阅读说明：本技术 一种高粘度改性沥青防水卷材及其制备方法 (High-viscosity modified asphalt waterproof coiled material and preparation method thereof ) 是由 梁海益 于 2021-08-25 设计创作，主要内容包括：本发明提供了一种高粘度改性沥青防水卷材,所述防水卷材中采用的高粘度改性沥青是通过添加热塑性丁苯橡胶、聚醚型热塑性聚氨酯和特制的支化聚合物进行改性,最终能够提高防水卷材的力学性能,使其具有优异的抗异物入侵能力。(The invention provides a high-viscosity modified asphalt waterproof coiled material, wherein high-viscosity modified asphalt adopted in the waterproof coiled material is modified by adding thermoplastic styrene-butadiene rubber, polyether type thermoplastic polyurethane and a special branched polymer, and finally the mechanical property of the waterproof coiled material can be improved, so that the waterproof coiled material has excellent foreign matter invasion resistance.)

1. The high-viscosity modified asphalt waterproof coiled material is characterized by comprising a base and high-viscosity modified asphalt coated on the surface of the base;

the preparation method of the high-viscosity modified asphalt comprises the following steps: adding the basic asphalt into a reactor, controlling the temperature of the reactor to be 190-210 ℃, starting stirring, adding softening oil, stirring for 0.5-1 hour, adding thermoplastic styrene-butadiene rubber and polyether thermoplastic polyurethane, stirring for 0.5-1 hour, adding a branched polymer, stirring for 0.5-1 hour, and discharging;

the preparation method of the branched polymer comprises the following steps: under the nitrogen atmosphere, adding trimellitic anhydride and N, N-dimethylacetamide into a reactor, starting stirring, controlling the reactor to be at 30-35 ℃, slowly dropwise adding diethanolamine, reacting for 4-5 hours, adding triisopropanolamine, toluene and p-toluenesulfonic acid, adding a water separator on the reactor for reaction, controlling the temperature of the reactor to be 125-130 ℃, reacting for 2-4 hours, then carrying out reduced pressure distillation to remove the solvent, and discharging.

2. The waterproofing membrane according to claim 1, wherein the base asphalt is 90# asphalt; the thermoplastic styrene-butadiene rubber is a star-shaped polymer, and the mass ratio of styrene to butadiene is 1: 1.5-2.3, preferably the mass ratio is 1: 1.5, a melt index [ g/10min, 200 ℃, 5kg ] of 0.05 to 0.1, preferably 0.1.

3. The waterproof roll according to claim 1, wherein in the preparation method of the high-viscosity modified asphalt, the following components are calculated according to relative parts by mass:

the using amount of the base asphalt is 100 parts by mass;

the amount of the softening oil is 10-15 parts by mass;

the amount of the thermoplastic styrene-butadiene rubber is 5-10 parts by mass;

the using amount of the thermoplastic polyurethane is 5-10 parts by mass;

the amount of the branched polymer is 10-15 parts by mass.

4. The waterproofing membrane according to claim 1, wherein in the preparation method of the branched polymer, the relative parts by mass of the following components are as follows:

the using amount of the trimellitic anhydride is 20 parts by mass;

the dosage of the N, N-dimethylacetamide is 80-100 parts by mass;

the dosage of the diethanolamine is 10-12 parts by mass;

the dosage of the triisopropanolamine is 0.8-1 part by mass;

the amount of the toluene is 80-100 parts by mass;

the amount of the p-toluenesulfonic acid is 0.1-0.2 parts by mass.

5. The waterproofing membrane according to claim 1, wherein the preparation method of the polyether type thermoplastic polyurethane is: adding polytetrahydrofuran ether glycol, a chain extender, a catalyst, an antioxidant and polyethylene wax into a reactor, controlling the temperature of the reactor to be 100-120 ℃, starting stirring, adding diphenylmethane diisocyanate after uniformly mixing, injecting the mixture into a double-screw extruder after uniformly stirring, controlling the temperature of the extruder to be 160-180 ℃, and extruding and granulating to obtain the polyether type thermoplastic polyurethane;

preferably, the number average molecular weight of the polytetrahydrofuran ether glycol is 2000, the chain extender is 1, 4-butanediol, and the catalyst is dibutyltin dilaurate.

6. The waterproofing membrane according to claim 5, wherein in the preparation method of the polyether type thermoplastic polyurethane, the relative parts by mass of the following components are as follows:

the amount of the polytetrahydrofuran ether glycol is 70-90 parts by mass;

the using amount of the chain extender is 3-8 parts by mass;

the amount of the catalyst is 0.1-0.3 parts by mass;

the using amount of the antioxidant is 3-5 parts by mass;

the using amount of the polyethylene wax is 3-5 parts by mass;

the amount of the diphenylmethane diisocyanate is 10-30 parts by mass.

7. A preparation method of the waterproof roll as claimed in any one of claims 1 to 6, characterized in that the high-viscosity modified asphalt is added into a reactor, the temperature of the reactor is controlled at 190 to 210 ℃, stirring is started, and after the high-viscosity modified asphalt is melted, the high-viscosity modified asphalt is uniformly and flatly coated on the surface of the base to obtain the waterproof roll.

Technical Field

The invention relates to a high-viscosity modified asphalt waterproof coiled material, a preparation method thereof and a preparation method of the waterproof coiled material.

Background

The development of the building waterproof material in China is faster in recent years, the product structure is upgraded, and the development of the asphalt waterproof coiled material with excellent polymer modification is promoted. The performance of the polymer modified asphalt determines the quality of the waterproof coiled material manufactured by the asphalt, and the asphalt is characterized by being beneficial to improving the heat resistance of the asphalt, reducing the low-temperature brittleness of the asphalt and effectively improving the elasticity, low-temperature deformability and plasticity of the asphalt. At present, polymers used for asphalt-based waterproof coiled materials are usually SBS resin, EVA resin and the like, and performance improvement brought by the resin modified asphalt waterproof coiled materials is still insufficient to meet the requirements of people.

Therefore, it is required to provide a modified asphalt waterproofing membrane with excellent properties in all aspects to solve the problems in the prior art.

Disclosure of Invention

The invention provides a high-viscosity modified asphalt waterproof coiled material, wherein high-viscosity modified asphalt adopted in the waterproof coiled material is modified by adding thermoplastic styrene-butadiene rubber, polyether type thermoplastic polyurethane and a special branched polymer, and finally the mechanical property of the waterproof coiled material can be improved, so that the waterproof coiled material has excellent foreign matter invasion resistance.

The above purpose of the invention is realized by the following technical scheme:

the high-viscosity modified asphalt waterproof coiled material is characterized by comprising a base and high-viscosity modified asphalt coated on the surface of the base;

the preparation method of the high-viscosity modified asphalt comprises the following steps: adding the basic asphalt into a reactor, controlling the temperature of the reactor to be 190-210 ℃, starting stirring, adding softening oil, stirring for 0.5-1 hour, adding thermoplastic styrene-butadiene rubber and thermoplastic polyurethane resin, stirring for 0.5-1 hour, adding a branched polymer, stirring for 0.5-1 hour, and discharging;

the preparation method of the branched polymer comprises the following steps: under the nitrogen atmosphere, adding trimellitic anhydride and N, N-dimethylacetamide into a reactor, starting stirring, controlling the reactor to be at 30-35 ℃, slowly dropwise adding diethanolamine, reacting for 4-5 hours, adding triisopropanolamine, toluene and p-toluenesulfonic acid, adding a water separator on the reactor for reaction, controlling the temperature of the reactor to be 125-130 ℃, reacting for 2-4 hours, then carrying out reduced pressure distillation to remove the solvent, and discharging.

The invention adopts thermoplastic styrene butadiene rubber (SBS), polyether type thermoplastic polyurethane and special branched polymer to modify asphalt. The thermoplastic styrene-butadiene rubber is a commonly used asphalt modifier in the field, but the improvement of the mechanical property of the waterproof coiled material is limited by only adopting the thermoplastic styrene-butadiene rubber to modify the asphalt. The polyether type thermoplastic polyurethane added in the invention has good compatibility with other components, and can further improve the elasticity of the waterproof roll. The added special branched polymer has proper branching degree, ensures good compatibility with other components, further improves the mechanical property of the waterproof roll, and can increase the foreign matter invasion resistance of the waterproof roll when being used together with other components.

In the preparation method of the branched polymer, trimellitic anhydride and diethanol amine are selected to react in advance, triisopropanolamine is added to carry out further branching reaction, the types of raw materials are limited, and raw material molecules are ensured to have proper steric hindrance and reactivity, so that the purpose is to ensure that the synthesis process of the branched polymer is stable, the generated branched polymer has good modification effect on asphalt, and finally, various performances of the waterproof coiled material are improved.

The base asphalt is 90# asphalt; the thermoplastic styrene-butadiene rubber is a star-shaped polymer, and the mass ratio of styrene to butadiene is 1: 1.5-2.3, preferably the mass ratio is 1: 1.5 and a melt index (g/10min, 200 ℃, 5kg) of 0.05 to 0.1, preferably 0.1. The thermoplastic styrene-butadiene rubber selects a star-shaped polymer, namely, polymer molecules have a certain branching degree, the mass ratio of styrene to butadiene and the melt index are limited to be in a preferable range, on one hand, the thermoplastic styrene-butadiene rubber can be promoted to be good in compatibility with other components, and on the other hand, the thermoplastic styrene-butadiene rubber can be guaranteed to have a sufficient promotion effect on all aspects of performances of the waterproof coiled material.

In the preparation method of the high-viscosity modified asphalt, the following components are calculated according to relative parts by mass:

the using amount of the base asphalt is 100 parts by mass;

the amount of the softening oil is 10-15 parts by mass;

the amount of the thermoplastic styrene-butadiene rubber is 5-10 parts by mass;

the using amount of the thermoplastic polyurethane is 5-10 parts by mass;

the amount of the branched polymer is 10-15 parts by mass.

In the preparation method of the branched polymer, the relative parts by mass of the following components are as follows:

the using amount of the trimellitic anhydride is 20 parts by mass;

the dosage of the N, N-dimethylacetamide is 80-100 parts by mass;

the dosage of the diethanolamine is 10-12 parts by mass;

the dosage of the triisopropanolamine is 0.8-1 part by mass;

the amount of the toluene is 80-100 parts by mass;

the amount of the p-toluenesulfonic acid is 0.1-0.2 parts by mass.

The preparation method of the polyether type thermoplastic polyurethane comprises the following steps: adding polytetrahydrofuran ether glycol, a chain extender, a catalyst, an antioxidant and polyethylene wax into a reactor, controlling the temperature of the reactor to be 100-120 ℃, starting stirring, adding diphenylmethane diisocyanate after uniformly mixing, injecting the mixture into a double-screw extruder after uniformly stirring, controlling the temperature of the extruder to be 160-180 ℃, and extruding and granulating to obtain the polyether type thermoplastic polyurethane;

preferably, the number average molecular weight of the polytetrahydrofuran ether glycol is 2000, the chain extender is 1, 4-butanediol, and the catalyst is dibutyltin dilaurate.

Polyether type thermoplastic polyurethane selects polytetrahydrofuran ether glycol as main raw materials, cooperates other components to synthesize thermoplastic polyurethane, can ensure that it has suitable compatibility with other polymers on the one hand, and on the other hand, the polyether type thermoplastic polyurethane of this application synthesis has better promotion to waterproofing performance of waterproofing membrane.

In the preparation method of the polyether type thermoplastic polyurethane, the polyether type thermoplastic polyurethane comprises the following components in parts by weight:

the amount of the polytetrahydrofuran ether glycol is 70-90 parts by mass;

the using amount of the chain extender is 3-8 parts by mass;

the amount of the catalyst is 0.1-0.3 parts by mass;

the using amount of the antioxidant is 3-5 parts by mass;

the using amount of the polyethylene wax is 3-5 parts by mass;

the amount of the diphenylmethane diisocyanate is 10-30 parts by mass.

Adding the high-viscosity modified asphalt into a reactor, controlling the temperature of the reactor to be 190-210 ℃, starting stirring, and after the high-viscosity modified asphalt is melted, uniformly and flatly coating the high-viscosity modified asphalt on the surface of the base to obtain the waterproof coiled material.

It should be noted that the content of the present invention which is not described can be performed by referring to the technical solutions commonly used in the art, and the implementation of the present invention is not affected.

The invention has the beneficial effects that: thermoplastic styrene butadiene rubber (SBS), thermoplastic polyurethane resin and a special branched polymer are adopted to modify asphalt, and the components have good compatibility and suitable processing conditions; the three polymers are mutually matched, so that the mechanical property and the foreign matter invasion resistance of the prepared waterproof roll are further improved.

Detailed Description

The invention is further illustrated by the following specific examples. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

The examples and comparative examples used the following starting materials:

the base layer of the tire is a glass fiber tire with the thickness of 0.85mm and the mass per unit area of 120g/m²Bona high performance materials (changzhou) ltd;

base asphalt, 90# asphalt, majesty people's Hao commercial and trade company Limited;

softening oil, triple line-lightening softening oil, alpha (Jiangyin) bitumen;

thermoplastic styrene-butadiene rubber 1, the brand 4402-1, a star polymer, and a styrene-butadiene mass ratio of 1: 1.5, melt index (g/10min, 200 ℃, 5kg)0.1, ba ling petrochemical company;

thermoplastic styrene-butadiene rubber 2, the brand number 4303-2, star polymer, the mass ratio of styrene to butadiene is 1: 2.3, melt index (g/10min, 200 ℃, 5kg)0.05, ba ling petrochemical company;

diphenylmethane diisocyanate, basf corporation;

polytetrahydrofuran ether glycol, number average molecular weight 2000, basf;

polybutylene adipate diol, number average molecular weight 2000, basf;

antioxidant 1010, Shanghai Kayin chemical Co., Ltd;

polyethylene wax, number average molecular weight 2000, honewire corporation.

The preparation methods of the branched polymers 1 and 2 and the comparative branched polymers 1 to 3 are as follows: under the nitrogen atmosphere, adding trimellitic anhydride and N, N-dimethylacetamide into a reactor, starting stirring, controlling the reactor to be at 35 ℃, slowly dropwise adding diethanolamine (replacing diisopropanolamine in the comparative branched polymers 2 and 3), reacting for 4 hours, adding triisopropanolamine (replacing triethanolamine in the comparative branched polymers 1 and 3), toluene and p-toluenesulfonic acid, adding a water separator on the reactor for reacting, controlling the temperature of the reactor to be 125 ℃, removing the solvent by reduced pressure distillation after reacting for 3 hours, and discharging.

The amounts of the respective raw materials for preparing the branched polymer are shown in Table 1 in terms of relative parts by mass between the respective components.

TABLE 1 preparation of branched polymers the amounts of the respective raw materials (parts by mass)

The preparation method of the polyether type thermoplastic polyurethane 1 and 2 and the polyester type thermoplastic polyurethane comprises the following steps: adding polytetrahydrofuran ether glycol (polyester type thermoplastic polyurethane is replaced by polybutylene adipate glycol), 1, 4-butanediol, dibutyltin dilaurate, an antioxidant 1010 and polyethylene wax into a reactor, controlling the temperature of the reactor at 110 ℃, starting stirring, adding diphenylmethane diisocyanate after uniformly mixing, injecting the mixture into a double-screw extruder after uniformly stirring, controlling the temperature of the extruder at 165 ℃, and extruding and granulating to obtain the thermoplastic polyurethane.

The respective raw materials for preparing the thermoplastic polyurethane are listed in table 2 in terms of relative parts by mass between the respective components.

TABLE 2 amounts (parts by mass) of respective raw materials for preparing thermoplastic polyurethane

The preparation methods of the high-viscosity modified asphalt used in the examples and comparative examples were: adding the basic asphalt into a reactor, controlling the temperature of the reactor at 210 ℃, starting stirring, adding softening oil, stirring for 1 hour, adding the thermoplastic styrene-butadiene rubber and the polyether thermoplastic polyurethane (the polyester thermoplastic polyurethane is replaced in the comparative example 1), stirring for 1 hour, adding the branched polymer (the branched polymer is replaced in the comparative examples 2-4, the branched polymer is not added in the comparative example 5, directly discharging, stirring for 1 hour, and discharging.

The preparation method of the waterproof roll in the examples and the comparative examples comprises the following steps: adding high-viscosity modified asphalt into a reactor, controlling the temperature of the reactor at 210 ℃, starting stirring, after the high-viscosity modified asphalt is melted, uniformly and flatly coating the asphalt layer on the surface of a base to enable the thickness of the asphalt layer to be 3mm, and compacting to obtain the waterproof coiled material.

The raw materials used in the examples and comparative examples are shown in table 3 in relative parts by mass between the components.

TABLE 3 EXAMPLES AND COMPARATIVE EXAMPLES the amounts of raw materials (parts by mass)

The modified asphalt samples in the examples and the comparative examples were subjected to penetration test with the test standard GB/T4509-2010.

The waterproof coiled material samples of the examples and the comparative examples are subjected to performance tests, and the test standard is GB/T328.1-27-2007.

The results of the tests of the examples and comparative examples are shown in Table 4.

Table 4 test results of examples and comparative examples

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.