A TPO waterproof metal fusion plate and its preparation method

Abstract

This invention relates to the field of waterproof building materials technology, specifically to a TPO waterproof metal fusion board and its preparation method. The TPO waterproof metal fusion board comprises, from bottom to top, a metal plate, an adhesive layer, and a TPO waterproof layer. The adhesive layer comprises the following weight components: 40-50 parts low-density polyethylene, 15-25 parts maleic anhydride-grafted polyolefin, 10-20 parts POE, 10-15 parts phenolic resin, 5-10 parts tackifier, 2-4 parts talc, 1-3 parts coupling agent, 3-5 parts polyethylene wax, and 0.5-0.8 parts antioxidant. This invention involves preheating and bonding one side of the TPO waterproof layer and adhesive layer at 120-140°C; then pressing the metal plate onto the other side of the adhesive layer, performing hot-pressing bonding at 140-160°C, and cooling to room temperature to obtain the TPO waterproof metal fusion board.

Description

Technical Field

[0001] This invention relates to the field of waterproof building materials technology, specifically to a TPO waterproof metal fusion board and its preparation method. Background Technology

[0002] With the rapid development of the construction industry and industrial equipment, the demand for waterproofing materials is increasing, especially in critical areas such as roofs, basements, and exterior walls. Thermoplastic polyolefin (TPO), as a new type of waterproofing material, has attracted widespread attention due to its excellent weather resistance, UV resistance, good ductility, and recyclability. TPO waterproofing membranes are typically composed of a blend of polypropylene and polyethylene, exhibiting strong chemical resistance and aging resistance.

[0003] To further improve the waterproofing performance of TPO and reduce its defects during application, metal fusion panels have been gradually introduced into the waterproofing field as an emerging material in recent years. TPO waterproof metal fusion panels are a new type of material that combines TPO waterproof membranes with metal sheets. It combines the waterproofing performance of TPO membranes with the strength and durability of metal sheets, featuring integrated waterproofing and structural design, and a balance of rigidity and flexibility. It possesses both the plasticity of steel and the flexibility of waterproofing materials. These TPO waterproof metal fusion panels are widely used in building roofs, industrial equipment protection, chemical storage tanks, and other fields. Compared to traditional ordinary color steel tiles, it offers advantages such as integrated composite design, weather and corrosion resistance, labor and time savings, energy efficiency, and suitability for photovoltaic roofing.

[0004] Therefore, we propose a TPO waterproof metal fusion plate and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide a TPO waterproof metal fusion plate and its preparation method to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A TPO waterproof metal fusion panel, comprising, from bottom to top, a metal plate, an adhesive layer, and a TPO waterproof layer. The adhesive layer comprises the following components by weight: 40-50 parts low-density polyethylene, 15-25 parts maleic anhydride grafted polyolefin, 10-20 parts POE, 10-15 parts phenolic resin, 5-10 parts tackifier, 2-4 parts talc, 1-3 parts coupling agent, 3-5 parts polyethylene wax, and 0.5-0.8 parts antioxidant.

[0008] Furthermore, the maleic anhydride-grafted polyolefin is maleic anhydride-grafted polypropylene (MAH-g-PP) or maleic anhydride-grafted polyethylene (MAH-g-PE).

[0009] Furthermore, the coupling agent is 3-aminopropyltrimethoxysilane.

[0010] Furthermore, the preparation method of the thickener is as follows:

[0011] Step 1: Under nitrogen protection, eugenol and epichlorohydrin are mixed and benzyltriethylammonium chloride is used as a catalyst. The mixture is reacted at 100-110℃ for 3-5 hours. The temperature is then lowered to 50-60℃, sodium hydroxide solution is added, and the reaction continues for 2-4 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether is obtained.

[0012] Step 2: Under nitrogen protection, acrylic acid-modified rosin is dissolved in toluene, eugenol glycidyl ether, triethylamine and hydroquinone are added, and the mixture is reacted at 110-120℃ for 4-6 hours to obtain rosin diesters.

[0013] Step 3: Mix rosin diester, hyperbranched unsaturated resin, fluorinated mercapto silicone and photoinitiator evenly, and then irradiate with ultraviolet light to obtain a tackifier.

[0014] Further, in step one, the mass ratio of eugenol, epichlorohydrin, benzyltriethylammonium chloride and sodium hydroxide solution is 1:(2-4):(0.03-0.05):(0.8-1.5), and the concentration of sodium hydroxide solution is 30-40wt%.

[0015] Furthermore, in step two, the molar ratio of acrylic acid-modified rosin to eugenol glycidyl ether is 1:(2.0-2.2).

[0016] Furthermore, the mass of the triethylamine is 0.5-0.8% of the mass of the acrylic rosin.

[0017] Furthermore, the mass of hydroquinone is 0.5-0.8% of the mass of eugenol glycidyl ether.

[0018] Further, the mass ratio of the rosin diester, hyperbranched unsaturated resin, fluorinated mercapto organosilicon and photoinitiator is 1:(0.4-0.6):(1.5-2.0):(0.3-0.5).

[0019] Furthermore, the preparation method of the hyperbranched unsaturated resin is as follows:

[0020] Hydroxyl-terminated hyperbranched polyester, isocyanate methacrylate, and dibutyltin dilaurate were mixed evenly and reacted at 60-70℃ for 4-6 hours. After cooling to room temperature, the mixture was filtered, washed, and dried to obtain a hyperbranched unsaturated resin.

[0021] Further, the mass ratio of the hydroxyl-terminated hyperbranched polyester, isocyanate methacrylate, and dibutyltin dilaurate is 1:(0.3-0.8):(0.01-0.03).

[0022] Furthermore, the preparation method of the fluorinated mercapto organosilicon is as follows:

[0023] Trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol were reacted at 120-140℃ for 4-6 h under p-toluenesulfonic acid catalysis, followed by vacuum distillation to obtain fluorinated mercaptosilicone.

[0024] Furthermore, the molar ratio of the trifluoropropanetrimethoxysilane to mercaptopropyltrimethoxysilane is (0.5-1):1.

[0025] Furthermore, the amount of neopentyl glycol used is 1.2-2.0 times the total molar amount of trifluoropropanetrimethoxysilane and mercaptopropylalkoxysilane.

[0026] Furthermore, the mass of the p-toluenesulfonic acid is 1-3% of the total mass of trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol.

[0027] Furthermore, the photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0028] Furthermore, the process conditions for ultraviolet irradiation are: irradiation with 360-400nm ultraviolet light for 30-50 minutes, with an irradiation intensity of 20-30mW / cm². 2 .

[0029] A method for preparing a TPO waterproof metal fusion panel includes the following steps:

[0030] Step S1: Mix maleic anhydride-grafted polyolefin, low-density polyethylene, POE, phenolic resin, tackifier, talc, coupling agent, polyethylene wax and antioxidant evenly, melt extrude and calender to obtain adhesive layer.

[0031] Step S2: Preheat and bond one side of the TPO waterproof layer and adhesive layer at 120-140℃; then press the metal plate onto the other side of the adhesive layer and hot-press it at 140-160℃, then cool it to room temperature to obtain the TPO waterproof metal fusion plate.

[0032] Furthermore, the melt extrusion temperature is 180-200℃.

[0033] Furthermore, the thickness of the adhesive layer is 20-60 μm.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] This invention discloses a TPO waterproof metal fusion plate and its preparation method. Under the action of a catalyst, eugenol and epichlorohydrin are mixed to undergo an epoxy ring-opening reaction, followed by a ring-closing reaction with an alkaline solution to synthesize eugenol glycidyl ether. Using acrylic acid-modified rosin containing two carboxyl groups and eugenol glycidyl ether as raw materials, triethylamine as a catalyst, and hydroquinone as a polymerization inhibitor, a rosin diester containing two hydroxyl groups is prepared, which enhances the material's heat resistance and UV resistance. At the same time, the double bond of eugenol is introduced as an active site, which can undergo a mercapto-alkene click reaction with hyperbranched unsaturated resin and fluorinated mercapto-organosilicon to construct a three-dimensional cross-linked network. The hyperbranched structure and fluorinated segments of organosilicon are further introduced. The hyperbranched molecule surface is rich in hydroxymethyl and hydroxyl groups, which can synergistically enhance the chemical bonding with the metal plate / TPO under the action of a catalyst. The fluorinated segments of organosilicon can improve the hydrophobic properties of the material. This improvement enhances the hydrophobic properties and overall bonding strength of the material, making the TPO waterproof metal fusion plate of this invention outstanding in terms of waterproofness and durability, and with a wider range of application prospects. Detailed Implementation

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0037] In this embodiment, maleic anhydride-grafted polyolefin: maleic anhydride-grafted polypropylene, brand name Exxelor PO 1020; low-density polyethylene: brand name 2426H, purchased from BASF Yangtze; POE: brand name Dow 8150; phenolic resin: model 2402, purchased from Shenzhen Yunlin Chemical Co., Ltd.; acrylic acid-modified rosin: purchased from Pande (Shanghai) International Trading Co., Ltd.; hydroxyl-terminated hyperbranched polyester: model HB-20, Boltorn TM H2O; Talc powder: 5000 mesh, purchased from Jiangyin Guangyuan Ultrafine Powder Co., Ltd.; Polyethylene wax: Honeywell AC-6A; Antioxidant: Antioxidant 1010; Metal plate: Zinc-free hot-dip galvanized steel plate, DAx52D, 0.5mm thick, purchased from Jiangyin Haimei Metal New Materials Co., Ltd.; TPO waterproof layer: TPO waterproof membrane, 0.3mm thick, purchased from Weifang Jiankai Waterproof Materials Co., Ltd.

[0038] Unless otherwise specified, all the following quantities are parts by weight.

[0039] Example 1: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0040] Step S1: Mix 15 parts maleic anhydride grafted polyolefin, 40 parts low-density polyethylene, 10 parts POE, 10 parts phenolic resin, 5 parts tackifier, 2 parts talc, 1 part 3-aminopropyltrimethoxysilane, 3 parts polyethylene wax and 0.5 parts antioxidant evenly, melt extrude (temperature is 180℃) and calender to obtain adhesive layer;

[0041] Step S2: Preheat and bond one side of the TPO waterproof layer and adhesive layer at 120°C; then press the metal plate onto the other side of the adhesive layer and hot-press it at 140°C. Cool it to room temperature to obtain the TPO waterproof metal fusion board.

[0042] The preparation method of the thickener is as follows:

[0043] Step 1: Under nitrogen protection, 5 parts of eugenol and 10 parts of epichlorohydrin were mixed, and 0.15 parts of benzyltriethylammonium chloride were used as catalysts. The mixture was reacted at 100°C for 3 hours. The temperature was then lowered to 50°C, and 4 parts of 30wt% sodium hydroxide solution were added. The reaction was continued for 2 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether was obtained.

[0044] Step 2: Under nitrogen protection, acrylic-modified rosin was dissolved in toluene, and eugenol glycidyl ether, triethylamine, and hydroquinone were added. The mixture was reacted at 110°C for 4 hours to obtain rosin diesters. The molar ratio of acrylic-modified rosin to eugenol glycidyl ether was 1:2; the mass of triethylamine was 0.5% of the mass of acrylic-modified rosin; and the mass of hydroquinone was 0.5% of the mass of eugenol glycidyl ether.

[0045] Step 3: Mix 5 parts of rosin diester, 2 parts of hyperbranched unsaturated resin, 7.5 parts of fluorinated mercapto-based organosilicon, and 1.5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone evenly, and irradiate with 360nm ultraviolet light for 50 minutes at an irradiation intensity of 20mW / cm². 2 This yields a thickener;

[0046] The preparation method of hyperbranched unsaturated resin is as follows:

[0047] Two parts of hydroxyl-terminated hyperbranched polyester, 0.6 parts of isocyanate methacrylate and 0.02 parts of dibutyltin dilaurate were mixed evenly and reacted at 60°C for 4 hours. After cooling to room temperature, the mixture was filtered, washed and dried to obtain hyperbranched unsaturated resin.

[0048] The preparation method of fluorinated mercapto organosilicon is as follows:

[0049] Fluorinated mercaptosilane was prepared by reacting trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol at 120 °C for 4 h under p-toluenesulfonic acid catalysis and followed by vacuum distillation. The molar ratio of trifluoropropanetrimethoxysilane to mercaptopropyltrimethoxysilane was 0.5:1; the amount of neopentyl glycol was 1.2 times the total molar amount of trifluoropropanetrimethoxysilane and mercaptopropylalkoxysilane; and the mass of p-toluenesulfonic acid was 1% of the total mass of trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol.

[0050] Example 2: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0051] Step S1: Mix 20 parts maleic anhydride grafted polyolefin, 45 parts low-density polyethylene, 15 parts POE, 12 parts phenolic resin, 8 parts tackifier, 3 parts talc, 2 parts 3-aminopropyltrimethoxysilane, 4 parts polyethylene wax and 0.6 parts antioxidant evenly, melt extrude (temperature is 190℃) and calender to obtain adhesive layer;

[0052] Step S2: Preheat and bond one side of the TPO waterproof layer and adhesive layer at 130°C; then press the metal plate onto the other side of the adhesive layer and hot-press it at 150°C. Cool it to room temperature to obtain the TPO waterproof metal fusion board.

[0053] The preparation method of the thickener is as follows:

[0054] Step 1: Under nitrogen protection, 8 parts of eugenol and 24 parts of epichlorohydrin were mixed, and 0.32 parts of benzyltriethylammonium chloride were used as catalysts. The mixture was reacted at 105°C for 4 hours. The temperature was then lowered to 55°C, and 8 parts of 35wt% sodium hydroxide solution were added. The reaction was continued for 3 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether was obtained.

[0055] Step 2: Under nitrogen protection, acrylic-modified rosin was dissolved in toluene, and eugenol glycidyl ether, triethylamine, and hydroquinone were added. The mixture was reacted at 115°C for 5 hours to obtain rosin diesters. The molar ratio of acrylic-modified rosin to eugenol glycidyl ether was 1:2.1; the mass of triethylamine was 0.6% of the mass of acrylic-modified rosin; and the mass of hydroquinone was 0.6% of the mass of eugenol glycidyl ether.

[0056] Step 3: Mix 8 parts of rosin diester, 4 parts of hyperbranched unsaturated resin, 16 parts of fluorinated mercapto-based organosilicon, and 3.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone evenly, and irradiate with 380nm ultraviolet light for 40 minutes at an irradiation intensity of 25mW / cm². 2 This yields a thickener;

[0057] The preparation method of hyperbranched unsaturated resin is as follows:

[0058] Four parts of hydroxyl-terminated hyperbranched polyester, two parts of isocyanate methacrylate and 0.08 parts of dibutyltin dilaurate were mixed evenly and reacted at 65°C for 5 hours. After cooling to room temperature, the mixture was filtered, washed and dried to obtain hyperbranched unsaturated resin.

[0059] The preparation method of fluorinated mercapto organosilicon is as follows:

[0060] Fluorinated mercaptosilane was prepared by reacting trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol at 130°C for 5 h under p-toluenesulfonic acid catalysis, followed by vacuum distillation. The molar ratio of trifluoropropanetrimethoxysilane to mercaptopropyltrimethoxysilane was 0.8:1; the amount of neopentyl glycol was 1.5 times the total molar amount of trifluoropropanetrimethoxysilane and mercaptopropylalkoxysilane; and the mass of p-toluenesulfonic acid was 2% of the total mass of trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol.

[0061] Example 3: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0062] Step S1: Mix 25 parts maleic anhydride grafted polyolefin, 50 parts low-density polyethylene, 20 parts POE, 15 parts phenolic resin, 10 parts tackifier, 4 parts talc, 3 parts 3-aminopropyltrimethoxysilane, 5 parts polyethylene wax and 0.8 parts antioxidant evenly, melt extrude (temperature 200℃) and calender to obtain the adhesive layer;

[0063] Step S2: Preheat and bond one side of the TPO waterproof layer and adhesive layer at 140°C; then press the metal plate onto the other side of the adhesive layer and hot-press it at 160°C. Cool it to room temperature to obtain the TPO waterproof metal fusion board.

[0064] The preparation method of the thickener is as follows:

[0065] Step 1: Under nitrogen protection, 10 parts of eugenol and 40 parts of epichlorohydrin were mixed, and 0.5 parts of benzyltriethylammonium chloride were used as catalysts. The mixture was reacted at 110°C for 5 hours, then cooled to 60°C, and 15 parts of 40wt% sodium hydroxide solution were added. The reaction was continued for 4 hours. After filtration, washing, rotary evaporation and drying, eugenol glycidyl ether was obtained.

[0066] Step 2: Under nitrogen protection, acrylic-modified rosin was dissolved in toluene, and eugenol glycidyl ether, triethylamine, and hydroquinone were added. The mixture was reacted at 120°C for 6 hours to obtain rosin diesters. The molar ratio of acrylic-modified rosin to eugenol glycidyl ether was 1:2.2; the mass of triethylamine was 0.8% of the mass of acrylic-modified rosin; and the mass of hydroquinone was 0.8% of the mass of eugenol glycidyl ether.

[0067] Step 3: Mix 10 parts of rosin diester, 6 parts of hyperbranched unsaturated resin, 20 parts of fluorinated mercapto-based organosilicon, and 5 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone evenly, and irradiate with 400nm ultraviolet light for 50 minutes at an irradiation intensity of 30mW / cm². 2 This yields a thickener;

[0068] The preparation method of hyperbranched unsaturated resin is as follows:

[0069] Six parts of hydroxyl-terminated hyperbranched polyester, 4.8 parts of isocyanate methacrylate and 0.18 parts of dibutyltin dilaurate were mixed evenly and reacted at 70°C for 6 hours. After cooling to room temperature, the mixture was filtered, washed and dried to obtain hyperbranched unsaturated resin.

[0070] The preparation method of fluorinated mercapto organosilicon is as follows:

[0071] Fluorinated mercaptosilane was prepared by reacting trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol at 140 °C for 6 h under p-toluenesulfonic acid catalysis and followed by vacuum distillation. The molar ratio of trifluoropropanetrimethoxysilane to mercaptopropyltrimethoxysilane was 1:1; the amount of neopentyl glycol was 2.0 times the total molar amount of trifluoropropanetrimethoxysilane and mercaptopropylalkoxysilane; and the mass of p-toluenesulfonic acid was 3% of the total mass of trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol.

[0072] Comparative Example 1: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0073] Compared with Example 2, Comparative Example 1 replaced the tackifier with the same mass of acrylic-modified rosin, and the other steps were the same as in Example 2.

[0074] Comparative Example 2: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0075] Compared with Example 2, Comparative Example 2 replaced the tackifier with the same mass of rosin diester, and the other steps were the same as in Example 2.

[0076] Comparative Example 3: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0077] The preparation method of the thickener is as follows:

[0078] Step 1: Under nitrogen protection, 8 parts of eugenol and 24 parts of epichlorohydrin were mixed, and 0.32 parts of benzyltriethylammonium chloride were used as catalysts. The mixture was reacted at 105°C for 4 hours. The temperature was then lowered to 55°C, and 8 parts of 35wt% sodium hydroxide solution were added. The reaction was continued for 3 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether was obtained.

[0079] Step 2: Under nitrogen protection, acrylic-modified rosin was dissolved in toluene, and eugenol glycidyl ether, triethylamine, and hydroquinone were added. The mixture was reacted at 115°C for 5 hours to obtain rosin diesters. The molar ratio of acrylic-modified rosin to eugenol glycidyl ether was 1:2.1; the mass of triethylamine was 0.6% of the mass of acrylic-modified rosin; and the mass of hydroquinone was 0.6% of the mass of eugenol glycidyl ether.

[0080] Step 3: Mix 8 parts of rosin diester, 16 parts of fluorinated mercaptosilicone, and 3.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone evenly, and irradiate with 380nm ultraviolet light for 40 minutes at an irradiation intensity of 25mW / cm². 2 This yields a thickener;

[0081] Compared with Example 2, Comparative Example 3 did not introduce hyperbranched unsaturated resin, and the other steps were the same as in Example 2.

[0082] Comparative Example 4: A method for preparing a TPO waterproof metal fusion panel, comprising the following processes:

[0083] The preparation method of the thickener is as follows:

[0084] Step 1: Under nitrogen protection, 8 parts of eugenol and 24 parts of epichlorohydrin were mixed, and 0.32 parts of benzyltriethylammonium chloride were used as catalysts. The mixture was reacted at 105°C for 4 hours. The temperature was then lowered to 55°C, and 8 parts of 35wt% sodium hydroxide solution were added. The reaction was continued for 3 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether was obtained.

[0085] Step 2: Under nitrogen protection, acrylic-modified rosin was dissolved in toluene, and eugenol glycidyl ether, triethylamine, and hydroquinone were added. The mixture was reacted at 115°C for 5 hours to obtain rosin diesters. The molar ratio of acrylic-modified rosin to eugenol glycidyl ether was 1:2.1; the mass of triethylamine was 0.6% of the mass of acrylic-modified rosin; and the mass of hydroquinone was 0.6% of the mass of eugenol glycidyl ether.

[0086] Step 3: Mix 8 parts of rosin diester, 4 parts of hyperbranched unsaturated resin, and 3.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-propanone evenly, and irradiate with 380nm ultraviolet light for 40 minutes at an irradiation intensity of 25mW / cm². 2 This yields a thickener;

[0087] Compared with Example 2, Comparative Example 4 did not introduce fluorinated mercaptosilicone, and the other steps were the same as in Example 2.

[0088] Experiment: TPO waterproof metal fusion panels obtained in Examples 1-3 and Comparative Examples 1-4 were used to prepare samples. Their performance was tested and the test results were recorded.

[0089] Peel strength test: After aging the sample in a standard oven at 115℃ for 28 days, the peel strength test was carried out in accordance with T / CBMCA 017-2020 "Clad Steel Sheets for Construction".

[0090] Cross-cut test followed by boiling: Refer to the adhesion (cross-cut method) in T / CBMCA 017-2020 "Covered Steel Sheets for Construction" for cross-cut test. Then boil the cross-cut samples in boiling water for 48 hours and observe whether the samples bulge or peel off. If there are no such phenomena, it is OK; otherwise, it is NG.

[0091] The test results are shown in Table 1.

[0092] Table 1 Performance test results of TPO waterproof metal fusion board

[0093]

[0094] Based on the data in the table above, the following conclusions can be clearly drawn:

[0095] 1. Compared with Examples 1-3, the peel strength and water resistance of the products obtained in Comparative Examples 1, 2 and 4 all decreased, indicating that the present invention effectively improves the mechanical properties and water resistance of the material by modifying acrylic rosin and introducing hyperbranched structure and organosilicon fluorinated segments.

[0096] 2. Compared with Examples 1-3, the peel strength of the product obtained in Comparative Example 3 decreased, indicating that the introduction of hyperbranched unsaturated resin in this invention can further improve the adhesion of the material.

[0097] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A TPO waterproof metal fusion panel, characterized in that: The TPO waterproof metal fusion panel comprises, from bottom to top, a metal plate, an adhesive layer, and a TPO waterproof layer. The adhesive layer comprises the following components by weight: 40-50 parts low-density polyethylene, 15-25 parts maleic anhydride grafted polyolefin, 10-20 parts POE, 10-15 parts phenolic resin, 5-10 parts tackifier, 2-4 parts talc, 1-3 parts coupling agent, 3-5 parts polyethylene wax, and 0.5-0.8 parts antioxidant. The preparation method of the thickener is as follows: Step 1: Under nitrogen protection, eugenol and epichlorohydrin are mixed and benzyltriethylammonium chloride is used as a catalyst. The mixture is reacted at 100-110℃ for 3-5 hours. The temperature is then lowered to 50-60℃, sodium hydroxide solution is added, and the reaction continues for 2-4 hours. After filtration, washing, rotary evaporation, and drying, eugenol glycidyl ether is obtained. Step 2: Under nitrogen protection, acrylic acid-modified rosin is dissolved in toluene, eugenol glycidyl ether, triethylamine and hydroquinone are added, and the mixture is reacted at 110-120℃ for 4-6 hours to obtain rosin diesters. Step 3: Mix rosin diester, hyperbranched unsaturated resin, fluorinated mercapto silicone and photoinitiator evenly, and then irradiate with ultraviolet light to obtain a tackifier; The preparation method of the hyperbranched unsaturated resin is as follows: Hydroxyl-terminated hyperbranched polyester, isocyanate methacrylate and dibutyltin dilaurate are mixed evenly and reacted at 60-70℃ for 4-6 hours. After cooling to room temperature, the mixture is filtered, washed and dried to obtain hyperbranched unsaturated resin. The preparation method of the fluorinated mercapto organosilicon is as follows: Trifluoropropanetrimethoxysilane, mercaptopropyltrimethoxysilane, and neopentyl glycol were reacted at 120-140℃ for 4-6 h under p-toluenesulfonic acid catalysis, followed by vacuum distillation to obtain fluorinated mercaptosilicone.

2. The TPO waterproof metal fusion plate according to claim 1, characterized in that: The maleic anhydride-grafted polyolefin is maleic anhydride-grafted polypropylene or maleic anhydride-grafted polyethylene.

3. The TPO waterproof metal fusion plate according to claim 1, characterized in that: In step one, the mass ratio of eugenol, epichlorohydrin, benzyltriethylammonium chloride and sodium hydroxide solution is 1:(2-4):(0.03-0.05):(0.8-1.5), and the concentration of sodium hydroxide solution is 30-40wt%.

4. The TPO waterproof metal fusion plate according to claim 1, characterized in that: In step two, the molar ratio of acrylic acid-modified rosin to eugenol glycidyl ether is 1:(2.0-2.2).

5. The TPO waterproof metal fusion plate according to claim 1, characterized in that: In step three, the mass ratio of rosin diester, hyperbranched unsaturated resin, fluorinated mercapto silicone and photoinitiator is 1:(0.4-0.6):(1.5-2.0):(0.3-0.5).

6. The TPO waterproof metal fusion plate according to claim 1, characterized in that: The coupling agent is 3-aminopropyltrimethoxysilane.

7. A method for preparing a TPO waterproof metal fusion plate according to any one of claims 1-6, characterized in that: Includes the following steps: Step S1: Mix maleic anhydride-grafted polyolefin, low-density polyethylene, POE, phenolic resin, tackifier, talc, coupling agent, polyethylene wax and antioxidant evenly, melt extrude and calender to obtain adhesive layer; Step S2: Preheat and bond one side of the TPO waterproof layer and adhesive layer at 120-140℃; then press the metal plate onto the other side of the adhesive layer and hot-press it at 140-160℃, then cool it to room temperature to obtain the TPO waterproof metal fusion plate.

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