yarn layer is woven from modified aramid fiber, and the density of the yarn layer is 60g / m 2 , thickness is 0.5mm.

[0050] Furthermore, the preparation method of the modified aramid fiber comprises the following steps:

[0051] (1) Aramid fiber cleaning: The aramid fiber was soaked in anhydrous ethanol and ultrasonically cleaned for 2 hours, then washed with deionized water 5 times, and then placed in a drying oven and dried at 85°C;

[0052] (2) Modification treatment with CaCl2 ethanol solution: The cleaned aramid fiber was placed in a CaCl2 ethanol solution with a CaCl2 mass fraction of 12%, and the temperature was raised to 90°C. After reacting for 4.5 hours, the fiber was taken out, rinsed with deionized water 5 times, and then placed in a drying oven and dried at 85°C to obtain pretreated aramid fiber.

[0053] (3) Preparation of dopamine aqueous solution: Add tris(hydroxymethyl)aminomethane to a 5 g / L dopamine aqueous solution to adjust the pH value of the solution to 8.5 to obtain a dopamine pretreatment solution;

[0054] (4) Dopamine modification: The pretreated aramid fiber was immersed in the dopamine pretreatment solution for 27 hours, then washed with deionized water for 5 times, and then placed in a drying oven for drying at 85°C to obtain modified aramid fiber.

[0055] Furthermore, the PU composite film is made of a PU composite adhesive; the PU composite adhesive includes the following raw materials in parts by weight: 45 parts of polyurethane emulsion, 22 parts of polyethylene, 16 parts of hydantoin epoxy resin, 8 parts of modified coupling agent and 3 parts of accelerator.

[0056] Furthermore, the polyethylene is polyethylene with a model number of 2426H produced by Shenhua Chemical; and the hydantoin epoxy resin is hydantoin epoxy resin with a CAS number of 15336-81-9 produced by Wuhan Huaxiang Kejie Biotechnology Co., Ltd.

[0057] Furthermore, the accelerator is dibutyltin diacetate.

[0058] Furthermore, the preparation method of the modified coupling agent comprises the following steps:

[0059] (1) adding vinyl tris(2-methoxyethoxy)silane and maleic anhydride into a reaction tube, then adding anhydrous dichloromethane and stirring to dissolve, and finally adding a metal compound catalyst to obtain a pre-reaction solution;

[0060] (2) The pre-reaction solution was heated to 45° C. and reacted for 16 hours. After the reaction was completed, the modified coupling agent was separated by column chromatography.

[0061] Furthermore, the molar ratio of vinyltris(2-methoxyethoxy)silane to maleic anhydride is 2:1, and the molar content of the metal compound catalyst is 8 mol%.

[0062] Furthermore, the metal compound catalyst is based on Grubbs 2 nd Catalysts and Hoveyda-Grubbs 2 nd The catalyst is compounded in a molar ratio of 1.3:1.

[0063] Furthermore, the preparation method of the polyurethane emulsion comprises the following steps:

[0064] (1) Polyether diol and phthalic anhydride polyester polyol were placed in a reaction vessel, stirred and heated to 120° C., the pressure in the reaction vessel was controlled at -0.04 MPa, and dehydrated; nitrogen was then introduced, the temperature was lowered to 65° C., toluene diisocyanate and a catalyst were added, and the catalytic reaction was continued for 2 hours. The temperature was then lowered to 66° C., dimethylolpropionic acid was added, and the reaction was continued for 2 hours. After the reaction was completed, mixture A was obtained;

[0065] (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

[0066] Furthermore, the molar ratio of the polyether diol, phthalic anhydride polyester polyol and toluene diisocyanate is 0.5:0.3:1.

[0067] Furthermore, the molar ratio of dimethylolpropionic acid to toluene diisocyanate is 0.08:1.

[0068] Furthermore, the catalyst is dibutyltin dilaurate, and the molar content of the catalyst is 3 mol%.

[0069] Furthermore, the molar content of the deionized water is 10 mol%.

[0070] Furthermore, the polyether diol is a polyether diol of model 330HP produced by Arkema of France; and the phthalic anhydride polyester polyol is a phthalic anhydride polyester polyol of model 20-32-56 produced by Shandong New Kinetic Energy Chemical Co., Ltd.

[0071] Furthermore, the preparation method of the PU composite adhesive comprises the following steps:

[0072] (1) Polyethylene is placed in a reaction vessel, heated to 112°C with stirring to melt, nitrogen is introduced, polyurethane emulsion and modified coupling agent are added to the reactor, reacted for 1.2 hours, and then an accelerator is added to continue the reaction for 1.2 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture;

[0073] (2) The system temperature was cooled to 70°C, and then hydantoin epoxy resin was added to the polyurethane / polyethylene mixture and reacted for 1.2 hours to obtain a PU composite adhesive.

[0074] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0075] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0076] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0077] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 90° C., the drying time is 3 minutes, and the coating thickness of the PU composite adhesive is 0.05 mm.

[0078] Example 2

[0079] In this embodiment, the PU composite film includes a PU composite adhesive; the PU composite adhesive includes the following raw materials in parts by weight: 48 parts of polyurethane emulsion, 24 parts of polyethylene, 17 parts of hydantoin epoxy resin, 9 parts of modified coupling agent and 3 parts of accelerator.

[0080] Furthermore, the preparation method of the polyurethane emulsion comprises the following steps:

[0081] (1) Polyether diol and phthalic anhydride polyester polyol were placed in a reaction vessel, stirred and heated to 120° C., the pressure in the reaction vessel was controlled at -0.04 MPa, and dehydrated; nitrogen was then introduced, the temperature was lowered to 65° C., toluene diisocyanate and a catalyst were added, and the catalytic reaction was continued for 2 hours. The temperature was then lowered to 66° C., dimethylolpropionic acid was added, and the reaction was continued for 2 hours. After the reaction was completed, mixture A was obtained;

[0082] (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

[0083] Furthermore, the preparation method of the PU composite adhesive comprises the following steps:

[0084] (1) Polyethylene is placed in a reaction vessel, heated to 112°C with stirring to melt, nitrogen is introduced, polyurethane emulsion and modified coupling agent are added to the reactor, reacted for 1.2 hours, and then an accelerator is added to continue the reaction for 1.2 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture;

[0085] (2) The system temperature was cooled to 70°C, and then hydantoin epoxy resin was added to the polyurethane / polyethylene mixture and reacted for 1.2 hours to obtain a PU composite adhesive.

[0086] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0087] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0088] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0089] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 95° C., and the drying time is 3 minutes.

[0090] The rest of the content of this embodiment is the same as that of embodiment 1.

[0091] Example 3

[0092] In this embodiment, the PU composite film includes a PU composite adhesive; the PU composite adhesive includes the following raw materials in parts by weight: 51 parts of polyurethane emulsion, 26 parts of polyethylene, 18 parts of hydantoin epoxy resin, 10 parts of modified coupling agent and 4 parts of accelerator.

[0093] Furthermore, the preparation method of the polyurethane emulsion comprises the following steps:

[0094] (1) Polyether diol and phthalic anhydride polyester polyol were placed in a reaction vessel, stirred and heated to 120° C., the pressure in the reaction vessel was controlled at -0.04 MPa, and dehydrated; nitrogen was then introduced, the temperature was lowered to 65° C., toluene diisocyanate and a catalyst were added, and the catalytic reaction was continued for 2 hours. The temperature was then lowered to 66° C., dimethylolpropionic acid was added, and the reaction was continued for 2 hours. After the reaction was completed, mixture A was obtained;

[0095] (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

[0096] Furthermore, the preparation method of the PU composite adhesive comprises the following steps:

[0097] (1) Polyethylene is placed in a reaction vessel, heated to 112°C with stirring to melt, nitrogen is introduced, polyurethane emulsion and modified coupling agent are added to the reactor, reacted for 1.2 hours, and then an accelerator is added to continue the reaction for 1.2 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture;

[0098] (2) The system temperature was cooled to 70°C, and then hydantoin epoxy resin was added to the polyurethane / polyethylene mixture and reacted for 1.2 hours to obtain a PU composite adhesive.

[0099] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0100] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0101] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0102] Furthermore, the drying step of the PU composite adhesive is specifically as follows: online drying temperature is 100° C., and drying time is 3 minutes.

[0103] The rest of the content of this embodiment is the same as that of embodiment 1.

[0104] Example 4

[0105] In this embodiment, the PU composite film includes a PU composite adhesive; the PU composite adhesive includes the following raw materials in parts by weight: 54 parts of polyurethane emulsion, 28 parts of polyethylene, 19 parts of hydantoin epoxy resin, 10 parts of modified coupling agent and 4 parts of accelerator.

[0106] Furthermore, the preparation method of the polyurethane emulsion comprises the following steps:

[0107] (1) Polyether diol and phthalic anhydride polyester polyol were placed in a reaction vessel, stirred and heated to 120° C., the pressure in the reaction vessel was controlled at -0.04 MPa, and dehydrated; nitrogen was then introduced, the temperature was lowered to 65° C., toluene diisocyanate and a catalyst were added, and the catalytic reaction was continued for 2 hours. The temperature was then lowered to 66° C., dimethylolpropionic acid was added, and the reaction was continued for 2 hours. After the reaction was completed, mixture A was obtained;

[0108] (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

[0109] Furthermore, the preparation method of the PU composite adhesive comprises the following steps:

[0110] (1) Polyethylene is placed in a reaction vessel, heated to 112°C with stirring to melt, nitrogen is introduced, polyurethane emulsion and modified coupling agent are added to the reactor, reacted for 1.2 hours, and then an accelerator is added to continue the reaction for 1.2 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture;

[0111] (2) The system temperature was cooled to 70°C, and then hydantoin epoxy resin was added to the polyurethane / polyethylene mixture and reacted for 1.2 hours to obtain a PU composite adhesive.

[0112] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0113] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0114] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0115] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 105° C., and the drying time is 3 minutes.

[0116] The rest of the content of this embodiment is the same as that of embodiment 1.

[0117] Example 7

[0118] In this embodiment, the yarn layer is woven from modified polyethylene fibers.

[0119] It should be further explained that the modified polyethylene fiber is 60D FDY polyethylene fiber with the product number JYX from Shenzhen Teli Chemical Fiber Co., Ltd. The yarn layer is woven from the modified polyethylene fiber, and the density of the yarn layer is 60g / m 2 , thickness is 0.5mm.

[0120] Furthermore, the preparation method of the modified polyethylene fiber comprises the following steps:

[0121] (1) Polyethylene fiber cleaning: The polyethylene fiber was soaked in anhydrous ethanol and ultrasonically cleaned for 2 hours, then washed with deionized water 5 times, and then placed in a drying oven and dried at 85°C;

[0122] (3) Preparation of dopamine aqueous solution: Add tris(hydroxymethyl)aminomethane to a 5 g / L dopamine aqueous solution to adjust the pH value of the solution to 8.5 to obtain a dopamine pretreatment solution;

[0123] (4) Dopamine modification: The cleaned polyethylene fiber was soaked in a dopamine pretreatment solution for 27 hours, then washed with deionized water for 5 times, and then placed in a drying oven for drying at 85°C to obtain modified polyethylene fiber.

[0124] The rest of the content of this embodiment is the same as that of embodiment 1.

[0125] Comparative Example 1

[0126] The difference between this comparative example and Example 1 is that an equal amount of polyurethane emulsion is used instead of polyethylene in the PU composite adhesive.

[0127] That is, in this comparative example, the PU composite adhesive includes the following raw materials in parts by weight: 67 parts of polyurethane emulsion, 16 parts of hydantoin epoxy resin, 8 parts of modified coupling agent and 3 parts of accelerator.

[0128] Furthermore, the preparation method of the PU composite adhesive comprises the following steps:

[0129] (1) Adding polyurethane emulsion and modified coupling agent into a reactor, introducing nitrogen, and heating to 100°C for reaction for 1.2 hours. Then, adding accelerator and continuing the reaction for 1.2 hours before stopping the reaction to obtain mixture B;

[0130] (2) The system temperature was cooled to 70°C, and then hydantoin epoxy resin was added to mixture B and reacted for 1.2 hours to obtain a PU composite adhesive.

[0131] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0132] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0133] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0134] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 105° C., and the drying time is 5 minutes.

[0135] Comparative Example 2

[0136] The difference between this comparative example and Example 1 is that an equal amount of polyurethane emulsion is used in place of hydantoin epoxy resin in the PU composite adhesive.

[0137] That is, in this comparative example, the PU composite adhesive includes the following raw materials in parts by weight: 61 parts of polyurethane emulsion, 22 parts of polyethylene, 8 parts of modified coupling agent and 3 parts of accelerator.

[0138] Furthermore, the preparation method of the PU composite adhesive includes the following steps: placing polyethylene in a reaction vessel, stirring and heating to 112°C to melt, introducing nitrogen, adding a polyurethane emulsion and a modified coupling agent into the reactor, cooling to 100°C and reacting for 1.2 hours, then adding a promoter and continuing the reaction for 1.2 hours before stopping the reaction to obtain the PU composite adhesive.

[0139] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0140] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0141] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0142] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 105° C., and the drying time is 5 minutes.

[0143] Comparative Example 3

[0144] The difference between this comparative example and Example 1 is that aramid fiber is used instead of modified aramid fiber.

[0145] The present invention also provides a method for preparing the above-mentioned high-strength polyethylene modified TPU high and low temperature film, comprising the following steps:

[0146] (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A;

[0147] (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

[0148] Furthermore, the drying step of the PU composite adhesive is specifically as follows: the online drying temperature is 105° C., and the drying time is 5 minutes.

[0149] Performance testing

[0150] The high-strength polyethylene modified TPU high-low temperature films prepared in Examples 2-6 and Comparative Examples 1-3 were subjected to performance tests. The density, tensile properties, water resistance, and Shore hardness of the high-strength polyethylene modified TPU high-low temperature films were tested. The test data are shown in Table 1 below:

[0151] Table 1

[0152]

[0153]

[0154] The tensile strength test was carried out according to GB / T 1040.3-2006, and the tensile rate was 100 mm / min.

[0155] The water resistance test is to cut the membrane into 2cm×2cm small squares, dry them in an oven at a constant temperature of 80℃ for 24 hours, then put them in a desiccator, weigh the mass (m1) after cooling for 30 minutes, soak them in water (room temperature), take them out after 24 hours, absorb the moisture with filter paper, weigh the mass (m2), and calculate the water absorption rate. Water absorption rate (%) = (m2-m1) / m1×100%.

[0156] The notched impact strength test was conducted in accordance with GB / T 1043.1-2008, using a simple supported beam impact strength test of an unnotched specimen. The high-strength polyethylene modified TPU high and low temperature film was tested using a 10*10*2 mm sample.

[0157] The aging resistance test was conducted using QUV 340nm for 1000 hours with a light intensity of 0.8W / cm 2 .

[0158] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the scope of protection of the present invention.

Claims

1. A high-strength polyethylene modified TPU high and low temperature film, characterized by: The invention comprises a first TPU film layer, a yarn layer, and a second TPU film layer arranged in sequence from top to bottom, wherein a PU composite film layer is provided between the first TPU film layer and the yarn layer, and between the second TPU film layer and the yarn layer; the yarn layer is woven from modified aramid fiber or modified polyethylene fiber; the PU composite film comprises a PU composite adhesive; the PU composite adhesive comprises the following raw materials in parts by weight: 45-55 parts of polyurethane emulsion, 22-28 parts of polyethylene, 16-19 parts of hydantoin epoxy resin, 8-10 parts of modified coupling agent, and 3-4 parts of accelerator; the preparation method of the PU composite adhesive comprises the following steps: (1) placing polyethylene in a reaction vessel, stirring and heating to 110-115° C. to melt, introducing nitrogen, adding a polyurethane emulsion and a modified coupling agent into the reactor, reacting for 1-1.5 hours, then adding an accelerator and continuing the reaction for 1-1.5 hours before stopping the reaction to obtain a polyurethane / polyethylene mixture; (2) Cooling the system temperature to 75-85°C, adding hydantoin epoxy resin to the polyurethane / polyethylene mixture and reacting for 1-1.5 hours to obtain a PU composite adhesive; The preparation method of the modified coupling agent comprises the following steps: (1) adding vinyl tris(2-methoxyethoxy)silane and maleic anhydride into a reaction tube, then adding anhydrous dichloromethane and stirring to dissolve, and finally adding a metal compound catalyst to obtain a pre-reaction solution; (2) heating the pre-reaction solution to 40-50° C. for 15-18 hours. After the reaction is complete, separating the modified coupling agent by column chromatography; The preparation method of the modified aramid fiber comprises the following steps: (1) Aramid fiber cleaning: Soak the aramid fiber in anhydrous ethanol and clean it with ultrasound for 1.5-2.5 hours, then wash it with deionized water for 4-5 times, and then dry it at 80-90℃; (2) Modification treatment with CaCl2 ethanol solution: The cleaned aramid fiber is placed in a CaCl2 ethanol solution with a CaCl2 mass fraction of 10-15%, and the temperature is raised to 85-95°C. After reacting for 4-5 hours, the fiber is taken out and rinsed with deionized water 4-5 times, and then dried at 80-90°C to obtain pretreated aramid fiber; (3) Preparation of dopamine aqueous solution: Add tris(hydroxymethyl)aminomethane to a 4-6 g / L dopamine aqueous solution to adjust the pH value of the solution to 8.3-8.7 to obtain a dopamine pretreatment solution; (4) Dopamine modification: The pretreated aramid fiber was immersed in a dopamine pretreatment solution for 25-30 hours, then washed with deionized water for 4-5 times, and then dried at 80-90°C to obtain modified aramid fiber.

2. The high-strength polyethylene modified TPU high and low temperature film according to claim 1, characterized in that: The molar ratio of vinyl tris(2-methoxyethoxy)silane to maleic anhydride is 1.8-2.2:1, and the molar content of the metal compound catalyst is 5-10 mol%.

3. The high-strength polyethylene modified TPU high and low temperature film according to claim 1, characterized in that: The metal compound catalyst is based on Grubbs 2 nd Catalysts and Hoveyda-Grubbs 2 nd The catalyst is compounded in a molar ratio of 1.2-1.5:

1.

4. The high-strength polyethylene modified TPU high and low temperature film according to claim 1, characterized in that: The preparation method of the polyurethane emulsion comprises the following steps: (1) placing polyether diol and phthalic anhydride polyester polyol in a reaction vessel, stirring and heating to 115-130° C., controlling the pressure in the reaction vessel to -0.02 to -0.06 MPa, and dehydrating; then filling with nitrogen, cooling to 60-70° C., adding toluene diisocyanate and a catalyst, and catalytically reacting for 1-3 hours, cooling to 64-70° C., adding dimethylolpropionic acid, and continuing the reaction for 1-2 hours, and completing the reaction to obtain mixture A; (2) The system temperature was lowered to room temperature, ethylenediamine was added to the mixture A for neutralization, and deionized water was slowly added and stirred to obtain a polyurethane emulsion.

5. The high-strength polyethylene modified TPU high and low temperature film according to claim 1, characterized in that: The molar ratio of the polyether diol, phthalic anhydride polyester polyol and toluene diisocyanate is 0.25-0.5:(0.25-0.5):

1.

6. A method for preparing a high-strength polyethylene modified TPU high and low temperature film according to any one of claims 1 to 5, characterized in that: The steps include: (S1) taking a yarn layer, coating the upper surface of the yarn layer with a PU composite adhesive, laminating the lower surface of the first TPU film layer to the upper surface of the yarn layer, and drying and forming the composite film layer A; (S2) coating the lower surface of the composite film layer A with a PU composite adhesive, laminating the upper surface of the second TPU film layer to the lower surface of the yarn layer, and drying and forming the film to obtain a high-strength polyethylene modified TPU high and low temperature film.

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