Photovoltaic floor containing modified rosin grease bio-based adhesive film

Abstract

The invention discloses a photovoltaic floor containing a modified rosin grease bio-based adhesive film, and relates to the technical field of photovoltaic building integration, and the photovoltaic floor is formed by laying a first glass plate, a rosin glue solution, a battery piece, a rosin glue solution and a second glass plate in sequence. S1, the rosin glue solution comprises rosin modified thermocuring, and S2, the rosin modified thermocuring comprises the following materials in parts by weight: 50-80 parts of abietic acid and 20-40 parts of glacial acetic acid (gt); and S3, adding 50-80 parts of abietic acid into a 250mL round-bottom flask, arranging a magnetic stirrer, a dropping funnel, an N2 inlet and a thermometer, continuously flushing the round-bottom flask with nitrogen in the whole reaction process, and continuously stirring the round-bottom flask with the nitrogen until the volume of the round-bottom flask is less than 80%, so as to obtain the abietic acid. The method comprises the following steps: heating and stirring 20-40 parts of glacial acetic acid (gt; 80%) until the glacial acetic acid is molten;

Description

Technical Field

[0001] The invention relates to the technical field of photovoltaic building integration, in particular to a photovoltaic floor containing a modified rosin grease bio-based adhesive film. Background Art

[0002] Traditional thermal power generation has the disadvantages of high energy consumption and large amounts of greenhouse gas emissions. Photovoltaic power generation is a clean, renewable energy source. Existing photovoltaic power generation equipment often takes up more space and is therefore mainly used in sparsely populated areas. Combining photovoltaics with building structures, vegetable oils (glycerol-derived triglycerides and different long-chain unsaturated fatty acids) are promising alternatives to renewable polymer raw materials and are widely used in different fields due to their low toxicity, low cost and easy access15-19. Vegetable oils are flexible, elastic, hydrophobic and have a low glass transition temperature (Tg). Epoxidized vegetable oil (EPO) is a typical vegetable oil derivative, which is formed by oxidation of double bonds with peroxide acids. Among vegetable oils, soybean oil is second only to palm oil in terms of usage. Rosin consists of nearly 10% neutral and 90% acidic compounds and has been used as adhesives, tackifiers, paints, soaps, sealing waxes, plasters and varnishes. The rigid hydrogenated phenanthrene ring of rosin makes it a potential substitute for traditional petroleum-based monomers. Therefore, rosin acid and its derivatives have been used as raw materials for polymer materials in recent years. Existing photovoltaic floors cannot combine photovoltaic tiles with buildings to build photovoltaic floors. The application range of photovoltaic tiles is limited, increasing dependence on petroleum resources.

[0003] The defects of existing photovoltaic floors are:

[0004] 1. Patent document CN111576783A discloses an indoor low-deformation photovoltaic floor, "including a substrate with a cavity extending in the horizontal direction, vertical plates extending upward from both sides of the substrate, a support surface sunken and arranged between the two vertical plates, and installation cavities arranged on both sides of the support surface, wherein a photovoltaic assembly is arranged in the installation cavity, and the photovoltaic assembly includes at least one group of photovoltaic cells arranged horizontally, a transparent shell is arranged on the outside of the photovoltaic cells, and a circuit board is connected to the bottom of the photovoltaic cells. Through the indoor low-deformation photovoltaic floor, it can be easily adapted to the high-temperature use environment indoors, its thermal deformation is small, it is not easy to be damaged, and it has good life and safety", but the existing photovoltaic floor cannot combine photovoltaic tiles with buildings to build photovoltaic floors, the application scope of photovoltaic tiles is limited, and the dependence on oil resources is increased;

[0005] 2. Patent document CN112832482A discloses a compact photovoltaic floor installation assembly, "including a rectangular photovoltaic power generation panel, the photovoltaic power generation panel includes a glass surface layer, a photovoltaic layer, and a glass back layer stacked in sequence, and long strip long side support frames are provided on both sides of the width direction of the photovoltaic power generation panel, and the inner side of the long side support frame is bonded to the photovoltaic power generation panel through a first structural adhesive layer, and a long strip support plate is provided on the inner side of the long side support frame corresponding to the lower side of the photovoltaic power generation panel, and the lower side of the photovoltaic power generation panel is placed on the two support plates and bonded through a second structural adhesive layer sandwiched between the photovoltaic power generation panel and the support plate, and long strip short side support frames are provided on both sides of the length direction of the photovoltaic power generation panel, and the two sides of the short side support frame in the length direction extend to the two sides of the width direction of the photovoltaic power generation panel, and the inner side of the short side support frame close to the photovoltaic power generation panel is bonded to the photovoltaic power generation panel through a third structural adhesive layer. This assembly has a simple and compact structure, and the installation structure occupies a small area, does not occupy public space, and the overall photovoltaic panel area accounts for a large proportion", but the existing photovoltaic floor combines photovoltaic tiles with buildings to build photovoltaic floors, and the application range of photovoltaic tiles is limited, increasing dependence on oil resources;

[0006] 3. Patent document CN108442643A discloses a non-slip and non-shielding photovoltaic floor, "including several photovoltaic modules located at the top, spacers located between adjacent photovoltaic modules, a support frame located at the bottom, plugs and fixing accessories located on both sides; the support frame is provided with a convex card slot matching the size of the photovoltaic module, the side of the convex card slot is concave to form a first receiving slot that penetrates the support frame, and the bottom of the convex card slot is concave to form a second receiving slot that penetrates the support frame; the photovoltaic module includes a light-transmitting upper panel and a supporting lower panel, and a photovoltaic battery group is installed on the supporting lower panel; the photovoltaic battery group includes more than two photovoltaic cells connected in parallel, and a bypass diode reversely connected to the photovoltaic cell cell is also connected in parallel; the top of the support frame is flush with the photovoltaic module and is provided with anti-slip grooves. While providing friction and ensuring the safety of pedestrians, it fully utilizes ground solar energy to generate electricity and solves the technical problem that partial shielding affects the power generation performance of the system", but the existing photovoltaic floor combines photovoltaic tiles with buildings to build photovoltaic floors. The application scope of photovoltaic tiles is limited, increasing dependence on oil resources;

[0007] 4. Patent document CN208122174U discloses a photovoltaic heating floor, "including a plate body, the side of the plate body is provided with side holes, the top surface of the plate body is provided with anti-slip grooves, the plate body is divided into a surface layer, a chip layer, a central reinforcement layer, a shock-absorbing layer and a bottom layer; the chip layer is provided with heating chips, the heating chips are interconnected by copper wires, the end of the copper wire away from the heating chip is fixedly connected with an external ring, and the central reinforcement layer is provided with mutually staggered reinforcement plates. The utility model is provided with a soft material through the shock-absorbing layer, the soft material can effectively reduce the shock of the floor, and can also preserve heat, so that users have a good experience during use, the bottom layer is provided with a woven layer, the woven layers are staggered, the woven layers have the advantages of being firm and durable, and at the same time, the bottom of the plate body has the advantages of being earthquake-resistant and heat-insulating, so that the service life of the device is extended and the effect is improved", but the existing photovoltaic floor combines photovoltaic tiles with buildings to construct photovoltaic floors, the application range of photovoltaic tiles is limited, and the dependence on petroleum resources is increased. Summary of the invention

[0008] The purpose of the present invention is to provide a photovoltaic floor containing a modified rosin oil bio-based adhesive film to solve the technical problem raised in the above background technology that the existing photovoltaic floor combines photovoltaic tiles with buildings to construct photovoltaic floors, the application range of photovoltaic tiles is limited, and the dependence on petroleum resources is increased.

[0009] To achieve the above object, the present invention provides the following technical solution: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a No. 1 glass plate, rosin adhesive, a battery cell, rosin adhesive, and a No. 2 glass plate;

[0010] The preparation steps of the rosin sizing solution are as follows:

[0011] S1. Rosin glue includes rosin modified thermosetting;

[0012] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0013] S3. The specific production process according to the materials in S2 is as follows: 50 to 80 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 20 to 40 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180° C. to 190° C. and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230° C. to 250° C., 10 to 30 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230° C. to 240° C. for 5 hours. The crude product is collected after being cooled to 170° C. to 180° C., and washed three times with water to remove unreacted raw materials to obtain substance A.

[0014] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0015] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 5-12 parts of tetrabutyl titanate (0.03 mol%) dissolved in xylene is added, the temperature is increased to 220°C-230°C, and the vacuum reaction is maintained at 70-100Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form a rosin glue solution. The carboxyl-terminated polymerization between SEA and 1,2-PDO is carried out in the same manner.

[0016] Preferably, the photovoltaic floor further comprises a substrate film, and the substrate film is one of a PET film and a glass cloth.

[0017] Preferably, rosin glue is applied to the surface of the substrate film, and the rosin glue is formed into a bio-based adhesive film by heating, ultraviolet light irradiation or chemical cross-linking. The bio-based adhesive film is located between the rosin glue, the No. 1 glass plate and the battery cell.

[0018] Preferably, 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin glue solution and mixed to prevent the rosin glue solution from oxidative degradation during the preparation and use process and to improve the stability of the rosin glue solution.

[0019] Preferably, the photovoltaic floor is hot-pressed at 140°C to 160°C for 0.5 hour after vacuum evacuation, so that the rosin glue is in contact with the No. 1 glass plate and the battery cell. During hot pressing, the distance between the No. 1 glass plate and the No. 2 glass plate is 3mm to 5mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film.

[0020] Preferably, the photovoltaic floor of the modified rosin grease bio-based adhesive film is put into use after edge cutting and wiring treatment.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The present invention is equipped with a 250mL round-bottom flask, a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 20 to 40 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 10 to 30 parts of acrylic acid are dropwise added within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, washed with water three times, and unreacted raw materials are removed to obtain substance A, so that the viscosity of the photovoltaic floor adhesive film of the present invention is significantly improved, the artistry and interest of the product are increased, and the application range and adhesion strength of the photovoltaic tiles are expanded;

[0023] 2. The present invention is equipped with a 250mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 20 to 40 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 10 to 30 parts of acrylic acid are dropwise added within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, washed three times with water, and unreacted raw materials are removed to obtain substance A, so that the utilization rate of petroleum resources of the photovoltaic floor of the present invention is significantly reduced, which is conducive to reducing dependence on petroleum resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a front view structural schematic diagram of the present invention;

[0025] Figure 2It is a schematic diagram of experimental data of the present invention.

[0026] In the figure: 1. Glass plate No. 1; 2. Rosin glue; 3. Battery cell; 4. Glass plate No. 2. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "front end", "rear end", "two ends", "one end", "the other end" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0029] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "provided with", "connected", etc. should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0030] Example 1: Please refer to Figure 1 and Figure 2 , an embodiment provided by the present invention: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a first glass plate 1, a rosin adhesive solution 2, a battery cell 3, a rosin adhesive solution 2, and a second glass plate 4;

[0031] The preparation steps of the rosin glue solution 2 are as follows:

[0032] S1, rosin glue 2 includes rosin modified thermal curing;

[0033] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0034] S3. The specific production process according to the materials in S2 is as follows: 60 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 30 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 20 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0035] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0036] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 8 parts of tetrabutyl titanate (0.03 mol%) dissolved in xylene is added, the temperature is raised to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form rosin glue 2. The carboxyl-terminated poly (propyl ester) between SEA and 1,2-PDO is carried out in the same manner. The photovoltaic floor also includes a substrate film, which is one of a PET film and a glass cloth. The surface of the substrate film is coated with rosin glue 2, and the rosin glue 2 is formed by heating, ultraviolet light irradiation or chemical crosslinking. A bio-based adhesive film is formed, and the bio-based adhesive film is located between the rosin adhesive liquid 2, the first glass plate 1 and the battery cell 3. 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin adhesive liquid 2, and mixed to prevent the rosin adhesive liquid 2 from oxidative degradation during the preparation and use process to improve the stability of the rosin adhesive liquid 2. The photovoltaic floor is vacuum-evacuated and hot-pressed at 140° C. to 160° C. for 0.5 hour to make the rosin adhesive liquid 2 contact with the first glass plate 1 and the battery cell 3. During the hot pressing, the distance between the first glass plate 1 and the second glass plate 4 is 3 mm to 5 mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film. The photovoltaic floor with the modified rosin oil bio-based adhesive film is put into use after edge chamfering and wiring treatment.

[0037] Example 2: Please refer to Figure 1 and Figure 2 , an embodiment provided by the present invention: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a first glass plate 1, a rosin adhesive solution 2, a battery cell 3, a rosin adhesive solution 2, and a second glass plate 4;

[0038] The preparation steps of the rosin glue solution 2 are as follows:

[0039] S1, rosin glue 2 includes rosin modified thermal curing;

[0040] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0041] S3. The specific production process according to the materials in S2 is as follows: 70 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 35 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 25 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0042] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0043] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 9 parts of tetrabutyl titanate (0.03 mol%) dissolved in xylene is added, the temperature is raised to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form rosin glue 2. The carboxyl-terminated poly (propyl ester) between SEA and 1,2-PDO is carried out in the same manner. The photovoltaic floor also includes a substrate film, which is one of a PET film and a glass cloth. The surface of the substrate film is coated with rosin glue 2, and the rosin glue 2 is formed by heating, ultraviolet light irradiation or chemical crosslinking. A bio-based adhesive film is formed, and the bio-based adhesive film is located between the rosin adhesive liquid 2, the first glass plate 1 and the battery cell 3. 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin adhesive liquid 2, and mixed to prevent the rosin adhesive liquid 2 from oxidative degradation during the preparation and use process to improve the stability of the rosin adhesive liquid 2. The photovoltaic floor is vacuum-evacuated and hot-pressed at 140° C. to 160° C. for 0.5 hour to make the rosin adhesive liquid 2 contact with the first glass plate 1 and the battery cell 3. During the hot pressing, the distance between the first glass plate 1 and the second glass plate 4 is 3 mm to 5 mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film. The photovoltaic floor with the modified rosin oil bio-based adhesive film is put into use after edge chamfering and wiring treatment.

[0044] Example 3: Please refer to Figure 1 and Figure 2, an embodiment provided by the present invention: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a first glass plate 1, a rosin adhesive solution 2, a battery cell 3, a rosin adhesive solution 2, and a second glass plate 4;

[0045] The preparation steps of the rosin glue solution 2 are as follows:

[0046] S1, rosin glue 2 includes rosin modified thermal curing;

[0047] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0048] S3. The specific production process according to the materials in S2 is as follows: 75 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 25 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 15 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0049] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0050] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 10 parts of dimethylbenzene tetrabutyl titanate (0.03 mol%) is added, the temperature is increased to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form rosin glue 2. The carboxyl-terminated poly (propyl ester) between SEA and 1,2-PDO is carried out in the same manner. The photovoltaic floor also includes a substrate film, which is one of a PET film and a glass cloth. The surface of the substrate film is coated with rosin glue 2, and the rosin glue 2 is formed by heating, ultraviolet light irradiation or chemical crosslinking. A bio-based adhesive film is formed, and the bio-based adhesive film is located between the rosin adhesive liquid 2, the first glass plate 1 and the battery cell 3. 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin adhesive liquid 2, and mixed to prevent the rosin adhesive liquid 2 from oxidative degradation during the preparation and use process to improve the stability of the rosin adhesive liquid 2. The photovoltaic floor is vacuum-evacuated and hot-pressed at 140° C. to 160° C. for 0.5 hour to make the rosin adhesive liquid 2 contact with the first glass plate 1 and the battery cell 3. During the hot pressing, the distance between the first glass plate 1 and the second glass plate 4 is 3 mm to 5 mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film. The photovoltaic floor with the modified rosin oil bio-based adhesive film is put into use after edge chamfering and wiring treatment.

[0051] Example 4: Please refer to Figure 1 and Figure 2 , an embodiment provided by the present invention: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a first glass plate 1, a rosin adhesive solution 2, a battery cell 3, a rosin adhesive solution 2, and a second glass plate 4;

[0052] The preparation steps of the rosin glue solution 2 are as follows:

[0053] S1, rosin glue 2 includes rosin modified thermal curing;

[0054] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0055] S3. The specific production process according to the materials in S2 is as follows: 55 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 28 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 28 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0056] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0057] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 11 parts of dimethylbenzene tetrabutyl titanate (0.03 mol%) is added, the temperature is increased to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form rosin glue 2. The carboxyl-terminated poly (propyl ester) between SEA and 1,2-PDO is carried out in the same manner. The photovoltaic floor also includes a substrate film, which is one of a PET film and a glass cloth. The surface of the substrate film is coated with rosin glue 2, and the rosin glue 2 is formed by heating, ultraviolet light irradiation or chemical crosslinking. A bio-based adhesive film is formed, and the bio-based adhesive film is located between the rosin adhesive liquid 2, the first glass plate 1 and the battery cell 3. 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin adhesive liquid 2, and mixed to prevent the rosin adhesive liquid 2 from oxidative degradation during the preparation and use process to improve the stability of the rosin adhesive liquid 2. The photovoltaic floor is vacuum-evacuated and hot-pressed at 140° C. to 160° C. for 0.5 hour to make the rosin adhesive liquid 2 contact with the first glass plate 1 and the battery cell 3. During the hot pressing, the distance between the first glass plate 1 and the second glass plate 4 is 3 mm to 5 mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film. The photovoltaic floor with the modified rosin oil bio-based adhesive film is put into use after edge chamfering and wiring treatment.

[0058] Example 5: Please refer to Figure 1 and Figure 2, an embodiment provided by the present invention: a photovoltaic floor containing a modified rosin grease bio-based adhesive film, comprising: a photovoltaic floor formed by laying in the order of a first glass plate 1, a rosin adhesive solution 2, a battery cell 3, a rosin adhesive solution 2, and a second glass plate 4;

[0059] The preparation steps of the rosin glue solution 2 are as follows:

[0060] S1, rosin glue 2 includes rosin modified thermal curing;

[0061] S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (>80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0062] S3. The specific production process according to the materials in S2 is as follows: 80 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 40 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, and 30 parts of acrylic acid are added dropwise within 20 minutes. The mixture is then maintained isothermally at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0063] S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5-7.5:2-3.5:1.2-3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor;

[0064] S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 12 parts of tetrabutyl titanate (0.03 mol%) dissolved in xylene is added, the temperature is raised to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form rosin glue 2. The carboxyl-terminated poly (propyl ester) between SEA and 1,2-PDO is carried out in the same manner. The photovoltaic floor also includes a substrate film, which is one of a PET film and a glass cloth. The surface of the substrate film is coated with rosin glue 2, and the rosin glue 2 is formed by heating, ultraviolet light irradiation or chemical crosslinking. A bio-based adhesive film is formed, and the bio-based adhesive film is located between the rosin adhesive liquid 2, the first glass plate 1 and the battery cell 3. 10 to 15 parts by weight of butylated hydroxytoluene is added to the rosin adhesive liquid 2, and mixed to prevent the rosin adhesive liquid 2 from oxidative degradation during the preparation and use process to improve the stability of the rosin adhesive liquid 2. The photovoltaic floor is vacuum-evacuated and hot-pressed at 140° C. to 160° C. for 0.5 hour to make the rosin adhesive liquid 2 contact with the first glass plate 1 and the battery cell 3. During the hot pressing, the distance between the first glass plate 1 and the second glass plate 4 is 3 mm to 5 mm, forming a photovoltaic floor with a modified rosin oil bio-based adhesive film. The photovoltaic floor with the modified rosin oil bio-based adhesive film is put into use after edge chamfering and wiring treatment.

[0065] Comparative experiment:

[0066] The difference between Comparative Example 1 and Example 1 is that;

[0067] The rosin-modified thermal curing agent includes the following materials in parts by weight: 50 to 80 parts of rosin acid, 20 to 40 parts of glacial acetic acid (>80%), 10 to 30 parts of acrylic acid, and 5 to 12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0068] S3. The specific production process according to the materials in S2 is as follows: 60 parts of rosin acid are added into a 250 mL round-bottom flask, and equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 30 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added into the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize into levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 20 parts of acrylic acid are dropwise added within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0069] The difference between Comparative Example 1 and Example 2 is that;

[0070] The rosin-modified thermal curing agent includes the following materials in parts by weight: 50 to 80 parts of rosin acid, 20 to 40 parts of glacial acetic acid (>80%), 10 to 30 parts of acrylic acid, and 5 to 12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0071] S3. The specific production process according to the materials in S2 is as follows: 70 parts of rosin acid are added into a 250 mL round-bottom flask, and equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 35 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added into the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize into levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 25 parts of acrylic acid are dropwise added within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0072] The difference between Comparative Example 1 and Example 3 is that;

[0073] The rosin-modified thermal curing agent includes the following materials in parts by weight: 50 to 80 parts of rosin acid, 20 to 40 parts of glacial acetic acid (>80%), 10 to 30 parts of acrylic acid, and 5 to 12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0074] S3. The specific production process according to the materials in S2 is as follows: 75 parts of rosin acid are added into a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 25 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added into the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize into levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 15 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0075] The difference between Comparative Example 1 and Example 4 is that;

[0076] The rosin-modified thermal curing agent includes the following materials in parts by weight: 50 to 80 parts of rosin acid, 20 to 40 parts of glacial acetic acid (>80%), 10 to 30 parts of acrylic acid, and 5 to 12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0077] S3. The specific production process according to the materials in S2 is as follows: 55 parts of rosin acid are added into a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 28 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added into the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C to 190°C and maintained for 4 hours to isomerize into levorotatory pimaric acid. The temperature is then increased to 230°C to 250°C, 28 parts of acrylic acid are dropwise added within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0078] The difference between Comparative Example 1 and Example 5 is that;

[0079] The rosin-modified thermal curing agent includes the following materials in parts by weight: 50 to 80 parts of rosin acid, 20 to 40 parts of glacial acetic acid (>80%), 10 to 30 parts of acrylic acid, and 5 to 12 parts of xylene tetrabutyl titanate (0.03 mol%);

[0080] S3. The specific production process according to the materials in S2 is as follows: 80 parts of rosin acid are added into a 250 mL round-bottom flask, and equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 40 parts of glacial acetic acid (>80%) are heated and stirred until melted, and added into the round-bottom flask to form a mixture A. Then the mixture A is heated to 180°C to 190°C and maintained for 4 hours to isomerize into levorotatory pimaric acid. Then the temperature is increased to 230°C to 250°C, 30 parts of acrylic acid are added dropwise within 20 minutes, and then the temperature is maintained at 230°C to 240°C for 5 hours. The crude product is collected after being cooled to 170°C to 180°C, and washed three times with water to remove unreacted raw materials to obtain substance A.

[0081] The photovoltaic floors of Examples 1, 2, 3, 4 and 5 of the present invention and the traditional photovoltaic floor (Comparative Example 1) were subjected to experiments on the utilization rate of petroleum resources and the viscosity of adhesive films, and their values ​​were calculated and statistically analyzed. The results are shown in the table:

[0082] Oil resource utilization rate (%) Film viscosity (cps) Example 1 1 15000 Example 2 1.3 15500 Example 3 0.8 16000 Example 4 0.9 14900 Example 5 1.2 15100 Comparative Example 1 2 13500

[0083] From the data in Table 1, it can be seen that the viscosity of the adhesive film of the photovoltaic floor using Examples 1, 2, 3, 4 and 5 of the present invention are 15000, 15500, 16000, 14900 and 15100 respectively, which are significantly higher than the viscosity of the adhesive film of the photovoltaic floor in Comparative Example 1. This shows that the viscosity of the adhesive film of the photovoltaic floor of the present invention is significantly improved, which increases the artistry and interest of the product and expands the application range and adhesion strength of the photovoltaic tiles.

[0084] From the data in Table 1, it can be seen that the petroleum resource utilization rates of the photovoltaic floors in Examples 1, 2, 3, 4 and 5 of the present invention are 1, 1.3, 0.8, 0.9 and 1.2 respectively, which are significantly lower than the petroleum resource utilization rate of the photovoltaic floor in Comparative Example 1. This indicates that the petroleum resource utilization rate of the photovoltaic floor of the present invention is significantly reduced, which is beneficial to reducing dependence on petroleum resources.

[0085] It will be apparent to those skilled in the art that the 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 features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A photovoltaic floor containing a modified rosin grease bio-based adhesive film, characterized in that: include: The photovoltaic floor is formed by laying out in the order of a No. 1 glass plate (1), rosin glue (2), a battery cell (3), rosin glue (2), and a No. 2 glass plate (4); The preparation steps of the rosin sizing solution (2) are as follows: S1, rosin glue (2) including rosin modified thermosetting; S2, rosin modified thermosetting comprising the following materials in parts by weight: 50-80 parts of rosin acid, 20-40 parts of glacial acetic acid (> 80%), 10-30 parts of acrylic acid, 5-12 parts of xylene tetrabutyl titanate (0.03 mol%); S3. The specific production process according to the materials in S2 is as follows: 50-80 parts of rosin acid are added to a 250 mL round-bottom flask equipped with a magnetic stirrer, a dropping funnel, a N2 inlet and a thermometer. During the entire reaction process, the round-bottom flask is continuously flushed with nitrogen to prevent oxidation and remove water vapor generated during the polymerization process. 20-40 parts of glacial acetic acid (> 80%) are heated and stirred until melted, and added to the round-bottom flask to form a mixture A. The mixture A is then heated to 180°C-190°C and maintained for 4 hours to isomerize to levorotatory pimaric acid. The temperature is then increased to 230°C-250°C, and 10-30 parts of acrylic acid are added dropwise within 20 minutes. The mixture is then maintained isothermally at 230°C-240°C for 5 hours. The crude product is collected after being cooled to 170°C-180°C, and washed three times with water to remove unreacted raw materials to obtain substance A. S4, according to S3, substance A, 1,2-PDO and ARA are placed in a round-bottom flask in a ratio of 5~7.5:2~3.5:1.2~3 to form a mixture B, wherein a Dean-Stark apparatus, an Allihn condenser and a mechanical stirrer are installed. During the entire transesterification reaction, the mixture is continuously purged with a nitrogen flow to prevent oxidation and remove water vapor; S5. According to S4, the mixture is first heated to 180°C-190°C and maintained for 4 hours, and then 5-12 parts of tetrabutyl titanate (0.03 mol%) dissolved in xylene is added, the temperature is raised to 220°C-230°C, and the vacuum reaction is maintained at 70-100 Pa for 7 hours to obtain a carboxyl-terminated polymer, which is cooled to room temperature and poured out from the reactor to form a rosin glue solution (2). The carboxyl-terminated polymerization between SEA and 1,2-PDO is carried out in the same manner.

2. The photovoltaic floor containing modified rosin grease bio-based adhesive film according to claim 1, characterized in that: The photovoltaic floor further comprises a substrate film, and the substrate film is one of a PET film and a glass cloth.

3. The photovoltaic floor containing modified rosin grease bio-based adhesive film according to claim 2, characterized in that: A rosin glue liquid (2) is applied to the surface of the substrate film, and the rosin glue liquid (2) is subjected to heating, ultraviolet light irradiation or chemical cross-linking to form a bio-based glue film, wherein the bio-based glue film is located between the rosin glue liquid (2), the first glass plate (1) and the battery cell (3).

4. The photovoltaic floor containing modified rosin grease bio-based adhesive film according to claim 1, characterized in that: 10 to 15 parts by weight of butylated hydroxytoluene are added to the rosin glue solution (2) and mixed to prevent the rosin glue solution (2) from oxidative degradation during the preparation and use process, thereby improving the stability of the rosin glue solution (2).

5. The photovoltaic floor containing modified rosin grease bio-based adhesive film according to claim 1 or 3, characterized in that: The photovoltaic floor is subjected to vacuum evacuation and then hot-pressed at 140°C to 160°C for 0.5 hours, so that the rosin glue (2) is in contact with the first glass plate (1) and the battery cell (3). During the hot-pressing, the distance between the first glass plate (1) and the second glass plate (4) is 3 mm to 5 mm, thereby forming a photovoltaic floor with a modified rosin oil bio-based glue film.

6. The photovoltaic floor containing modified rosin grease bio-based adhesive film according to claim 5, characterized in that: The photovoltaic floor of the modified rosin grease bio-based adhesive film is put into use after edge cutting and wiring treatment.

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