Waterproof membrane based on biomass modified asphalt and biomass polyester base

Abstract

The invention discloses a waterproofing coiled material based on biomass modified asphalt and biomass polyester base. The method steps of preparing the waterproofing coiled material with prepared raw materials are as follows: a. heating the modified biomass asphalt, adding the prepared heavy calcium filler into the modified biomass asphalt after heating and stirring to obtain a composition, and then pumping the composition into the modified biomass asphalt tank; b. sending the bio-based polyethylene furandicarboxylate base into the modified biomass asphalt tank for soaking; c. scraping off the excess asphalt from the bio-based polyethylene furandicarboxylate base soaked with the modified biomass asphalt; d. cooling the surface of the bio-based polyethylene furandicarboxylate base after removing the excess modified biomass asphalt; e. after cooling the surface, a PE isolation layer coated with silicone oil is attached to the surface to obtain the finished waterproofing coiled material. The problem that the performance of the existing biomass waterproofing material in various aspects cannot be compared with that of the traditional waterproofing material is solved.

Description

Technical Field

[0001] The invention relates to the field of waterproofing coiled materials, in particular to a waterproofing coiled material based on biomass modified asphalt and a biomass polyester base. Background Art

[0002] With the continuous development of modern construction technology, waterproofing is an important part of ensuring the quality and service life of buildings. Although traditional waterproof materials can meet the waterproofing needs to a certain extent, they still need to be improved in terms of durability, environmental protection, anti-aging performance, etc. Especially in the current context of global advocacy of green, low-carbon and sustainable development, it is particularly important to develop a new waterproof material that is both efficient and environmentally friendly.

[0003] As a new type of environmentally friendly material, biomass modified asphalt has received extensive attention in the field of building waterproofing in recent years. It introduces biomass materials into asphalt, changes the chemical structure and physical properties of asphalt, and improves the elasticity, anti-aging and durability of asphalt. Compared with traditional petroleum asphalt, biomass modified asphalt is not only abundant and renewable, but also has less impact on the environment during the production process, which is in line with the current development trend of green building materials. At the same time, as an important component of waterproofing membrane, the quality and performance of polyester base directly affect the overall effect of waterproofing membrane. Traditional polyester bases are mostly made of petroleum-based materials. Although they have stable performance, they are expensive and not environmentally friendly. Therefore, developing a polyester base based on biomass materials can not only reduce production costs, but also improve the environmental performance of products.

[0004] Although the application of the above two materials in the field of waterproof membranes has a good prospect, there is no case of combining the two materials in the field of waterproof membranes. The specific reason is that although the current modified asphalt has improved the elasticity, aging resistance and durability of asphalt through the introduction of biomass materials, there is still a certain gap in performance compared with petroleum asphalt, and the polyester base based on biomass materials still has a certain difference in material strength from the base made of petroleum-based materials. Therefore, the performance of the waterproof membrane made by combining the two cannot reach the performance of traditional waterproof membranes. Moreover, as far as the current biomass materials are concerned, the adhesion of biomass modified asphalt is often insufficient, so it is even more difficult to combine well with the biomass polyester base. Forcing the two to be used together will affect the quality of the final waterproof membrane. Based on the above defects, the present invention proposes a waterproof membrane based on biomass modified asphalt and a biomass polyester base. Summary of the invention

[0005] The purpose of the present invention is to provide a waterproof roll material based on biomass modified asphalt and biomass polyester base, so as to solve the problem that the performance of the existing waterproof material made by combining biomass modified asphalt and biomass polyester base cannot be compared with that of traditional waterproof materials.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A waterproofing membrane based on biomass modified asphalt and biomass polyester base, the raw materials include modified biomass asphalt, heavy calcium filler and bio-based polyethylene furandicarboxylate base, and the method for preparing the waterproofing membrane using the above raw materials includes the following steps: a. heating the modified biomass asphalt, adding the prepared heavy calcium filler to the modified biomass asphalt after heating and stirring to obtain a composition, and then pumping the composition into a modified biomass asphalt tank; b. sending the bio-based polyethylene furandicarboxylate base into the modified biomass asphalt tank for soaking; c. scraping off excess asphalt from the bio-based polyethylene furandicarboxylate base soaked with modified biomass asphalt; d. cooling the bio-based polyethylene furandicarboxylate base after removing excess modified biomass asphalt on its surface; e. pasting a PE isolation layer coated with silicone oil on its surface after cooling treatment to obtain a finished waterproofing membrane.

[0008] As a further preferred embodiment of the present invention, the preparation method of the modified biomass asphalt includes the following steps: S1, preparing 95-105 parts of base asphalt, 4.75-5.25 parts of biomass oil and 4.5-6.1 parts of high-temperature tackifier by mass as raw materials for preparing modified biomass asphalt; S2, heating the prepared base asphalt, adding the prepared biomass oil to the base asphalt after heating and stirring it fully, and obtaining biomass asphalt after stirring fully; S3, further heating the obtained biomass asphalt, slowly and evenly adding the prepared high-temperature tackifier thereto after further heating, and stirring until the material is completely melted to obtain modified biomass asphalt.

[0009] High temperature tackifiers are added to improve asphalt properties, including;

[0010] 1. Improve the bonding strength between modified asphalt and bio-based polyethylene furandicarboxylate base, so that the overall strength of the roll is improved; improve the bonding effect between modified asphalt and the base interface such as cement-based layer, and prevent water leakage due to water seepage;

[0011] 2. High temperature adhesive can improve the high temperature performance of asphalt (increase the softening point), prevent the softening of asphalt at high temperature from causing deformation of waterproof membrane, thus affecting the waterproof effect;

[0012] 3. High-temperature adhesives can improve the elasticity of asphalt, allowing the waterproof membrane to maintain a certain deformation capacity under the action of external force, and quickly return to its original state after the external force disappears, thereby improving the fatigue resistance of the waterproof membrane.

[0013] The further heating in S3 is specifically heating based on S2, specifically raising the temperature from 135-140°C to 170°C-180°C.

[0014] Preferably, the mass fraction of the base asphalt is 100 parts, the mass fraction of the biomass oil is 5 parts, and the mass fraction of the high-temperature tackifier is 5 parts.

[0015] As a further preferred embodiment of the present invention, the preparation method of the biomass oil is to mix 20-25 parts of rice straw dried to constant weight, 67.5-84.4 parts of liquefier and 12.5-15.6 parts of catalyst evenly and place them in a reactor, seal it and introduce N2 protection, adjust the initial reaction pressure to 5MPa, react at 140℃-150℃ for 120min, and obtain the biomass oil after the above reaction is completed.

[0016] Preferably, the mass fraction of the rice straw dried to a constant weight is 20 parts, the mass fraction of the liquefier is 67.5 parts, and the mass fraction of the catalyst is 12.5 parts.

[0017] As a further preferred embodiment of the present invention, the liquefier is composed of glycerol, PEG 400, and phenol in a mass ratio of 3:7:10, and the catalyst is 20% sulfuric acid.

[0018] In the straw liquefier, propylene glycol is used as a stabilizer, which can prevent the condensation reaction between small molecules of the product and improve the product quality.

[0019] PEG-400 is used as a solvent and solubilizer in straw liquefiers. PEG-400 can effectively dissolve and disperse cellulose, hemicellulose and other organic components in straw. As a solubilizer, PEG-400 can improve the fluidity of the liquefier, help the liquid product to penetrate and act on the straw more evenly, and help the straw to liquefy better.

[0020] The role of phenol in straw liquefaction agent is mainly reflected in its degradation, solvent effect and ability to provide active hydrogen.

[0021] As a nucleophilic reagent with a lone pair of electrons and a π bond, phenol can easily undergo electrophilic substitution with electrophilic reagents on the aromatic ring. This chemical property enables phenol to effectively break certain chemical bonds in straw, especially the bonds of lignin β-O-4 and the glycosidic bonds between cellulose sugar rings. This breaking action helps to degrade macromolecules in straw into small molecular fragments, further promoting the liquefaction process of straw. Secondly, phenol also has a hydrogenated aromatic structure and a phenolic hydroxyl structure, which enables it to be used as a solvent and provide a large amount of active hydrogen. Under high temperature conditions, the lignin macromolecules in straw may undergo free radical reactions under the action of phenol, a hydrogen-donating solvent, and break into a large number of low-molecular fragments. These fragments further form low-molecular-weight compounds through the breaking of side chain CC bonds, CO bonds and aromatic ring CO bonds, thereby achieving efficient liquefaction of straw.

[0022] This ratio is obtained through experiments, taking into account the higher yield and better stability of biomass oil.

[0023] As a further preferred embodiment of the present invention, the high temperature tackifier is obtained by compounding SBS and SBR at a mass ratio of 1:0.2-0.5.

[0024] As a further preference of the present invention, the reaction conditions of each step in the preparation process of the modified biomass asphalt are as follows: heating the prepared base asphalt in the step S2 specifically refers to heating it to 135-140°C, and sufficient stirring refers to stirring at 900-950r / min for 40-50min; further heating the obtained biomass asphalt in the step S3 refers to heating the biomass asphalt obtained in the step S2 to 170°C-180°C, and slowly and evenly adding the prepared high-temperature tackifier thereto while stirring at a speed of 400-600 r / min.

[0025] Preferably, in S2, the prepared base asphalt is heated to 135° C., and fully stirred at 950 r / min for 45 minutes.

[0026] As a further preferred embodiment of the present invention, the preparation method of the bio-based polyethylene furandicarboxylate tire base includes the following steps: K1, esterifying the bio-based aromatic monomer FDCA with EG to synthesize PEF; K2, melting the PEF synthesized in K1 and adding glass fiber, and then extruding or calendering, and the bio-based polyethylene furandicarboxylate tire base can be obtained after extrusion or calendering.

[0027] As a further preferred embodiment of the present invention, the mass ratio of the bio-based aromatic monomer FDCA to EG in step K1 is 1:0.59-1:0.73, and the conditions for the esterification reaction are as follows:

[0028] First, oligomers were prepared through esterification reaction. FDCA and EG were put into a vacuum reactor according to the mass ratio, and the catalyst butyl titanate (the mass ratio of the catalyst to the mass ratio of FDCA was 1:200) and the antioxidant triphenyl phosphite (the mass ratio of the auxiliary agent to the mass ratio of FDCA was between 1:142.9 and 1:121.5) were added. Under the protection of N2, the temperature was slowly raised from 60 ° C to 180 ° C for direct esterification. After the reaction system reached the clear point, the reaction continued until no liquid precipitated in the condenser, and the esterification was terminated to form oligomers.

[0029] Then, continue to slowly evacuate to below 600 Pa, heat to 210~250 ℃ and stir at 200 r / min for pre-polycondensation, and the reaction is completed after 120 minutes. After the pre-polycondensation is completed, the reaction system is evacuated to high vacuum. As the reaction proceeds, the viscosity of the reactants increases, and the stirrer speed is increased to 400 r / min. After 45~60 minutes of reaction, the polycondensation is completed.

[0030] Finally, a phenol / tetrachloroethane mixed solution with a mass ratio of 1:1 was used as a solvent to completely dissolve the PHF product obtained by polycondensation and filter out the insoluble matter. Methanol was added to the solution to obtain a precipitate, which was filtered out after the precipitate no longer increased, and dissolved again. The above steps were repeated 3 times, and the precipitate was taken out and dried to obtain the purified product of PEF.

[0031] As a further preferred embodiment of the present invention, the mass ratio of the glass fiber added to the PEF is 1:200.

[0032] The influence of adding glass fiber on waterproof membrane is mainly reflected in the following aspects:

[0033] 1. Enhanced mechanical properties: As an inorganic non-metallic material, glass fiber has the characteristics of high strength and high modulus. When it is added to the base material, it can significantly enhance the tensile strength and tear strength of the coil, thereby improving the overall mechanical properties of the coil.

[0034] 2. Improve durability: Glass fiber has excellent chemical stability and corrosion resistance, which enables the waterproof membrane with glass fiber added to the base to show better resistance to chemical corrosive media such as acid and alkali, thereby extending the service life of the membrane.

[0035] 3. Improve thermal stability: Glass fiber has good thermal stability and can maintain the stable shape of the base material under the high temperature and tension environment during the production and processing of waterproof membranes without deformation or damage.

[0036] As a further preference of the present invention, the reaction conditions of each step in the process of preparing the waterproof membrane are as follows: heating the modified biomass asphalt in the step a specifically refers to heating the modified bio-asphalt to 160°C-165°C, adding the prepared heavy calcium filler to the modified biomass asphalt specifically refers to adding 120-150 mesh heavy calcium filler to the modified biomass asphalt, and the added amount is 27%-33% of the mass of the modified bio-asphalt. After adding, stirring at a speed of 400-500 r / min for 30-45 minutes can obtain a composition; after scraping off the excess asphalt in the step c, a biomass modified asphalt waterproof layer of a specified thickness can be formed, and the film thickness of the biomass modified asphalt after scraping off the excess asphalt is 1.2mm.

[0037] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0038] 1. Environmental sustainability: Biomass asphalt comes from animal and plant resources, such as waste wood, crop straw, waste animal and plant oils, etc. These resources are renewable. Compared with petroleum asphalt, its extraction and processing process produces less wastewater and waste gas, and the pollution to the environment is relatively low. Therefore, the use of biomass asphalt helps to reduce dependence on fossil energy, reduce greenhouse gas and pollutant emissions, and thus protect the ecological environment; due to the use of bio-based raw materials, polyethylene furandicarboxylate-based asphalt waterproofing membranes can be more easily decomposed by the natural environment after reaching the end of their service life, thereby reducing pollution to soil and water bodies, which is in line with the development trend of green buildings.

[0039] 2. Excellent waterproof performance: Biomass asphalt has good weather resistance, relatively suitable softening point and viscosity, and can maintain good performance stability in harsh environments such as high temperature, low temperature, and humidity. It improves the fatigue resistance of the mixture and is not prone to cracking and deterioration. This feature gives biomass asphalt a unique advantage in the field of building waterproofing; the polyethylene furandicarboxylate base has good tensile strength and elongation. Glass fiber is added during the production process to further improve the strength of the material, which can effectively resist deformation under the action of external forces and maintain the integrity of the waterproof layer.

[0040] 3. The specifications and sizes of this waterproofing membrane are usually relatively standard, which is convenient for transportation and storage. During construction, it can be laid by hot melt method or cold adhesive method, which is simple to operate, efficient and helps to shorten the construction period.

[0041] 4. Good aging resistance: The presence of carbonaceous particles and low polarizability molecules in biomass asphalt makes it have good anti-aging and UV resistance; the polyethylene furandicarboxylate base material has good weather resistance and chemical corrosion resistance, and can resist the erosion of natural factors such as ultraviolet rays and thermal oxidation, thereby extending the service life of the waterproof layer.

[0042] 5. Economical: Biomass asphalt is derived from animal and plant resources, such as waste wood, crop straw, waste animal and plant oils, etc. These resources are widely available, renewable, and easy to obtain. In addition, the preparation cost of biomass asphalt is relatively low, which makes it more competitive in some resource-scarce areas or projects with high environmental protection requirements. In addition, PEF is synthesized from bio-based monomers 2,5-furandicarboxylic acid (FDCA) and ethylene glycol as raw materials. FDCA as a raw material can be obtained from biomass resources such as starch and cellulose through a series of reactions, and ethylene glycol (EG) can also be obtained from biological raw materials. This characteristic of being derived from renewable biological resources reduces the purchase of petroleum raw materials in the production process of PEF. At the same time, as a recyclable and degradable polymer, PEF can be effectively recycled and processed after use, which can further reduce the cost of using materials.

[0043] 6. The waterproofing membrane tightly combines the biomass polyester base with modified asphalt to form a strong and durable waterproof layer. This waterproofing membrane not only inherits the excellent performance of biomass modified asphalt, but also further improves the durability and environmental protection of the waterproofing membrane by optimizing the base material; in the specific implementation, the present invention achieves an effective improvement in the performance of asphalt by carefully selecting biomass materials and modification processes. At the same time, by optimizing the production process and structural design of the base, the stability and reliability of the waterproofing membrane are ensured. In addition, the present invention also pays attention to the environmental performance of the product, and further reduces the environmental burden in the production process by selecting low-pollution and easily recyclable materials and production processes; in summary, the waterproofing membrane based on biomass modified asphalt and biomass polyester base of the present invention not only conforms to the current development trend in the field of building waterproofing, but also has broad market prospects and application value. With the further promotion and application of this technology, it is believed that it will bring revolutionary changes to the field of building waterproofing and make positive contributions to the sustainable development of society. DETAILED DESCRIPTION

[0044] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The components of the embodiments of the present invention described and shown herein can be arranged and designed in various different configurations.

[0045] Therefore, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. 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.

[0046] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features of the embodiments may be combined with each other. Specific embodiment 1:

[0048] A waterproofing roll based on biomass modified asphalt and biomass polyester base, wherein the modified biomass asphalt is heated to 160°C, and after heating, a prepared 120-mesh heavy calcium filler is added to the modified biomass asphalt and stirred at a speed of 450 r / min for 35 minutes to obtain a composition, wherein the amount of the heavy calcium filler added is 30% of the mass of the modified bio-asphalt, and then the composition is pumped into a modified biomass asphalt tank; b. a bio-based polyethylene furandicarboxylate base is sent into the modified biomass asphalt tank for soaking; c. excess asphalt is scraped off the bio-based polyethylene furandicarboxylate base soaked in the modified biomass asphalt, and the film thickness of the biomass modified asphalt after the excess asphalt is scraped off is 1.2 mm; d. after removing the excess modified biomass asphalt on the surface of the bio-based polyethylene furandicarboxylate base, the base is cooled; e. after the cooling treatment, a PE isolation layer coated with silicone oil is attached to the surface to obtain a finished waterproofing roll;

[0049] The preparation method of the modified biomass asphalt comprises the following steps: S1, preparing 100 parts of base asphalt, 5 parts of biomass oil and 5 parts of high-temperature tackifier by weight as raw materials for preparing the modified biomass asphalt; S2, heating the prepared base asphalt, adding the prepared biomass oil into the base asphalt after heating and stirring it fully, and obtaining the biomass asphalt after stirring it fully; S3, further heating the obtained biomass asphalt, slowly and evenly adding the prepared high-temperature tackifier thereto after further heating, and stirring until the material is completely melted to obtain the modified biomass asphalt;

[0050] The preparation method of the biomass oil is as follows: 20 parts of rice straw dried to a constant weight, 67.5 parts of a liquefier and 12.5 parts of a catalyst are mixed evenly and placed in a reactor, and N2 protection is introduced after sealing, and the initial reaction pressure is adjusted to 5 MPa, and the reaction is carried out at 140° C. for 120 min, and the biomass oil can be obtained after the above reaction is completed;

[0051] The liquefier is prepared by mixing glycerol, PEG 400 and phenol in a mass ratio of 3:7:10, and the catalyst is 20% sulfuric acid;

[0052] The high temperature tackifier is prepared by compounding SBS and SBR in a mass ratio of 1:0.2;

[0053] The reaction conditions of each step in the preparation process of the modified biomass asphalt are as follows: the heating of the prepared base asphalt in step S2 specifically refers to heating it to 135°C, and the sufficient stirring is stirring at 950r / min for 45min; the further heating of the obtained biomass asphalt in step S3 refers to heating the biomass asphalt obtained in step S2 to 180°C, and slowly and evenly adding the prepared high-temperature tackifier thereto while stirring at a speed of 500 r / min;

[0054] The preparation method of the bio-based polyethylene furandicarboxylate tire base comprises the following steps: K1, esterifying the bio-based aromatic monomer FDCA with EG to synthesize PEF; K2, melting the PEF synthesized in K1, adding glass fiber, and then extruding or calendering to obtain the bio-based polyethylene furandicarboxylate tire base;

[0055] In step K1, the mass ratio of the bio-based aromatic monomers FDCA and EG is 1:0.59, and the conditions for the esterification reaction are as follows:

[0056] First, oligomers were prepared through esterification reaction. FDCA and EG were put into a vacuum reactor according to the mass ratio, and the catalyst butyl titanate (the mass ratio of the catalyst to the mass ratio of FDCA was 1:200) and the antioxidant triphenyl phosphite (the mass ratio of the auxiliary agent to the mass ratio of FDCA was 1:130) were added. Under the protection of N2, the temperature was slowly raised from 60 ° C to 180 ° C for direct esterification. After the reaction system reached the clear point, the reaction continued until no liquid precipitated in the condenser, and the esterification was terminated to form oligomers;

[0057] Then, continue to slowly evacuate to below 600 Pa, heat to 210°C and stir at 200 r / min for pre-polycondensation, which is completed after 120 min. After the pre-polycondensation is completed, the reaction system is evacuated to high vacuum. As the reaction proceeds, the viscosity of the reactants increases, and the stirrer speed is increased to 400 r / min. After 60 min of reaction, the polycondensation is terminated.

[0058] Finally, a phenol / tetrachloroethane mixed solution with a mass ratio of 1:1 was used as a solvent to completely dissolve the PHF product obtained by polycondensation and filter out the insoluble matter. Methanol was added to the solution to obtain a precipitate, which was filtered out after the precipitate no longer increased, and dissolved again. The above steps were repeated 3 times, and the precipitate was taken out and dried to obtain the purified product of PEF;

[0059] The mass ratio of the added amount of the glass fiber to the PEF is 1:200. Specific embodiment 2:

[0061] A waterproofing roll based on biomass modified asphalt and biomass polyester base, wherein the modified biomass asphalt is heated to 165°C, and after heating, a prepared 130-mesh heavy calcium filler is added to the modified biomass asphalt and stirred at a speed of 500 r / min for 45 minutes to obtain a composition, wherein the amount of the heavy calcium filler added is 27% of the mass of the modified bio-asphalt, and then the composition is pumped into a modified biomass asphalt tank; b. a bio-based polyethylene furandicarboxylate base is sent into the modified biomass asphalt tank for soaking; c. excess asphalt is scraped off the bio-based polyethylene furandicarboxylate base soaked in the modified biomass asphalt, and the film thickness of the biomass modified asphalt after the excess asphalt is scraped off is 1.2 mm; d. after removing the excess modified biomass asphalt on the surface of the bio-based polyethylene furandicarboxylate base, the base is cooled; e. after the cooling treatment, a PE isolation layer coated with silicone oil is attached to the surface to obtain a finished waterproofing roll;

[0062] The preparation method of the modified biomass asphalt comprises the following steps: S1, preparing 105 parts of base asphalt, 4.75 parts of biomass oil and 6.1 parts of high-temperature tackifier by mass as raw materials for preparing modified biomass asphalt; S2, heating the prepared base asphalt, adding the prepared biomass oil into the base asphalt after heating and stirring it fully, and obtaining biomass asphalt after stirring it fully; S3, further heating the obtained biomass asphalt, slowly and evenly adding the prepared high-temperature tackifier thereto after further heating, and stirring until the material is completely melted to obtain modified biomass asphalt;

[0063] The preparation method of the biomass oil is as follows: 22 parts of rice straw dried to a constant weight, 80 parts of a liquefier and 15 parts of a catalyst are mixed evenly and placed in a reactor, and N2 protection is introduced after sealing, and the initial reaction pressure is adjusted to 5 MPa, and the reaction is carried out at 150° C. for 120 min, and the biomass oil can be obtained after the above reaction is completed;

[0064] The liquefier is prepared by mixing glycerol, PEG 400 and phenol in a mass ratio of 3:7:10, and the catalyst is 20% sulfuric acid;

[0065] The high temperature tackifier is prepared by compounding SBS and SBR in a mass ratio of 1:0.5;

[0066] The reaction conditions of each step in the preparation process of the modified biomass asphalt are as follows: the heating of the prepared base asphalt in step S2 specifically refers to heating it to 140°C, and the sufficient stirring is stirring at 900r / min for 40min; the further heating of the obtained biomass asphalt in step S3 refers to heating the biomass asphalt obtained in step S2 to 170°C, and slowly and evenly adding the prepared high-temperature tackifier thereto while stirring at a speed of 400r / min;

[0067] The preparation method of the bio-based polyethylene furandicarboxylate tire base comprises the following steps: K1, esterifying the bio-based aromatic monomer FDCA with EG to synthesize PEF; K2, melting the PEF synthesized in K1, adding glass fiber, and then extruding or calendering to obtain the bio-based polyethylene furandicarboxylate tire base;

[0068] In step K1, the mass ratio of the bio-based aromatic monomers FDCA and EG is 1:0.65, and the conditions for the esterification reaction are as follows:

[0069] First, oligomers were prepared through esterification reaction. FDCA and EG were put into a vacuum reactor according to the mass ratio, and the catalyst butyl titanate (the mass ratio of the catalyst to the mass ratio of FDCA was 1:200) and the antioxidant triphenyl phosphite (the mass ratio of the auxiliary agent to the mass ratio of FDCA was 1:142.9) were added. Under the protection of N2, the temperature was slowly raised from 60 °C to 180 °C for direct esterification. After the reaction system reached the clear point, the reaction continued until no liquid precipitated in the condenser, and the esterification was terminated to form oligomers.

[0070] Then, continue to slowly evacuate to below 600 Pa, raise the temperature to 230 °C and stir at 200 r / min for pre-polycondensation, which is completed after 120 min. After the pre-polycondensation is completed, the reaction system is evacuated to high vacuum. As the reaction proceeds, the viscosity of the reactants increases, and the stirrer speed is increased to 400 r / min. After 45 min of reaction, the polycondensation is terminated.

[0071] Finally, a phenol / tetrachloroethane mixed solution with a mass ratio of 1:1 was used as a solvent to completely dissolve the PHF product obtained by polycondensation and filter out the insoluble matter. Methanol was added to the solution to obtain a precipitate, which was filtered out after the precipitate no longer increased, and dissolved again. The above steps were repeated 3 times, and the precipitate was taken out and dried to obtain the purified product of PEF;

[0072] The mass ratio of the added amount of the glass fiber to the PEF is 1:200. Specific embodiment 3:

[0074] A waterproofing roll based on biomass modified asphalt and biomass polyester base, wherein the modified biomass asphalt is heated to 162°C, and after heating, a prepared 150-mesh heavy calcium filler is added to the modified biomass asphalt and stirred at a speed of 400 r / min for 30 minutes to obtain a composition, wherein the amount of the heavy calcium filler added is 33% of the mass of the modified bio-asphalt, and then the composition is pumped into a modified biomass asphalt tank; b. a bio-based polyethylene furandicarboxylate base is sent into the modified biomass asphalt tank for soaking; c. excess asphalt is scraped off the bio-based polyethylene furandicarboxylate base soaked in the modified biomass asphalt, and the film thickness of the biomass modified asphalt after the excess asphalt is scraped off is 1.2 mm; d. after removing the excess modified biomass asphalt on the surface of the bio-based polyethylene furandicarboxylate base, the base is cooled; e. after the cooling treatment, a PE isolation layer coated with silicone oil is attached to the surface to obtain a finished waterproofing roll;

[0075] The preparation method of the modified biomass asphalt comprises the following steps: S1, preparing 95 parts of base asphalt, 5.25 parts of biomass oil and 4.5 parts of high-temperature tackifier by weight as raw materials for preparing modified biomass asphalt; S2, heating the prepared base asphalt, adding the prepared biomass oil into the base asphalt after heating and stirring it fully, and obtaining biomass asphalt after stirring it fully; S3, further heating the obtained biomass asphalt, slowly and evenly adding the prepared high-temperature tackifier thereto after further heating, and stirring until the material is completely melted to obtain modified biomass asphalt;

[0076] The preparation method of the biomass oil is as follows: 25 parts of rice straw dried to a constant weight, 84.4 parts of a liquefier and 15.6 parts of a catalyst are mixed evenly and placed in a reactor, and N2 protection is introduced after sealing, and the initial reaction pressure is adjusted to 5MPa, and the reaction is carried out at 145°C for 120min, and the biomass oil can be obtained after the above reaction is completed;

[0077] The liquefier is prepared by mixing glycerol, PEG 400 and phenol in a mass ratio of 3:7:10, and the catalyst is 20% sulfuric acid;

[0078] The high temperature tackifier is prepared by compounding SBS and SBR in a mass ratio of 1:0.3;

[0079] The reaction conditions of each step in the preparation process of the modified biomass asphalt are as follows: the heating of the prepared base asphalt in step S2 specifically refers to heating it to 138°C, and the sufficient stirring is stirring at 920r / min for 50min; the further heating of the obtained biomass asphalt in step S3 refers to heating the biomass asphalt obtained in step S2 to 178°C, and slowly and evenly adding the prepared high-temperature tackifier thereto while stirring at a speed of 600 r / min;

[0080] The preparation method of the bio-based polyethylene furandicarboxylate tire base comprises the following steps: K1, esterifying the bio-based aromatic monomer FDCA with EG to synthesize PEF; K2, melting the PEF synthesized in K1, adding glass fiber, and then extruding or calendering to obtain the bio-based polyethylene furandicarboxylate tire base;

[0081] The mass ratio of the bio-based aromatic monomers FDCA and EG in step K1 is FDCA:EG:1:0.73, and the conditions for the esterification reaction are as follows:

[0082] First, oligomers were prepared through esterification reaction. FDCA and EG were put into a vacuum reactor according to the mass ratio, and the catalyst butyl titanate (the mass ratio of the catalyst to the mass ratio of FDCA was 1:200) and the antioxidant triphenyl phosphite (the mass ratio of the auxiliary agent to the mass ratio of FDCA was 1:121.5) were added. Under the protection of N2, the temperature was slowly raised from 60 °C to 180 °C for direct esterification. After the reaction system reached the clear point, the reaction continued until no liquid precipitated in the condenser, and the esterification was terminated to form oligomers.

[0083] Then, continue to slowly evacuate to below 600 Pa, heat to 250 °C and stir at 200 r / min for pre-polycondensation, which is completed after 120 min. After the pre-polycondensation is completed, the reaction system is evacuated to high vacuum. As the reaction proceeds, the viscosity of the reactants increases, and the stirrer speed is increased to 400 r / min. After 50 min of reaction, the polycondensation is terminated.

[0084] Finally, a phenol / tetrachloroethane mixed solution with a mass ratio of 1:1 was used as a solvent to completely dissolve the PHF product obtained by polycondensation and filter out the insoluble matter. Methanol was added to the solution to obtain a precipitate, which was filtered out after the precipitate no longer increased, and dissolved again. The above steps were repeated 3 times, and the precipitate was taken out and dried to obtain the purified product of PEF;

[0085] The mass ratio of the added amount of the glass fiber to the PEF is 1:200.

[0086] The product in Example 1 was tested, and the test results are as follows:

[0087] The detection method is carried out according to the method disclosed in GB 23441-2009 "Self-adhesive polymer modified bitumen waterproof membrane" PY type I.

[0088]

[0089] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A waterproofing roll based on biomass modified asphalt and biomass polyester base, characterized by: The raw materials include modified biomass asphalt, heavy calcium filler and bio-based polyethylene furandicarboxylate base. The method for preparing a waterproof roll material using the above raw materials includes the following steps: a. heating the modified biomass asphalt, adding the prepared heavy calcium filler to the modified biomass asphalt after heating and stirring to obtain a composition, and then pumping the composition into a modified biomass asphalt tank; b. sending the bio-based polyethylene furandicarboxylate base into the modified biomass asphalt tank for soaking; c. scraping off excess asphalt from the bio-based polyethylene furandicarboxylate base soaked with modified biomass asphalt; d. cooling the bio-based polyethylene furandicarboxylate base after removing excess modified biomass asphalt from the base; e. pasting a PE isolation layer coated with silicone oil on the surface after the cooling treatment to obtain a finished waterproof membrane; The preparation method of the bio-based polyethylene furandicarboxylate tire base comprises the following steps: K1, esterifying the bio-based aromatic monomer FDCA with EG to synthesize PEF; K2, melting the PEF synthesized in K1, adding glass fiber to blend, and then extruding or calendering to obtain the bio-based polyethylene furandicarboxylate tire base; In step K1, the mass ratio of the bio-based aromatic monomers FDCA and EG is 1:0.59-1:0.73; The mass ratio of the added amount of the glass fiber to the mass of the PEF is 1:200; The preparation method of the modified biomass asphalt includes the following steps: S1, preparing 95-105 parts of base asphalt, 4.75-5.25 parts of biomass oil and 4.5-6.1 parts of high-temperature tackifier by mass as raw materials for preparing modified biomass asphalt; S2, heating the prepared base asphalt, adding the prepared biomass oil into the base asphalt after heating and stirring it fully, and obtaining biomass asphalt after stirring fully; S3, further heating the obtained biomass asphalt, slowly and evenly adding the prepared high-temperature tackifier thereto after further heating, and stirring until the material is completely melted to obtain modified biomass asphalt.

2. The waterproofing roll based on biomass modified asphalt and biomass polyester base according to claim 1, characterized in that: The preparation method of the biomass oil comprises the following steps: uniformly mixing 20-25 parts of rice straw dried to a constant weight, 67.5-84.4 parts of a liquefier and 12.5-15.6 parts of a catalyst and placing the mixture in a reactor, sealing the reactor and introducing N2 for protection, adjusting the initial reaction pressure to 5MPa, reacting the mixture at 140°C-150°C for 120 minutes, and obtaining the biomass oil after the reaction is completed.

3. The waterproof roll material based on biomass modified asphalt and biomass polyester base according to claim 2, characterized in that: The liquefier is prepared from propylene glycol, PEG 400 and phenol in a mass ratio of 3:7:10, and the catalyst is 20% sulfuric acid.

4. The waterproofing roll based on biomass modified asphalt and biomass polyester base according to claim 1, characterized in that: The high temperature tackifier is obtained by compounding SBS and SBR in a mass ratio of 1:0.2-0.

5.

5. The waterproofing roll based on biomass modified asphalt and biomass polyester base according to claim 1, characterized in that: The reaction conditions of each step in the preparation process of the modified biomass asphalt are as follows: heating the prepared base asphalt in step S2 specifically refers to heating it to 135-140°C, and sufficient stirring is stirring at 900-950r / min for 40-50min; further heating the obtained biomass asphalt in step S3 refers to heating the biomass asphalt obtained in step S2 to 170°C-180°C, and slowly and evenly adding the prepared high-temperature tackifier thereto while stirring at a speed of 400-600 r / min.

6. The waterproofing roll based on biomass modified asphalt and biomass polyester base according to claim 1, characterized in that: The reaction conditions of each step in the process of preparing the waterproof membrane are as follows: heating the modified biomass asphalt in the step a specifically refers to heating the modified bio-asphalt to 160°C-165°C, adding the prepared heavy calcium filler to the modified biomass asphalt specifically refers to adding 120-150 mesh heavy calcium filler to the modified biomass asphalt, and the added amount is 27%-33% of the mass of the modified bio-asphalt. After adding, stirring at a speed of 400-500 r / min for 30-45 minutes can obtain a composition; the scraping of excess asphalt in the step c specifically refers to the film thickness of the biomass modified asphalt after scraping is 1.2-2.0mm, so as to form a biomass modified asphalt waterproof layer.

Images