High performance asphalt-based waterproofing membrane modifier and method of making

Abstract

This invention provides a high-performance asphalt-based waterproof membrane modifier and its preparation method, belonging to the field of waterproof membrane manufacturing. The invention comprises: a novel thermoplastic elastomer, a moderately pyrolyzed rubber polymer, and polyisobutylene rubber. The moderately pyrolyzed rubber polymer is obtained by mixing rubber powder and a first free radical scavenger through stirring and high-temperature pyrolysis. The novel thermoplastic elastomer is obtained by chemical grafting the moderately pyrolyzed rubber polymer, the thermoplastic elastomer, and a second free radical scavenger. The asphalt-based waterproof membrane prepared by the high-performance asphalt-based waterproof membrane modifier of this invention exhibits excellent resistance to heat, oxygen / UV aging, and adhesion; excellent high-temperature anti-flow and low-temperature crack resistance; and can significantly extend the service life of building waterproofing layers.

Description

Technical Field

[0001] This invention relates to the field of asphalt modification technology, and in particular to a high-performance asphalt-based waterproof membrane modifier and its preparation method, belonging to the field of waterproof membrane manufacturing technology. Background Technology

[0002] With economic development and societal progress, the requirements for building materials in the civil engineering and construction industry are becoming increasingly stringent. Among these, the quality of waterproofing materials has a significant impact on the sealing and water-resistant performance of buildings. Traditional asphalt felt, sealant, and low-quality waterproof membranes can no longer meet the demands of modern development. Currently, elastomeric (SBS) modified bitumen waterproof membranes, characterized by hot-melt application, and self-adhesive polymer-modified bitumen waterproof membranes, which require no open flame and can be applied cold, have become the main waterproofing materials in the construction industry.

[0003] SBS modified bitumen waterproof membrane is a type of waterproof membrane with excellent high-temperature resistance, usable in temperatures ranging from -25°C to +100°C. It exhibits high elasticity and fatigue resistance, elongation up to 150%, and strong puncture and tear resistance. It is suitable for waterproofing projects in cold regions and industrial and civil buildings subject to significant deformation and vibration. Performance characteristics include: good low-temperature flexibility (no cracking at -25°C); high heat resistance (no flow at 90°C); good elongation properties; long service life; easy construction; and low pollution. Self-adhesive polymer-modified bitumen waterproof membrane is a waterproof material made with self-adhesive rubber bitumen formulated with SBS and other synthetic rubbers, tackifiers, and petroleum asphalt as the base material, a strong high-density polyethylene film or aluminum foil as the upper surface material, and a peelable silicone-coated release film or silicone-coated release paper as the lower surface anti-sticking material. It is a promising new type of waterproof material with low-temperature flexibility, self-healing properties, and good adhesion. It can be applied at room temperature, has a fast construction speed, and meets environmental protection requirements.

[0004] Both types of waterproof membranes incorporate elastomeric materials, such as styrene-butadiene block copolymer (SBS / SBR), swelling oil, fillers, and other additives, into the asphalt during the manufacturing process. These are then stirred, ground, and coated onto the base material to form the waterproof membrane. The addition of elastomeric materials as modifiers gives the waterproof membrane excellent high and low temperature performance, adhesion, and puncture resistance. However, as partially exposed waterproofing materials, they must withstand multiple complex climatic conditions, including temperature differences, ultraviolet radiation, and thermo-oxidative stress. Besides basic high and low temperature performance, the early aging resistance of the waterproof membrane directly affects the service life of the building's waterproofing layer. Aging of the membrane under complex climatic conditions mainly involves the elastomeric material modifier and the thermo-oxidative / ultraviolet aging of the asphalt. Thermo-oxidative / ultraviolet aging of the elastomeric material modifier primarily involves the aging of unsaturated double bonds in the main chain, leading to a loss of elasticity and low-temperature performance. Thermo-oxidative / ultraviolet aging of the asphalt primarily involves the transformation of saturated / aromatic components into reconstituted / asphaltite components during thermo-oxidative / ultraviolet aging, causing the asphalt to harden and become brittle.

[0005] To address the aging resistance issue of modified bitumen waterproof membranes, domestic and international efforts have focused on multiple aspects. For the thermo-oxidative / UV aging problem of modifiers in elastomer materials, hydrogenation technology is used to convert the modifier segments into saturated CC segments to improve their aging resistance; appropriate amounts of thermo-oxidative-UV aging accelerators are added to delay the aging effect; and the amount of modifier added is increased to further delay the aging effect. For the aging resistance problem of bitumen, a large amount of aromatic hydrocarbon solvents and some high-molecular polymers are added to improve its aging resistance.

[0006] For the reasons mentioned above, it is necessary to provide a new type of modifier material with excellent comprehensive physical properties and significant aging resistance, so as to fundamentally improve the comprehensive physical properties and aging resistance of modified bitumen waterproof membranes and extend the service life of building waterproof layers. Summary of the Invention

[0007] This invention provides a new high-performance bitumen-based waterproof membrane modifier and its preparation method to solve the technical problem of poor performance of modifiers in the prior art.

[0008] The high-performance bitumen-based waterproof membrane modifier of this invention comprises: a novel thermoplastic elastomer, a moderately pyrolytic rubber polymer, and polyisobutylene rubber in a mass ratio of 75-90:10-20:8-15;

[0009] Among them, the moderately pyrolyzed rubber polymer is prepared by mixing rubber powder and a first free radical scavenger in a mass ratio of 40-70:0.1-0.8 through stirring and high-temperature pyrolysis; the novel thermoplastic elastomer is prepared by chemical grafting of moderately pyrolyzed rubber polymer, thermoplastic elastomer and a second free radical scavenger in a mass ratio of 40-70:30-60:0.1-0.5.

[0010] The first free radical scavenger and the second free radical scavenger are both combinations of one or more of diphenylamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, and 2,6-di-tert-butyl-4-methylphenol;

[0011] The thermoplastic elasticity is any one or more combinations of styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene;

[0012] The high-performance bitumen-based waterproof membrane modifier described above, wherein the acetone-soluble content of the moderately cracked rubber polymer is ≤10% by weight, the trichloroethylene-soluble content is ≥90% by weight, the Mn of the trichloroethylene-soluble content is between 2000-5000 g / mol, and the polymer polydispersity index (PDI) is between 2.5-5.0.

[0013] The high-performance bitumen-based waterproof membrane modifier described above, wherein the acetone-soluble content of the novel thermoplastic elastomer is ≤5% by weight, the trichloroethylene-soluble content is ≥95% by weight, Mn is between 100,000 and 550,000 g / mol, and PDI is between 3.0 and 5.0.

[0014] The high-performance bitumen-based waterproof membrane modifier described above, wherein the polyisobutylene rubber has an Mn ≥ 10000 g / mol, preferably, the Mn is between 20000-45000 g / mol.

[0015] The high-performance bitumen-based waterproof membrane modifier described above, wherein the waste rubber powder is made from any one or more combinations of waste all-steel radial tires, waste semi-steel radial tires, and waste bicycle tires, and its particle size ranges from 40 to 100 mesh.

[0016] This invention also provides a method for preparing the high-performance bitumen-based waterproof membrane modifier as described above, comprising the following steps:

[0017] The rubber powder and the first free radical scavenger are added to a high-speed mixer and mixed for 15-35 minutes until the temperature of the mixed rubber powder is 105-135℃.

[0018] The mixed rubber powder is added to the first-stage screw extruder, and the temperature of the first-stage screw extruder is controlled at 380-430℃;

[0019] The material obtained from the first-stage screw extruder is continuously injected into the second-stage venting screw extruder. The first venting temperature zone of the venting screw extruder is controlled at 270-310℃ and a vacuum is applied with a vacuum degree of 10. -2 -10 -3 pa; The second exhaust temperature zone of the exhaust screw extruder is controlled at 190-230℃ and a vacuum is applied, with a vacuum degree of 10. -4 -10 -6 pa;

[0020] The thermoplastic elastomer, polyisobutylene rubber, and the second free radical scavenger are added to a high-speed mixer and mixed for 5-10 minutes until the material temperature reaches 60-90℃ to obtain mixture A;

[0021] The material and mixture A obtained from the second-stage exhaust extrusion machine are continuously injected into the third-stage screw extruder. The temperature of the third-stage screw extruder is controlled at 190-230℃, and a high-performance bitumen-based waterproof membrane modifier is obtained by extrusion.

[0022] The preparation method of the high-performance bitumen-based waterproof membrane modifier as described above, wherein the first-stage screw extruder is a twin-screw extruder or a three-screw extruder with a screw speed of 50-90 rpm; the second-stage screw extruder is a vented twin-screw extruder or a three-screw extruder with a screw speed of 40-70 rpm; and the third-stage screw extruder is a twin-screw extruder or a three-screw extruder with a screw speed of 60-120 rpm.

[0023] The embodiments of the present invention have at least the following beneficial effects:

[0024] (1) The polymer molecular chain free radicals formed by the moderate cracking of rubber, without the participation of rubber desulfurizers and softening oils, can exist relatively stably under high temperature and oxygen-free conditions. These free radicals are then grafted with styrene-butadiene block copolymer (SBS) / styrene-isoprene-styrene block copolymer (SIS) at the molecular level to form a novel asphalt-based membrane modifier. This novel asphalt-based membrane modifier has stronger resistance to thermo-oxidative / ultraviolet aging, fundamentally improving the aging resistance of asphalt-based waterproof membranes during thermo-oxidative / ultraviolet aging. Furthermore, the novel asphalt-based membrane modifier of this invention has a significantly higher molecular weight than SBS / SIS. When applied to modified asphalt, it significantly enhances the cohesiveness, adhesion, and viscosity of the asphalt, further significantly improving the high and low temperature performance of the modified asphalt.

[0025] (2) Furthermore, in the preparation process of the novel asphalt-based roll material modifier, a free radical scavenger is introduced to effectively avoid oxidation caused by oxygen participation during the mixing and heating stage of waste rubber / SBS / SIS, and to ensure the activity of the moderately pyrolyzed rubber products and the molecular weight uniformity of SBS / SIS as much as possible, thereby increasing the molecular weight of the novel asphalt-based roll material modifier of this invention and further improving the high and low temperature performance and aging resistance of the asphalt-based roll material; a gradient vacuum treatment of the moderately pyrolyzed rubber mixture is introduced to separate the smaller molecular weight free radical fragments formed by the moderate pyrolysis of rubber as much as possible, retain the molecular weight uniform free radical fragments and react chemically with SBS / SIS, thereby increasing the molecular weight and uniformity (PDI) of the novel asphalt-based roll material modifier and further improving the high and low temperature performance and aging resistance of the asphalt-based roll material;

[0026] (3) In the preparation process of the novel asphalt-based roll material modifier of the present invention, an excessive amount of organic polymer with a molecular weight between 2000-5000 obtained by moderate cracking of rubber and gradient vacuum extraction is introduced. The molecular weight of this polymer is similar to that of the aromatics / rubber in asphalt and has good low-temperature flexibility. While effectively improving the heat and oxygen / ultraviolet aging resistance of the matrix asphalt, it can also effectively improve the low-temperature flexibility of the asphalt-based roll material.

[0027] (4) In the preparation process of the novel asphalt-based roofing membrane modifier of this invention, a special elastomer polymer—polyisobutylene rubber—is introduced. Polyisobutylene has the chemical characteristics of saturated hydrocarbon compounds, with tightly and symmetrically distributed methyl groups on its side chains, making it a polymer with unique properties. One of the characteristics of polyisobutylene is its excellent airtightness. Due to the presence of two substituted methyl groups, the molecular chain movement is slow and the free volume is small, resulting in a low diffusion coefficient and gas permeability. Another characteristic is its excellent self-healing properties and excellent puncture resistance. A third characteristic is its good low-temperature flexibility and tackifying properties. The addition of polyisobutylene can further enhance the adhesion, puncture resistance, and low-temperature flexibility of the novel asphalt-based roofing membrane modifier on the roofing membrane.

[0028] (5) Under the combined effect of the above factors, the high-performance asphalt-based roll modifier of the present invention is used to prepare asphalt-based rolls, which greatly improves the heat and oxygen / ultraviolet aging resistance, and has better high-temperature anti-flow, low-temperature anti-cracking, and anti-puncture properties, as well as excellent adhesion / cohesion. In addition, it can consume a large number of waste tires, turn waste into treasure, and increase the added value of waste tire recycling. Detailed Implementation

[0029] The high-performance bitumen-based waterproof membrane modifier and preparation method described in this invention can be made using the following materials and components, but are not limited to these materials and components, such as: rubber powder, antioxidant, membrane, bitumen, etc.

[0030] Examples 1-7:

[0031] Step 1: Add 40-mesh waste all-steel radial tire rubber powder and 2,6-di-tert-butyl-4-methylphenol to a high-speed mixer and mix for 20 minutes until the temperature of the mixed rubber powder reaches 115℃.

[0032] Step 2: Add the mixed rubber powder into the first-stage co-rotating parallel twin-screw extruder, and control the temperature of the first-stage extruder to 420℃;

[0033] Step 3: Continuously inject the material obtained from the first-stage screw extruder into the second-stage venting screw extruder. Control the first venting temperature zone of the venting screw extruder at 290℃ and apply a vacuum of 0.006 Pa; control the second venting temperature zone of the venting screw extruder at 220℃ and apply a vacuum of 10 Pa. -5 pa;

[0034] Step 4: Add SBS (Sinopec Yueyang Petrochemical model: 791-H: Mn: 98000g / mol, PDI: 3.2, trichloroethylene soluble content: 100%) and 2,6-di-tert-butyl-4-methylphenol into a high-speed mixer and mix for 7 minutes until the material temperature reaches 80℃ to obtain mixture A;

[0035] Step 5: The material and mixture A obtained from the second-stage screw extruder are continuously injected into the third-stage screw extruder. The temperature of the third-stage extruder is controlled at 220℃. After the material is melt-mixed and grafted, it is extruded to obtain a high-performance bitumen-based waterproof membrane modifier.

[0036] The difference between Examples 1-7 lies in the different proportions of the rubber powder, elastomer polymer, first / second free radical scavenger, and polyisobutylene rubber, as detailed in Table 1:

[0037] Table 1

[0038]

[0039] Examples 8-12:

[0040] Step 1: Add 55 parts by weight of rubber powder and 0.25 parts by weight of the first free radical scavenger into a high-speed mixer and mix for 20 minutes until the temperature of the mixed rubber powder is 115℃;

[0041] Step 2: Add the mixed rubber powder into the first-stage co-rotating parallel twin-screw extruder, and control the temperature of the first-stage extruder to 420℃;

[0042] Step 3: Continuously inject the material obtained from the first-stage screw extruder into the second-stage venting screw extruder. Control the first venting temperature zone of the venting screw extruder at 290℃ and apply a vacuum of 0.006 Pa; control the second venting temperature zone of the venting screw extruder at 220℃ and apply a vacuum of 10 Pa. -5 pa;

[0043] Step 4: Add 45 parts by weight of SBS (Sinopec Yueyang Petrochemical, model: 791-H: Mn: 98000 g / mol, PDI: 3.2, trichloroethylene soluble content: 100%) or SIS (Sinopec Yueyang Petrochemical, model: 1105, Mn: 185000, PDI: 3.6; trichloroethylene soluble content: 100%), 0.35 parts by weight of the second free radical scavenger, and 8 parts by weight of polyisobutylene to a high-speed mixer and mix for 7 minutes until the material temperature reaches 80°C to obtain mixture A.

[0044] Step 5: The material and mixture A obtained from the second-stage screw extruder are continuously injected into the third-stage screw extruder. The temperature of the third-stage extruder is controlled at 220℃. After the material is melt-mixed and grafted, it is extruded to obtain a high-performance bitumen-based waterproof membrane modifier.

[0045] The difference between Examples 8-12 lies in the different types of rubber powder, elastomeric polymer, and first / second free radical scavengers, as detailed in Table 2.

[0046] Table 2

[0047]

[0048] Comparative Example D1:

[0049] Step 1: Add 55 parts by weight of 40-mesh waste steel radial tire rubber powder and 0.25 parts by weight of antioxidant 264 into a high-speed mixer and mix for 20 minutes until the temperature of the mixed rubber powder is 115℃.

[0050] Step 2: Add the mixed rubber powder into the first-stage co-rotating parallel twin-screw extruder, and control the temperature of the first-stage extruder to 420℃;

[0051] Step 3: Continuously inject the material obtained from the first-stage screw extruder into the second-stage venting screw extruder. Control the first venting temperature zone of the venting screw extruder at 290℃ and apply a vacuum of 0.006 Pa; control the second venting temperature zone of the venting screw extruder at 220℃ and apply a vacuum of 10 Pa. -5 pa;

[0052] Step 4: The material obtained from the second-stage screw extruder is continuously injected into the third-stage co-rotating parallel twin-screw extruder. The temperature of the third-stage extruder is controlled at 50℃ and the screw speed is 50rpm. After cooling, the material is extruded to obtain a moderately pyrolyzed rubber polymer.

[0053] Comparative Example D2:

[0054] Step 1: Add 55 parts by weight of rubber powder into a high-speed mixer and mix for 20 minutes until the temperature of the mixed rubber powder reaches 115℃;

[0055] Step 2: Add the mixed rubber powder into the first-stage co-rotating parallel twin-screw extruder, and control the temperature of the first-stage extruder to 420℃;

[0056] Step 3: Continuously inject the material obtained from the first-stage screw extruder into the second-stage venting screw extruder. Control the first venting temperature zone of the venting screw extruder at 290℃ and apply a vacuum of 0.006 Pa; control the second venting temperature zone of the venting screw extruder at 220℃ and apply a vacuum of 10 Pa. -5 pa;

[0057] Step 4: Add 45 parts by weight of SBS (Sinopec Yueyang Petrochemical, model: 791-H: Mn: 98000 g / mol, PDI: 3.2, trichloroethylene soluble content: 100%) or SIS (Sinopec Yueyang Petrochemical, model: 1105, Mn: 185000, PDI: 3.6; trichloroethylene soluble content: 100%) and 8 parts by weight of polyisobutylene into a high-speed mixer and mix for 7 minutes until the material temperature reaches 80℃ to obtain mixture A;

[0058] Step 5: The material and mixture A obtained from the second-stage screw extruder are continuously injected into the third-stage screw extruder. The temperature of the third-stage extruder is controlled at 220℃. After the material is melt-mixed and grafted, it is extruded to obtain a high-performance bitumen-based waterproof membrane modifier.

[0059] Comparative Example D3:

[0060] Step 1: Add 55 parts by weight of rubber powder and 0.25 parts by weight of the first free radical scavenger into a high-speed mixer and mix for 20 minutes until the temperature of the mixed rubber powder is 115℃;

[0061] Step 2: Add the mixed rubber powder into the first-stage co-rotating parallel twin-screw extruder, and control the temperature of the first-stage extruder to 420℃;

[0062] Step 3: The material obtained from the first-stage screw extruder is continuously injected into the second-stage venting screw extruder. The first venting temperature zone of the venting screw extruder is controlled at 290℃; the second venting temperature zone of the venting screw extruder is controlled at 220℃.

[0063] Step 4: Add 45 parts by weight of SBS (Sinopec Yueyang Petrochemical, model: 791-H: Mn: 98000 g / mol, PDI: 3.2, trichloroethylene soluble content: 100%) or SIS (Sinopec Yueyang Petrochemical, model: 1105, Mn: 185000, PDI: 3.6; trichloroethylene soluble content: 100%), 0.35 parts by weight of the second free radical scavenger, and 8 parts by weight of polyisobutylene to a high-speed mixer and mix for 7 minutes until the material temperature reaches 80°C to obtain mixture A.

[0064] Step 5: The material and mixture A obtained from the second-stage screw extruder are continuously injected into the third-stage screw extruder. The temperature of the third-stage extruder is controlled at 220℃. After the material is melt-mixed and grafted, it is extruded to obtain a high-performance bitumen-based waterproof membrane modifier.

[0065] The above products were processed as follows:

[0066] First, acetone was used as the solvent, and Soxhlet extraction was performed continuously for 48 hours until the small organic molecules (acetone-soluble substances) were completely extracted and separated by acetone. Subsequently, the soluble fraction was dried in a vacuum drying oven until its mass remained constant, and the insoluble fraction was dried until its mass remained constant. Then, a second extraction was performed using trichloroethylene as the solvent to separate the large molecular soluble substances (trichloroethylene-soluble substances) and the insoluble substances.

[0067] The number-average molecular weight and polydispersity index (PDI) of trichloroethylene solubles were tested (GPC testing can simultaneously characterize molecular weight and PDI). The test method is as follows: the trichloroethylene solubles were fully swollen with toluene, and then the number-average molecular weight (Mn) of each component of the sample was determined using a Waters 515-2410 GPC analyzer. n The polydispersity index (PDI) of the polymer was measured, and the weight percentage of different molecular weight components was calculated by peak area. Tetrahydrofuran was used as the mobile phase, polystyrene was used as the standard, and the test temperature was 35℃.

[0068] The composition and formulation of each product are shown in Tables 3 and 4.

[0069] Table 3

[0070]

[0071]

[0072] Table 4

[0073]

[0074] (1) As can be seen from the above examples and Comparative Example 1, raw material SBS (791-H) and raw material SIS (1105), the product after extrusion granulation of the moderately pyrolyzed rubber polymer and SBS / SIS through oxygen-free high-temperature melt blending is not a simple physical blend of multiple materials. Among them, the weight percentage of component one with a smaller molecular weight is significantly lower than the weight percentage when feeding, and the weight percentage of component two with a larger molecular weight is significantly higher than the percentage when feeding. Moreover, the Mn of component two is significantly larger than that of Comparative Example 1 (moderately pyrolyzed rubber polymer) and SBS / SIS, indicating that the thermoplastic elastomer and the moderately pyrolyzed rubber polymer under high temperature and oxygen-free conditions have undergone a chemical reaction, and the moderately pyrolyzed rubber polymer is grafted onto the thermoplastic elastomer backbone.

[0075] (2) As can be seen from the above examples and Comparative Example 2, in the process of melting and mixing reaction of moderately pyrolyzed rubber polymer and thermoplastic elastomer, the free radical scavenger is more important for preventing oxidation during the heating and pyrolysis of rubber powder and the heating process of thermoplastic elastomer. The addition of the free radical scavenger can consume the influence of oxygen / water and other substances that are easy to form free radicals in the raw materials to a greater extent, and reduce the influence on the molecular weight and molecular weight distribution of the high-performance asphalt-based roll modifier.

[0076] (3) As can be seen from the above examples and Comparative Example 3, adding a gradient vacuum step to the second-stage extruder can effectively reduce the influence of free radicals of small organic molecules in the moderately cracked polymer of rubber on the molecular weight and molecular weight distribution of the high-performance asphalt-based roll modifier, and can significantly reduce the weight percentage of small organic molecules with smaller molecular weight in the high-performance asphalt-based roll modifier.

[0077] To illustrate the beneficial effects of the high-performance bitumen-based membrane modifier prepared by the present invention when applied in waterproof membranes, the following exemplary comparison of the performance of waterproof membranes prepared by the high-performance bitumen-based membrane modifier of the present invention and waterproof membranes prepared by conventional methods is provided.

[0078] (1) Self-adhesive polymer-modified bitumen waterproof membrane

[0079] Raw materials: Asphalt: Qinhuangdao No. 90 asphalt (CNPC Qinhuangdao Refinery, physical properties meet the technical requirements of matrix asphalt in JTG F40-2004); Elastomer polymer: SBS (Yueyang Petrochemical 791-H); Filler: Talc powder, mesh size: 400 mesh; Solubilizer: Aromatic oil; Rubber powder: 60 mesh waste radial tire rubber powder; Styrene-butadiene rubber (SBR): Sinopec Shanghai Gaoqiao Petrochemical.

[0080] Preparation steps:

[0081] Asphalt and solubilizer were mixed and heated to 185°C. Elastomer polymer, styrene-butadiene rubber, and a high-performance asphalt-based waterproof membrane modifier were added, and the mixture was stirred and kept at 185°C for swelling. The stirring speed was 800 rpm, and the swelling time was 120 min. Rubber powder was added and stirred and kept at 185°C for 150 min at 800 rpm. Filler was added, and the mixture was stirred and dispersed at 165°C for 1500 rpm and a dispersion time of 60 min. A colloid mill was then used for grinding and homogenization for 15 min at 165°C. The rubber compound was impregnated onto felt using an impregnation method, then coated using a roller coating method, and finally rolled, laminated, cooled, metered, cut, sampled, and tested. The waterproof membrane was then packaged and stored in rolls. The raw materials and formulations for the specific embodiments are shown in Table 5.

[0082] Table 5

[0083]

[0084] The properties of the prepared self-adhesive membrane were characterized. The testing methods and standards were in accordance with GB23441-2009 Self-adhesive Polymer Modified Bituminous Waterproof Membrane, as detailed in Table 6.

[0085] Table 6

[0086]

[0087] To more accurately demonstrate the resistance of the roll material to low-temperature damage during use, the following testing method was used:

[0088] (1) Perforation resistance test: The perforation resistance of the waterproof membrane was tested according to GBT12953-2003 at a test temperature of -30℃; (2) Crack resistance test: The crack resistance of the membrane was tested according to JCT852-1999 at a test temperature of -30℃. The results of the low-temperature damage resistance of the prepared membrane are shown in Table 7.

[0089] Table 7

[0090] Example Perforation resistance (-30℃) Crack resistance (-30℃) 13 Unperforated No cracks Comparative Example 4 perforation cracking Comparative Example 5 perforation cracking Comparative Example 6 perforation cracking Comparative Example 7 Unperforated No cracks

[0091] (2) Elastomer-modified bitumen waterproof membrane

[0092] Raw materials: Asphalt: Qinhuangdao No. 90 asphalt (CNPC Qinhuangdao Refinery, physical properties meet the technical requirements of matrix asphalt in JTG F40-2004); Elastomer polymer: SBS (Yueyang Petrochemical 791-H); Filler: Talc powder, mesh size: 400 mesh; Solubilizer: Aromatic oil; Rubber powder: 60 mesh waste radial truck tire rubber powder; Polymer resin: Polypropylene (PP).

[0093] Preparation steps: Mix asphalt and solubilizer, heat to 195℃, add elastomeric polymer, high molecular weight resin, and high-performance asphalt-based waterproof membrane modifier, stir, and maintain temperature for swelling. Maintain temperature: 195℃, stirring speed: 1200 rpm, swelling time: 150 min; add rubber powder, maintain temperature and stir for 180 min, temperature: 195℃, stirring speed: 1500 rpm; add filler, maintain temperature and stir, disperse, maintain temperature: 180℃, stirring speed: 1500 rpm, dispersion time: 60 min; turn on the colloid mill to grind and homogenize, grinding time: 15 min, temperature: 180℃; the adhesive compound is impregnated onto felt using the impregnation method, then coated using the roller coating method, then rolled into shape, laminated and cooled, metered and cut, sampled and tested, and the waterproof membrane is packaged and stored in rolls. The raw materials and formulations of specific embodiments are shown in Table 8.

[0094] Table 8

[0095]

[0096]

[0097] The physical properties of the prepared roll material were characterized (test method: GB18242-2008), and the results are shown in Table 9.

[0098] Table 9

[0099]

[0100] To more accurately demonstrate the resistance of the roll material to low-temperature damage during use, the following testing method was used:

[0101] (1) Perforation resistance test: The perforation resistance of the waterproof membrane was tested according to GBT12953-2003 at a test temperature of -30℃; (2) Crack resistance test: The crack resistance of the membrane was tested according to JCT852-1999 at a test temperature of -30℃. The results of the low-temperature damage resistance of the prepared membrane are shown in Table 10.

[0102] Table 10

[0103] Example Perforation resistance (-30℃) Crack resistance (-30℃) 14 Unperforated No cracks Comparative Example 8 perforation cracking Comparative Example 9 perforation cracking Comparative Example 10 perforation cracking Comparative Example 11 Unperforated No cracks

[0104] The performance results of the bitumen-based waterproof membrane in the above embodiments show that:

[0105] (1) Under the same addition ratio, compared with Comparative Example 4 / 8, the high and low temperature physical properties of the waterproof membrane prepared by the modifier of the present invention are greatly improved; the cohesion and toughness of the membrane are greatly increased, the adhesion performance of the membrane is greatly increased; and the membrane has stronger resistance to heat and oxygen aging and aging under complex climatic conditions.

[0106] (2) Under the same addition ratio, compared with Comparative Example 5 / 9, the high and low temperature physical properties of the waterproof membrane prepared by the modifier of the present invention are significantly improved; the cohesiveness and adhesive toughness of the membrane are significantly increased, and the adhesive performance of the membrane is significantly improved; the membrane has stronger resistance to heat and oxygen aging and aging under complex climatic conditions. The modifier of the present invention, formed by mixing and melting moderately pyrolytic rubber polymer and thermoplastic elastic and reacting fully, has a better modification effect on asphalt-based membranes.

[0107] (3) Under the same addition ratio, compared with Comparative Example 6 / 10, although the moderately cracked rubber polymer and thermoplastic elastomer were mixed and melted, the free radical scavenger therein had a certain impact on the physical properties of the modifier of the present invention.

[0108] (4) Under the same addition ratio, compared with Comparative Example 7 / 11, the addition of a gradient vacuum step in the second-stage extruder in Example 1 makes the overall physical properties of the modifier of the present invention more superior.

[0109] The sequence numbers of the above embodiments of the present invention are merely for descriptive purposes and do not represent the superiority or inferiority of the embodiments. Through the above description of the embodiments, those skilled in the art can clearly understand that the methods of the above embodiments can be implemented by means of some modifications and the superposition of necessary general technologies; of course, they can also be implemented by simplifying some important technical features. Based on this understanding, the technical solution of the present invention, in essence or the part that contributes to the prior art, is: the overall structure and connection method, and the structure described in the various embodiments of the present invention.

[0110] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance bitumen-based waterproof membrane modifier, characterized in that, include: Novel thermoplastic elastomers, moderately pyrolytic rubber polymers, and polyisobutylene rubbers with a mass ratio of 75-90:10-20:8-15; Among them, the moderately pyrolyzed rubber polymer is prepared by mixing rubber powder and a first free radical scavenger in a mass ratio of 40-70:0.1-0.8 through stirring and high-temperature pyrolysis; the novel thermoplastic elastomer is prepared by chemical grafting of moderately pyrolyzed rubber polymer, thermoplastic elastomer and a second free radical scavenger in a mass ratio of 40-70:30-60:0.1-0.

5. The first free radical scavenger and the second free radical scavenger are both combinations of one or more of diphenylamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, and 2,6-di-tert-butyl-4-methylphenol; The thermoplastic elasticity is any one or a combination of styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene.

2. The high-performance bitumen-based waterproof membrane modifier according to claim 1, characterized in that, The moderately cracked rubber polymer has an acetone-soluble content of ≤10% by weight, a trichloroethylene-soluble content of ≥90% by weight, a Mn content of trichloroethylene-soluble matter between 2000-5000 g / mol, and a polymer polydispersity index (PDI) between 2.5-5.

0.

3. The high-performance bitumen-based waterproof membrane modifier according to claim 2, characterized in that, The novel thermoplastic elastomer has an acetone-soluble content of ≤5% by weight and a trichloroethylene-soluble content of ≥95% by weight; Mn is between 100,000 and 550,000 g / mol, and PDI is between 3.0 and 5.

0.

4. The high-performance bitumen-based waterproof membrane modifier according to claim 1, characterized in that, The polyisobutylene rubber has an Mn ≥ 10000 g / mol, preferably between 20000-45000 g / mol.

5. The high-performance bitumen-based waterproof membrane modifier according to claim 1, characterized in that, The waste rubber powder is made from any one or more of waste all-steel radial tires, waste semi-steel radial tires, and waste bicycle tires, and its particle size ranges from 40 to 100 mesh.

6. A method for preparing a high-performance bitumen-based waterproof membrane modifier as described in any one of claims 1-5, characterized in that, Includes the following steps: The rubber powder and the first free radical scavenger are put into a high-speed mixer and mixed for 15-35 minutes until the temperature of the mixed rubber powder is 105-135℃. The mixed rubber powder is added to the first-stage screw extruder, and the temperature of the first-stage screw extruder is controlled at 380-430℃; The material obtained from the first-stage screw extruder is continuously injected into the second-stage venting screw extruder. The first venting temperature zone of the venting screw extruder is controlled at 270-310℃ and a vacuum is applied with a vacuum degree of 10. -2 -10 -3 pa; The second exhaust temperature zone of the exhaust screw extruder is controlled at 190-230℃ and a vacuum is applied, with a vacuum degree of 10. -4 -10 -6 pa; The thermoplastic elastomer, polyisobutylene rubber, and the second free radical scavenger are added to a high-speed mixer and mixed for 5-10 minutes until the material temperature reaches 60-90℃ to obtain mixture A; The material and mixture A obtained from the second-stage exhaust extrusion machine are continuously injected into the third-stage screw extruder. The temperature of the third-stage screw extruder is controlled at 190-230℃, and a high-performance bitumen-based waterproof membrane modifier is obtained by extrusion.

7. The preparation method of the high-performance bitumen-based waterproof membrane modifier according to claim 6, characterized in that, The first-stage screw extruder is a twin-screw extruder or a three-screw extruder with a screw speed of 50-90 rpm; the second-stage screw extruder is a vented twin-screw extruder or a three-screw extruder with a screw speed of 40-70 rpm; and the third-stage screw extruder is a twin-screw extruder or a three-screw extruder with a screw speed of 60-120 rpm.

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