CN109837767B

CN109837767B - Self-adhesive polymer modified asphalt waterproof coiled material and preparation method thereof

Info

Publication number: CN109837767B
Application number: CN201711195680.7A
Authority: CN
Inventors: 董进学; 郭敬伟; 魏艳萍
Original assignee: Beijng Environmental Protection Technology Co ltd Wing Tai Luther
Current assignee: Beijng Environmental Protection Technology Co ltd Wing Tai Luther
Priority date: 2017-11-24
Filing date: 2017-11-24
Publication date: 2021-11-30
Anticipated expiration: 2037-11-24
Also published as: CN109837767A

Abstract

The invention provides a self-adhesive polymer modified asphalt waterproof coiled material and a preparation method thereof. The coiled material comprises, by weight, 37-55 parts of asphalt, 25-50 parts of a modifier and 10-25 parts of a first filler, wherein the modifier comprises linearized active rubber, a second filler and a rubber crosslinking aid, the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules is more than or equal to 75%. The modifier contains the linearization active rubber which is obtained by desulfurization treatment of waste rubber powder with higher linearization degree, and the linearization active rubber and the coiled material component can form close interface combination. The linearized active rubber comprises gradient small molecules and can play the role of a softener, and the adhesiveness of the coiled material can be effectively improved without adding small molecule softeners and the like in the application process. The above factors are matched with the proportional relationship among the components, so that the coiled material has excellent mechanical property, high viscosity and low micromolecule migration.

Description

Self-adhesive polymer modified asphalt waterproof coiled material and preparation method thereof

Technical Field

The invention relates to the technical field of organic materials, in particular to a self-adhesive polymer modified asphalt waterproof coiled material and a preparation method thereof.

Background

In view of the safety of open fire and the problem of environmental pollution in the construction process of the traditional elastomer coiled material (SBS modified asphalt coiled material), the problem of weak bonding with a base layer caused by the fact that the coiled material is baked, and the like, the self-adhesive coiled material (self-adhesive polymer modified asphalt waterproof coiled material) has the advantages of construction performance and bonding performance, so that the application range of the self-adhesive coiled material is more and more extensive, and the traditional elastomer coiled material is greatly replaced.

The adhesiveness and adhesive strength of the self-adhesive coil are generally formed by the action of components such as small molecule softening oil, petroleum resin, high molecular polymer and the like in a self-adhesive polymer modified asphalt system. In addition, in order to reduce the manufacturing cost of the self-adhesive coiled material, a proper amount of waste rubber powder or desulfurized rubber powder is also added.

Patent CN102492368A discloses a high-temperature resistant self-adhesive polymer modified asphalt waterproof coiled material and a preparation method thereof, and the patent method uses part of rubber powder to improve the comprehensive performance of the self-adhesive coiled material. Patent CN104263261A discloses a high initial viscosity self-adhesive waterproof coiled material and a preparation method thereof, wherein in order to improve the performances of the coiled material such as elongation and the like, partial desulfurized rubber powder or regenerated rubber is added. Patent CN106281211A discloses a creep reaction type high polymer rubber self-adhesive waterproof roll and a preparation method thereof, wherein modified tire rubber powder is desulfurized rubber powder or SBS (styrene-butadiene-styrene) leftovers.

The comprehensive performance of the self-adhesive coiled material is poor, and the self-adhesive coiled material mainly comprises the following two aspects:

(1) the waste rubber powder is in a cross-linking structure, and cannot form tight interface combination with other components when serving as a modifier, so that a plurality of stress concentration points are formed, and the comprehensive physical properties of the coiled material can be seriously influenced by the stress concentration points. And because of the interface problem, the interface effect can be improved only by stirring and developing at high temperature for a long time when the waste rubber powder is added into the self-adhesive coiled material in actual production, so that the production efficiency is influenced and the production energy consumption is increased. Meanwhile, the crosslinked waste rubber powder cannot fully exert the low-temperature flexibility and elasticity, and the elastomer polymers (SBS, SBR and the like) with a large amount of addition are often needed to improve the comprehensive performance of the coiled material, so that the cost cannot be effectively reduced. And because most of the existing devulcanized rubber powder is of a core-shell structure and comprises a crosslinked rubber hard core and a crosslinked macromolecular shell layer, the devulcanized rubber powder with the structure can improve the problems to a certain extent, but the improvement range is limited.

(2) In order to ensure the adhesiveness and initial adhesiveness of the self-adhesive coiled material, a part of softening agent (aromatic oil, line-reducing oil, base oil and the like) is filled in a formula by the traditional method, the wetting property of the softening agent with a base layer is good, the compatibility with an asphalt matrix is good, and the adhesiveness and initial adhesiveness of the self-adhesive coiled material can be obviously improved. However, the softening agent is easy to migrate after the coiled material is stored and constructed, and the migration to a cement base layer can cause the damage of the base layer and further cause water seepage; migration to the coil surface results in a decrease in the oil permeability of the coil. These two types of migration can lead to a reduction in the continuous bonding capacity of the web and, in severe cases, to non-sticking of the self-adhesive web, i.e. loss of the initial tack of the web itself. Meanwhile, a large amount of volatile matters are easily formed in the production process due to the addition of the traditional softener, and the volatile matters have low flash points and are easy to form safety accidents. Secondly, the addition of the waste rubber powder can absorb light components of asphalt and a softening agent due to the oil absorption and swelling of the crosslinked rubber, so that the initial viscosity of the self-adhesive coiled material is reduced. In addition, some patents add part of petroleum resin to improve the initial tack and sustained tack of the self-adhesive web, which can significantly improve the initial tack and sustained tack of the self-adhesive web, but the petroleum resin itself has poor low temperature resistance, i.e., the addition of petroleum resin can lead to poor low temperature flexibility of the self-adhesive web. Further, petroleum resins are derived from petroleum-based refinery products, which are themselves expensive and have no cost advantage.

For the above reasons, there is a need for a self-adhesive roll material with high mechanical properties, high viscosity and low small molecule mobility.

Disclosure of Invention

The invention mainly aims to provide a self-adhesive polymer modified asphalt waterproof coiled material and a preparation method thereof, and aims to solve the problem that the self-adhesive coiled material in the prior art cannot have high mechanical property, high viscosity and low micromolecule mobility.

In order to achieve the purpose, according to one aspect of the invention, the self-adhesive polymer modified asphalt waterproof coiled material is provided, and the raw materials of the coiled material comprise, by weight, 37-55 parts of asphalt, 25-50 parts of a modifier and 10-25 parts of a first filler, wherein the modifier comprises linearized active rubber, a second filler and a rubber crosslinking aid, the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%.

Furthermore, the linearized molecules in the linearized active rubber comprise gradient small molecules and macromolecular polymers, the molecular weight of the gradient small molecules is 500-10000, and the molecular weight of the macromolecular polymers is more than 10000.

Furthermore, in the linearized molecules, the weight percentage content of the gradient small molecules is 10-20%, and the weight percentage content of the macromolecular polymer is 80-90%.

Further, in the modifier, the weight ratio of the linearized active rubber, the second filler and the rubber crosslinking assistant is 100: 20-60: 0.05 to 2.

Further, the asphalt is alkyl petroleum asphalt; preferably, the penetration degree of the asphalt at 25 ℃ is 50-200 mm^-1(ii) a Preferably, the first filler and the second filler are respectively and independently selected from one or more of talcum powder, heavy calcium carbonate, light calcium carbonate and diatomite; more preferably, the mesh numbers of the first filler and the second filler are respectively more than 300 meshes; preferably, the rubber crosslinking coagent is one or more of DCP, pro-TMTM, pro-DM, pro-H and bromomethyl-p-tert-butylphenol formaldehyde resin.

Further, the raw materials of the coiled material also comprise 0.5-7 parts by weight of elastomer polymer, preferably 0.5-2 parts by weight of elastomer polymer; preferably, the elastomeric polymer is one or more of SBS, SIS, SEBS, and SBR.

According to another aspect of the present invention, there is also provided a method for preparing a self-adhesive polymer modified asphalt waterproofing membrane, which comprises the following steps: mixing and dispersing asphalt, a modifier and a first filler to obtain a rubber material; and dipping or coating the rubber material on the surface of the felt cloth, and pressing the felt cloth by a roller to form the coiled material.

Further, in the process of mixing and dispersing the asphalt, the modifier and the first filler, the elastomer polymer is added simultaneously; preferably, the step of preparing the compound comprises: mixing and swelling bitumen and an elastomeric polymer to obtain a first mixture; mixing the first mixture with a modifier and swelling to obtain a second mixture; grinding the second mixture to obtain a secondary homogenized material; stirring and dispersing the secondary homogenized material and the first filler to obtain a sizing material;

further, the step of preparing the first mixture comprises: heating asphalt to 130-160 ℃, then adding an elastomer polymer into the asphalt, and carrying out first heat preservation swelling under the stirring condition to obtain a first mixture; preferably, the stirring speed in the first heat preservation swelling process is 200-600 rpm, the heat preservation temperature is 130-160 ℃, and the swelling time is 30-90 min; the step of preparing the second mixture comprises: adding a modifier into the first mixture, and carrying out second heat preservation swelling under the stirring condition to obtain a second mixture; preferably, the stirring speed of the second heat-preservation swelling process is 200-600 rpm, the heat-preservation temperature is 130-160 ℃, and the swelling time is 15-45 min; the preparation method of the secondary homogenizing material comprises the following steps: grinding the second mixture for 15-30 min by using a colloid mill at the temperature of 130-160 ℃ to obtain a secondary homogenized material; the step of preparing the compound comprises: and dispersing the secondary homogenized material and the first filler for 20-60 min under the conditions of a stirring speed of 200-600 rpm and a temperature of 130-160 ℃ to obtain the rubber material.

Further, the preparation method further comprises the step of preparing the modifier before the step of mixing and swelling the first mixture with the modifier, wherein the modifier is prepared by the following method: carrying out banburying mixing on the linearized active rubber, the second filler and the rubber crosslinking assistant to obtain a mixture; extruding and molding the mixture to obtain a modifier; preferably, the linearized active rubber is prepared by the following method: in supercritical carbon dioxide, placing a mixture of waste rubber powder and a photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain linear active rubber; more preferably, the photocatalyst is a composite inorganic photocatalyst; more preferably, the photocatalyst is selected from Co-doped TiO₂、ZrO₂/ZnO composite and ZrO₂/TiO₂One or more of the complexes; further preferably, the amount of the photocatalyst is 0.5 to 3% by weight of the waste rubber powder.

The technical scheme provided by the invention is applied to provide a self-adhesive polymer modified asphalt waterproof coiled material, and the coiled material comprises, by weight, 37-55 parts of asphalt, 25-50 parts of a modifier and 10-25 parts of a first filler, wherein the modifier comprises linearized active rubber, a second filler and a rubber crosslinking aid, the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%. The self-adhesive polymer modified asphalt waterproof coiled material provided by the invention has high mechanical property, high viscosity and low micromolecule migration.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

As described in the background section, the self-adhesive web in the prior art cannot combine high mechanical properties, high viscosity, and low small molecule mobility.

In order to solve the problems, the invention provides a self-adhesive polymer modified asphalt waterproof coiled material, which comprises, by weight, 37-55 parts of asphalt, 25-50 parts of a modifier and 10-25 parts of a first filler, wherein the modifier comprises linearized active rubber, a second filler and a rubber crosslinking aid, the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage of linearized molecules in the linearized active rubber is more than or equal to 75%.

The raw materials of the self-adhesive coiled material provided by the invention are added with a modifier with a higher dosage besides the asphalt and the first filler with a smaller dosage. The modifier adopts linear active rubber which is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linear molecules in the linear active rubber is more than or equal to 75%. The linearized active rubber basically belongs to linearized macromolecules or has high content of the linearized macromolecules, and can form close interface combination with other components when used for modifying the self-adhesive coiled material, so that the mechanical property of the self-adhesive coiled material can be effectively improved.

Secondly, because the linearized active rubber comprises gradient small molecules, the linearized active rubber plays the role of a softening agent in the modification process, and the adhesiveness and the initial adhesiveness of the self-adhesive coiled material can be effectively improved without adding a softening agent or petroleum resin additionally in the application process. Meanwhile, the molecular weight of the gradient micromolecules in the linearized active rubber is distributed in a gradient manner, the motion property of the molecular chain end is far weaker than that of the traditional micromolecule softener, the motion migration capability of the micromolecule softener is greatly weakened, and the softener-like migration cannot occur. And because the linearized active rubber contains more linearized molecular components, the corresponding crosslinking degree is very low, and the initial viscosity of the self-adhesive coiled material cannot be reduced due to oil absorption swelling. For this reason, the self-adhesive web provided by the present invention also has high tack and low small molecule migration.

In addition to the linearized active rubber, the self-adhesive web modifier described above also includes a second filler and a rubber crosslinking coagent. The second filler is added into the modifier in advance, so that the second filler is more uniformly dispersed when the second filler is mixed into the asphalt at the later stage, and the problem of dispersibility of the second filler when the second filler is added into the modified asphalt independently is solved. The mechanical property of the self-adhesive coiled material can be obviously improved by matching with the first filler. The addition of the rubber crosslinking assistant in the modifier can form micro-crosslinking of the elastomer polymer in the linearized active rubber and the modified asphalt to form a stable network structure, thereby achieving the purpose of further improving the mechanical property of the self-adhesive coiled material. In addition, the addition of the rubber crosslinking auxiliary agent can also effectively avoid the risk of easy ignition caused by adding the rubber crosslinking auxiliary agent into the modified asphalt independently at high temperature.

In addition, it should be noted that, the weight percentage content of the linearized molecules of the linearized active rubber in the modifier is more than or equal to 75%, so that the low-temperature flexibility and elasticity can be fully exerted, the addition amount of the elastomeric polymer in the self-adhesive coiled material is favorably reduced, even no additional elastomeric polymer is needed to be added, and the production cost of the self-adhesive coiled material is favorably further reduced. More preferably, the weight percentage of the linearized molecules of the linearized active rubber in the modifier is more than or equal to 80%.

In a word, the self-adhesive polymer modified asphalt waterproof coiled material provided by the invention has high mechanical property, high viscosity and low micromolecule migration.

It should be further noted that the raw materials of the self-adhesive polymer modified asphalt waterproof roll of the present invention include felt cloth as a roll base material in addition to the above components, which is clear to those skilled in the art and will not be described herein again.

The linear active rubber adopted by the modifier is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linear molecules in the linear active rubber is more than or equal to 75%, so that the interface effect between the modifier and other components of the self-adhesive coiled material can be obviously improved, and the low-temperature flexibility and elasticity of the rubber can be effectively exerted. In a preferred embodiment, the linearized molecules in the linearized active rubber comprise a gradient of small molecules with a molecular weight of 500 to 10000 and a macromolecular polymer with a molecular weight > 10000.

The term "gradient small molecule" as used herein refers to a gradient distribution of molecular weights of small molecules over a range, not just one molecular weight.

The gradient micromolecules can completely replace micromolecule softening oil added in the traditional self-adhesive coiled material, and the adhesiveness (initial adhesion and sustained adhesion) of the self-adhesive coiled material is improved. Meanwhile, the molecular chain end of the micromolecule contains a large number of active functional groups, and the surface activity of the functional groups is durable and stable, and the wettability between the functional groups and a base layer and a coiled material is good. In addition, the molecular weight of the small molecules is larger than that of the traditional softening oil, the motion property of the chain segment of the small molecules is weaker than that of the traditional small molecule softening agent, and the probability of surface migration is further effectively reduced. The combined action of the factors greatly enhances the adhesiveness of the self-adhesive coiled material (initial adhesion and holding adhesion), and greatly improves the stability. And the macromolecular polymer with the molecular weight more than 10000 can more effectively exert the low-temperature flexibility and elasticity and improve the comprehensive use performance of the self-adhesive coiled material.

In order to further integrate the beneficial effects brought by the gradient small molecules and the macromolecular polymers, in a preferred embodiment, the weight percentage of the gradient small molecules in the linearized molecules is 10-20%, and the weight percentage of the macromolecular polymers is 80-90%.

In a preferred embodiment, the weight ratio of the linearized active rubber, the filler and the rubber crosslinking assistant in the modifier is 100: 20-60: 0.05 to 2. The dosage relation of the three is controlled in the range, and the comprehensive performance of the self-adhesive coiled material can be further improved.

In a preferred embodiment, the bitumen is an alkyl petroleum bitumen; preferably, the penetration degree of the asphalt at 25 ℃ is 50-200 mm^-1。

The rubber crosslinking agent can be selected from the types commonly used in the art, and preferably, the rubber crosslinking auxiliary agent includes, but is not limited to, one or more of DCP (dicumyl peroxide), TMTM (tetramethylthiodicarbamide), DM (2, 2' -dithiodibenzothiazyl), H (hexamethylenetetramine) and bromomethyl p-tert-butylphenol formaldehyde resin. The vulcanization accelerator has a good vulcanization accelerating effect, and the vulcanization activity can be further improved by adding the modifier.

The first filler and the second filler may be of the type commonly used in the art. Preferably, the first filler and the second filler are respectively and independently selected from one or more of talcum powder, heavy calcium carbonate, light calcium carbonate and diatomite; more preferably, the mesh numbers of the first filler and the second filler are respectively more than 300 meshes.

In a preferred embodiment, the raw material of the coiled material further comprises 0.5-7 parts by weight of an elastomer polymer. The additional addition of some elastomeric polymers has a better improvement on the heat resistance, peel strength and tack of the self-adhesive web. And because of the high linearity degree of the linear active rubber in the modifier, the low-temperature flexibility can be exerted by adding a small amount of the elastomer polymer, and the performance of the coiled material is improved. For the purpose of comprehensively considering the coil property and saving the cost, the raw material preferably comprises 0.5-2 of elastomer polymer.

Preferably, the elastomeric polymer is one or more of SBS, SIS, SEBS, and SBR. The elastomer polymers have more excellent low-temperature flexibility and better compatibility with asphalt, and are favorable for further improving the comprehensive performance of the self-adhesive coiled material.

In the above-mentioned production method, the raw materials used are a modifier in addition to the asphalt and the first filler. The modifier adopts linear active rubber which is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linear molecules in the linear active rubber is more than or equal to 75%. The linearized active rubber basically belongs to linearized macromolecules or has high content of the linearized macromolecules, and can form close interface combination with other components when used for modifying the self-adhesive coiled material, so that the mechanical property of the self-adhesive coiled material can be effectively improved. Secondly, because the linearized active rubber comprises gradient small molecules, the linearized active rubber plays the role of a softening agent in the modification process, and the adhesiveness and the initial adhesiveness of the self-adhesive coiled material can be effectively improved without adding a softening agent or petroleum resin additionally in the application process. Meanwhile, the molecular weight of the gradient micromolecules in the linearized active rubber is distributed in a gradient manner, the motion property of the molecular chain end is far weaker than that of the traditional micromolecule softener, the motion migration capability of the micromolecule softener is greatly weakened, and the softener-like migration cannot occur. And because the linearized active rubber contains more linearized molecular components, the corresponding crosslinking degree is very low, and the initial viscosity of the self-adhesive coiled material cannot be reduced due to oil absorption swelling. For this reason, the self-adhesive web produced by the above production method also has high tackiness and low small molecule migration property.

In addition, due to the good interface compatibility between the modifier and the asphalt, the conditions of the mixing process are milder, and a rubber material with uniform dispersion can be formed without long-time high-temperature development, so that the production time is greatly shortened, and the production energy consumption and the production cost are reduced.

In a preferred embodiment, the elastomeric polymer is added simultaneously with the mixing and dispersing of the bitumen, modifier and first filler. The addition of the elastomeric polymer can further improve the heat resistance, peel strength and tack of the self-adhesive web. Specifically, the step of preparing the compound comprises: mixing and swelling bitumen and an elastomeric polymer to obtain a first mixture; mixing the first mixture with a modifier and swelling to obtain a second mixture; grinding the second mixture to obtain a secondary homogenized material; and stirring and dispersing the secondary homogenized material and a second filler to obtain the rubber material.

In order to more uniformly disperse the components, in a preferred embodiment, the step of preparing the first mixture comprises: heating asphalt to 130-160 ℃, then adding an elastomer polymer into the asphalt, and carrying out first heat preservation swelling under the stirring condition to obtain a first mixture; preferably, the stirring speed in the first heat preservation swelling process is 200-600 rpm, the heat preservation temperature is 130-160 ℃, and the swelling time is 30-90 min; the step of preparing the second mixture comprises: adding a modifier into the first mixture, and carrying out second heat preservation swelling under the stirring condition to obtain a second mixture; preferably, the stirring speed of the second heat-preservation swelling process is 200-600 rpm, the heat-preservation temperature is 130-160 ℃, and the swelling time is 15-45 min; the preparation method of the secondary homogenizing material comprises the following steps: grinding the second mixture for 15-30 min by using a colloid mill at the temperature of 130-160 ℃ to obtain a secondary homogenized material; the step of preparing the compound comprises: and dispersing the secondary homogenized material and the first filler for 20-60 min under the conditions of a stirring speed of 200-600 rpm and a temperature of 130-160 ℃ to obtain the rubber material.

In a preferred embodiment, the preparation method further comprises the step of preparing the modifier before the step of mixing and swelling the first mixture with the modifier, the modifier being prepared by the following method: carrying out banburying mixing on the linearized active rubber, the second filler and the rubber crosslinking assistant to obtain a mixture; extruding and molding the mixture to obtain a modifier;

in a preferred embodiment, the linearized active rubber is prepared by the following process: in supercritical carbon dioxide, the mixture of waste rubber powder and photocatalyst is put under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber. The waste rubber powder can be swelled by using the supercritical carbon dioxide, so that the aperture of the three-dimensional cross-linked network in the waste rubber powder is increased, and the photocatalyst is permeated into the waste rubber powder from the surface by virtue of the diffusion effect of the supercritical carbon dioxide fluid. Secondly, the photocatalyst generates a large amount of active groups under the irradiation of ultraviolet light to catalyze the breakage of S-S bonds in the waste rubber powder, thereby realizing the desulfurization and crosslinking of the waste rubber powder. Particularly, since the supercritical carbon dioxide also has an excellent dissolving effect, the linear molecules formed by the desulfurization and de-crosslinking on the surface of the waste rubber powder can be rapidly peeled off from the surface of the waste rubber powder and dissolved in the supercritical carbon dioxide. Along with the continuous reaction, the waste rubber powder continuously carries out the cyclic reciprocating of 'catalyst surface permeation, photocatalytic desulfurization and desulfurization linear molecule stripping dissolution' until the waste rubber powder integrally completes desulfurization and de-crosslinking to form the linear active rubber.

Different from the traditional mechanical shearing desulfurization regeneration method, the photocatalytic desulfurization is carried out under the swelling action of the supercritical carbon dioxide, so that the method has high selectivity on the breaking point of a crosslinked network, and the breaking point is mostly S-S bond crosslinking positions. The breaking point of the traditional mechanical shearing desulfurization is diversified, and the breaking point is not selective to S-S bond crosslinking. Therefore, based on the preparation method of the invention, the linearization structure of the rubber can be more completely maintained, and the regenerated linearization active rubber has higher molecular weight and correspondingly maintains higher performance, so that the rubber can be more widely applied to various fields.

Meanwhile, in the preparation method provided by the invention, reagents such as a desulfurizing agent, an organic softening agent and the like are not required, harmful reagent residues on the regenerated linearized active rubber are not caused, and the preparation method can be applied to various fields such as rubber products, asphalt modification and the like. Particularly, the photocatalyst can also be used as a filler of linearized active rubber, so that the performance of the rubber and the product thereof is not influenced, the filler consumption of downstream products can be saved, and the two aims can be fulfilled.

The above-mentioned photocatalyst may be of a type commonly used in the field of photocatalytic technology. In a preferred embodiment, the photocatalyst is a composite inorganic photocatalyst. The composite inorganic photocatalyst has higher catalytic activity and higher selective fracture performance on S-S crosslinking points in the waste rubber powder. More preferably, the photocatalyst is selected from Co-doped TiO₂、ZrO₂/ZnO composite and ZrO₂/TiO₂One or more of the complexes. The surface areas of the composite inorganic photocatalysts are greatly increased, so that the probability of exciting the photohole electrons under ultraviolet irradiation is further increased, and the composite inorganic photocatalysts have higher catalytic activity. At the same time, these photocatalysts remain in the linearized active rubber and are more suitable as fillers.

In a preferred embodiment, the preparation method comprises the following steps: mixing waste rubber powder with a photocatalyst to obtain a mixture; under the condition of stirring, putting the mixture into supercritical carbon dioxide for swelling treatment to obtain a swelling mixture; and irradiating ultraviolet light to the swelling mixture in supercritical carbon dioxide to perform photocatalytic desulfurization reaction, thereby obtaining the linearized active rubber.

Thus, mixing the waste rubber powder with the photocatalyst in advance enables the photocatalyst to be dispersed in the waste rubber powder in advance. Secondly, the mixture is placed in supercritical carbon dioxide under the condition of stirring for swelling treatment, so that the diffusion effect of supercritical carbon dioxide fluid can be more fully exerted, the waste rubber powder is swelled as soon as possible, and the photocatalyst is enabled to permeate into the surface of the waste rubber powder more quickly. Finally, irradiating ultraviolet light to the system for photocatalytic desulfurization reaction. In the actual operation process, the desulfurization efficiency of the waste rubber powder can be further improved according to the process.

In a preferred embodiment, the swelling treatment step comprises: injecting carbon dioxide gas into a system in which the mixture is located, and then adjusting the temperature of the system to 80-140 ℃ and the pressure to 10-35 MPa to convert the carbon dioxide gas into a supercritical state so as to form supercritical carbon dioxide; and swelling the mixture for 30-120 min under the stirring condition that the stirring speed is 200-700 rpm, so as to obtain a swelling mixture. The swelling treatment is carried out in the technical process, the aperture of the cross-linked network of the waste rubber powder is larger, and the photocatalyst can be more fully permeated and more uniformly dispersed in the rubber network, so that on one hand, the desulfurization efficiency of the waste rubber powder can be further improved, and simultaneously, the fracture number of S-S bonds can be further improved, thereby improving the desulfurization degree of the waste rubber powder and obtaining the desulfurized rubber with higher linearization degree.

More preferably, the swelling treatment step comprises: injecting carbon dioxide gas into a system in which the mixture is located, and then adjusting the temperature of the system to 105-140 ℃ and the pressure to 28-35 MPa to convert the carbon dioxide gas into a supercritical state so as to form supercritical carbon dioxide; and swelling the mixture for 90-120 min under the condition that the stirring speed is 500-700 rpm, so as to obtain a swelling mixture. The desulfurization efficiency and desulfurization degree under the process condition are higher.

In a preferred embodiment, in the step of photocatalytic desulfurization, the reaction temperature is 80-140 ℃ and the reaction pressure is 10-35 MPa. Under the reaction conditions, the S-S bond desulfurization selectivity of the photocatalyst is higher, and the desulfurization degree and the desulfurization linearization degree of the waste rubber powder are higher. More preferably, the reaction temperature in the step of the photocatalytic desulfurization reaction is 105-140 ℃, and the reaction pressure is 28-35 MPa. In the actual production process, after the photocatalytic desulfurization reaction is finished, the method preferably further comprises the following steps: and (3) decompressing the reaction system, recovering carbon dioxide, stopping illumination and cooling to obtain the linearized active rubber.

In a preferred embodiment, in the step of photocatalytic desulfurization, the illumination time of the ultraviolet light is 5 to 30min, preferably 20 to 30min, and the wavelength of the ultraviolet light is 300 to 400nm, preferably 350 to 390 nm. Under the illumination condition, the photocatalyst has higher activity, and the desulfurization effect of the waste rubber powder is better.

In a preferred embodiment, the step of mixing the waste rubber powder with the photocatalyst comprises: and stirring and mixing the waste rubber powder and the photocatalyst for 5-30 min under the condition that the stirring speed is 700-1500 rpm to obtain a mixture. The waste rubber powder and the photocatalyst are mixed according to the process, and the waste rubber powder and the photocatalyst can be mutually dispersed more fully. Preferably, the waste rubber powder and the photocatalyst are stirred and mixed to the temperature of 60-85 ℃ to obtain a mixture. Shear heating can occur in the stirring process, the stirring and mixing temperature is controlled to be 60-85 ℃, and performance influence caused by overheating can be prevented on the basis of sufficient dispersion.

As described above, based on the diffusibility and good solubility of supercritical carbon dioxide, the cyclic process of "catalyst surface permeation-photocatalytic desulfurization-desulfurization linear molecule stripping dissolution" is continuously performed in the step of photocatalytic desulfurization reaction of waste rubber powder, which enables the preparation method of the present invention to achieve a higher desulfurization degree by using the cyclic process with less photocatalyst. For the purpose of saving energy and improving the desulfurization efficiency and the desulfurization degree, in a preferred embodiment, the amount of the photocatalyst is 0.5 to 3% by weight, preferably 2 to 3% by weight, based on the waste rubber powder.

In a preferred embodiment, the particle size of the waste rubber powder is 80-120 meshes; preferably, the waste rubber powder is one or more of waste tire rubber powder, waste mechanical tire rubber powder, waste sole rubber powder and waste conveyor belt rubber powder.

In addition, the preparation method is suitable for waste rubber powder commonly used in the field, such as one or more of waste nitrile rubber powder, waste natural rubber powder, waste butyl rubber powder, waste ethylene propylene rubber powder and waste styrene butadiene rubber powder.

The beneficial effects of the present invention are further illustrated by the following examples:

preparation of linearized active rubber:

examples 1 to 17

In these examples, the following processes were used to conduct the devulcanization regeneration of the waste rubber:

step 1: putting 80-mesh waste tire rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 1000rpm for 20min to 70 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture;

step 2: putting the mixture into a supercritical carbon dioxide reaction kettle, injecting carbon dioxide gas into the reaction kettle by using a high-pressure pump to adjust the pressure in the reaction kettle, and simultaneously heating to convert the carbon dioxide gas into a supercritical state; starting stirring to swell the mixture in supercritical carbon dioxide to obtain a swollen mixture;

and step 3: maintaining the supercritical carbon dioxide environment, starting a built-in ultraviolet light source to perform ultraviolet irradiation on the swelling mixture, and irradiating for a certain time;

and 4, step 4: and (5) releasing pressure and recovering carbon dioxide gas, stopping illumination and cooling, and taking out a target product and testing.

Examples 1 to 17 differ in the following parameters: the type and amount of the photocatalyst (weight percentage of the waste rubber powder), the temperature of the supercritical carbon dioxide system (same swelling temperature and desulfurization reaction temperature), the pressure (same swelling pressure and desulfurization reaction pressure), the swelling time, the ultraviolet light irradiation time and the ultraviolet light wavelength are shown in table 1:

TABLE 1

Example 18

The process flow in this example is the same as in example 9, except that:

step 1: and (3) putting 120-mesh waste tire rubber powder and a photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 700rpm for 30min to 60 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.

Example 19

The process flow in this example is the same as in example 10, except that:

step 1: and (3) putting the 120-mesh waste sole rubber powder and the photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 1500rpm for 30min to 85 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.

Example 20

The process flow in this example is the same as in example 10, except that:

step 1: and (3) putting the 80-mesh waste conveyor belt rubber powder and the photocatalyst into a high-speed stirring and mixing unit, stirring at the stirring speed of 600rpm for 10min to 40 ℃, stopping stirring, putting the materials into a cooling unit, cooling and discharging to obtain a mixture.

Example 21

100 parts of waste tire tread rubber powder with the particle size of 1mm is adopted, 6 parts of pine tar, 4 parts of naphthenic oil, 0.5 part of phenyl mercaptan and 0.5 part of n-butylamine are added as regenerants, and the mixture is mixed and stirred for 10min at the temperature of 100 ℃ in a stirrer and then is placed for 36h at the temperature of 50 ℃. It was then fed into a co-rotating twin-screw extruder (D30 mm, L/D52/1, six heating zones) via a feeding device: screw rotation speed 150rpm, 6 temperature zones: changing the internal thread composition of the screw at 120 ℃, 180 ℃, 230 ℃, 280 ℃, 150 ℃ and 100 ℃, and adding a right-handed thread element to ensure that the maximum pressure reaches 7.5 MPa. And (3) after reacting for 5min, extruding by a screw extruder die to obtain the liquid reclaimed rubber.

Comparative example 1

100 parts of waste tire rubber powder and 10 parts of nano cadmium sulfide are stirred and mixed uniformly by a high-speed plasticizing reaction unit. The rotating speed of the reaction unit is firstly adjusted to 1200rpm, when the temperature reaches 90 ℃, stirring is stopped, the materials are put into a cooling unit, the rotating speed is 50rpm, and when the temperature is about 30 ℃, discharging is carried out. Placing the stirred material into a stirrer, and irradiating the material with ultraviolet lamp for 30 min. The UV lamp used was a 3kw high pressure mercury lamp with UV wavelength of 365 nm.

The main machine rotating speed of the double-screw extruder is adjusted to be 220rpm, the feeding rotating speed is adjusted to be 15rpm, and the temperatures of 7 temperature zones of the double screws are as follows: 54-67-77-76-79-73-42 ℃, the temperature of each area is not higher than 100 ℃, the production state at normal temperature and normal pressure is realized, and the discharge detection is carried out.

Comparative example 2

The process flow in this comparative example is the same as in example 10, except that the system temperature: 30 ℃, pressure 7MPa, critical parameters of CO 2: 31.26 deg.C and 7.29MPa, carbon dioxide is in non-supercritical state.

The devulcanization effect characterization was performed on the devulcanized reclaimed rubbers prepared in examples 1 to 21, comparative examples 1 and 2(D1 and D2), and the characterization results are shown in table 2, and the characterization methods are as follows:

the following treatments were carried out on each of the above products:

firstly, acetone is used as a solvent, and a Soxhlet extraction method is adopted to continuously extract for 48 hours until small molecules (acetone soluble substances) are completely extracted and separated by the acetone. Subsequently, the soluble fraction was dried in a vacuum drying oven until the mass was unchanged, the insoluble fraction was dried until the mass was unchanged, and secondary extraction was continued using toluene as a solvent to separate a macromolecular soluble substance (toluene soluble substance) and a crosslinked insoluble substance (gel).

The average molecular weights of the acetone soluble substance and the toluene soluble substance and the polymer polydispersity number PDI are respectively tested (GPC test can be simultaneously characterized, and the molecular weights and the polydispersity numbers PDI are respectively tested) by the following methods: acetone-soluble and toluene-soluble substances were sufficiently swollen with toluene, and the number average molecular weight (M) of the sample was measured by using a GPC analyzer model 515-_n) And calculating the polydispersity index (PDI) by taking tetrahydrofuran as a mobile phase and polystyrene as a standard sample, and measuring the temperature at 35 ℃.

The crosslink density of the gel was measured as follows: the crosslinking density test employs an equilibrium swelling method. The weighed sample was placed in a ground conical flask with a stopper containing 150ml of a good solvent (toluene was used as a good solvent in this experiment), immersed in a constant temperature water bath, kept at 30 ℃ for 72 hours, taken out after equilibration, weighed with an analytical balance, and dried in a vacuum desiccator at 50 ℃ for 4 hours. When the sample swells to equilibrium in a suitable solvent, the solvent molecules enter the crosslinked network at the same rate as they are expelled. And obtaining a crosslinking density formula, namely a Flory-Rehner formula, according to the basis of the rubber elasticity statistical theory.

TABLE 2

The gel content, the sol content, the average molecular weight of the sol, the sol PDI and the gel crosslinking density are the most visual and accurate means for representing the degradation degree of the crosslinked rubber. Higher sol content, lower gel crosslink density, indicate higher rubber degradation. The higher the toluene solubles content and the higher the molecular weight at the same sol content, the higher the content of linearized macromolecules in the reclaimed rubber after decrosslinking. The weight percentage of the linearized molecule is the sol content/(sol content + gel content); the weight percentage of the gradient small molecules in the linearized molecule is acetone soluble content/(acetone soluble + toluene soluble content).

1. From the comparison of the data in the above examples and comparative example 2, it can be seen that: in the supercritical carbon dioxide fluid state, the same process means is adopted, and the desulfurization and degradation degree of the waste rubber is far higher than that in the non-supercritical state (the carbon dioxide critical point is 38 ℃ and 7.38 MPa). This is due to: in the supercritical state, the carbon dioxide fluid can fully exert the excellent dissolving and extracting performances of the rubber powder, and can fully dissolve linear macromolecules and micromolecules, the macromolecules firstly desulfurized and degraded on the surface of the waste rubber powder are disentangled through the swelling effect of the supercritical carbon dioxide fluid, and are peeled from the crosslinked rubber powder body and dissolved in the fluid. And then, under the action of illumination and a catalyst, the inner layer of the crosslinked rubber powder is continuously desulfurized and degraded and has the same action as the surface layer until the whole crosslinked waste rubber powder is desulfurized and degraded. The linearized active rubber is in a pasty and semi-fluid state at normal temperature. However, in a non-supercritical state, the surface of the waste rubber powder is subjected to desulfurization degradation under the action of illumination and a catalyst, and the surface layer subjected to desulfurization degradation still wraps the surface of the rubber powder due to the absence of the action of an external solvent, so that the rubber of the desulfurized surface layer blocks the penetration of ultraviolet light, namely, the illumination cannot reach the inside of the waste rubber powder, and the inside of the waste rubber powder still is in a three-dimensional cross-linked state. Therefore, even if photocatalytic degradation is carried out in a non-supercritical carbon dioxide state, the degradation efficiency and degree are low, sufficient desulfurization degradation of the crosslinked waste rubber component cannot be realized, and the basically fully uncrosslinked linearized rubber cannot be prepared;

2. as can be seen from the comparison of the data in the above examples and comparative examples 1 and 2, the method of the present invention provides a higher degree of desulfurization of the waste rubber crumb and a higher degree of linearization of the devulcanized rubber. Meanwhile, the linearized active rubber obtained by the method has no components such as a desulfurizer, an organic softener and the like. In particular, the twin-screw mechanical devulcanization used in example 21 was carried out without differential chain scission of the three-dimensional crosslinked network in the waste rubber powder, and therefore, the gel content was relatively low, but at the same time, the small molecules content was high, the large molecules content was low, and the molecular weight of the large molecular chains was relatively low. The preparation methods adopted in examples 1 to 20 have the advantage of selective chain scission for S-S bonds and S-C bonds in the three-dimensional cross-linked network of the waste rubber powder, so that the desulfurization linearized active rubbers prepared in examples 1 to 20 of the present invention have higher macromolecular content than that of example 21.

3. More particularly, as can be seen from the comparison of the data in examples 1 to 17 above, the use of the composite inorganic photocatalyst to optimize the processes in the swelling treatment step and the photocatalytic desulfurization reaction step can significantly improve the desulfurization regeneration degree of the waste rubber powder, resulting in a substantially fully uncrosslinked, linearized rubber. And the process is optimized, and the prepared fully-desulfurized de-crosslinked linearized rubber has high macromolecular polymer (rubber) content, large molecular weight and narrow macromolecular chain distribution coefficient (polydispersity index PDI).

4. The invention has no strict requirement on the wavelength of ultraviolet light and can be realized within the wavelength range of 350-420.

Preparation of the modifier

Examples 22 to 42, comparative examples 3 and 4

Examples 22 to 42 self-adhesive web modifiers were prepared, all as follows: carrying out banburying mixing on linear active rubber, filler (light calcium carbonate and diatomite in a weight ratio of 1:1) and rubber crosslinking assistant (DCP and TMTM in a weight ratio of 1:1) to obtain a mixture; and extruding and molding the mixture, and cutting into granules to obtain the modifier. Banburying and mixing at 80 deg.C for 30 min; the extrusion temperature was 50 ℃ and the extrusion rate was 100 rpm. The embodiments differ in that: the types of the linearized active rubber are different, the raw material proportions are different, and the details are shown in table 3.

Comparative examples 3 and 4 modifiers for self-adhesive webs were prepared as follows: banburying and mixing the desulfurized regenerated rubber, the filler (light calcium carbonate and diatomite in a weight ratio of 1:1) and the rubber crosslinking aid (DCP and TMTM in a weight ratio of 1:1) to obtain a mixture; and extruding and molding the mixture, and cutting into granules to obtain the modifier. Banburying and mixing at 80 deg.C for 30 min; the extrusion temperature was 50 ℃ and the extrusion rate was 100 rpm. The embodiments differ in that: the types of devulcanized reclaimed rubber vary and are detailed in Table 3.

TABLE 3

Preparation of self-adhesive coil

Examples 43 to 63, comparative examples 5 and 6

The same procedure was used to prepare self-adhesive webs in examples 43 to 63 and comparative examples 5 and 6, respectively, except that the modifiers were selected, as shown in Table 4. The preparation process comprises the following steps:

raw materials: the asphalt is alkyl petroleum asphalt, Qinhuang island No. 90 asphalt, and the penetration degree is as follows: 90, respectively; modifying agent: see table 4; elastomeric polymer: SBS (Yueyang petrochemical 791-H); filling: talc powder, mesh number: is larger than 500 meshes; the raw materials are as follows: asphalt modifier elastomeric polymer filler 44:37:2: 17.

The method comprises the following steps:

(a) heating the asphalt to 160 ℃, adding an elastomer polymer, stirring, preserving heat and swelling, wherein the preserving heat temperature is as follows: 160 ℃, stirring rate: 200rpm, swelling time: 60 min;

(b) adding a modifier, stirring, preserving heat, dispersing, swelling, and preserving heat: 160 ℃, stirring rate: 200rpm, dispersion swelling time: 20 min;

(c) grinding with colloid mill at 160 deg.C for 15min, and homogenizing for the second time

(d) Adding a filler, stirring and dispersing under the condition of heat preservation, wherein the heat preservation temperature is as follows: 160 ℃, stirring rate: 200rpm, dispersion time: 40 min; and (6) detecting and discharging.

(e) Impregnating felt cloth with a sizing material by a dipping method, then coating a cover by a roll coating method, then rolling and forming, coating a film and cooling, measuring and cutting the material, sampling and detecting, and packaging the waterproof coiled material into a roll and warehousing.

The performance of the prepared self-adhesive coiled material is characterized, the detection method and the detection standard are carried out according to GB23441-2009 self-adhesive polymer modified asphalt waterproof coiled material, and the test results are shown in Table 4:

TABLE 4

From the above experimental cases, it can be seen that the examples 43 to 55, 62 and 63 are the effects of the linearized active rubbers with different physical properties for preparing the self-adhesive coiled material. When the contents of the linearized molecules are basically close to each other, the higher the content of the linearized macromolecules in the self-adhesive coiled material is, the larger the molecular weight is, the more excellent the physical properties of the self-adhesive coiled material is, the specific properties are represented by heat resistance, low-temperature flexibility, viscosity retention and peel strength, the higher the molecular weight is, the higher the content is, under the action of the rubber crosslinking assistant, the linearized macromolecules, the elastomer polymer and the heavy asphalt form a micro-crosslinking structure, the structure can better resist the damage of external force, the higher the heat resistance and the higher the cohesion (peel strength and viscosity retention), the more excellent low-temperature flexibility is, in order to ensure the initial viscosity of the self-adhesive coiled material, the content of the gradient micromolecules is not small, but the excessive gradient micromolecules can cause the reduction of the cohesion of a micro-crosslinking network, and then influence the performance indexes such as heat resistance and peel strength;

examples 53 and 56 to 59 are that the ratio of different rubber crosslinking agents in the modifier affects the performance of the self-adhesive coiled material, and too little rubber crosslinking aid causes the strength (cohesive force) of a crosslinking network to be low, which further affects the comprehensive physical performance of the self-adhesive coiled material, and when the ratio is adjusted to a better range, the contribution to the comprehensive physical performance of the self-adhesive coiled material is larger;

examples 53, 59 to 62 are that the ratio of different linearized rubbers in the modifier affects the performance of the self-adhesive coiled material, the higher the ratio of the linearized active rubbers is, the higher the content of the linearized macromolecules therein is, the greater the contribution to the low-temperature flexibility of the coiled material is, the more dense the formed micro-crosslinked network is, the greater the cohesive force thereof is, and then the more excellent peel strength, the cohesive property and the heat resistance are expressed;

in the linearized rubbers prepared by different methods in examples 53 and 63, the ratio of the gradient small molecules to the solubilizing oil is high, and the molecular weight and content of the linearized large molecules are low, so that the relatively low comprehensive physical properties of the self-adhesive coiled material are reflected. It should be noted that the linearized rubber obtained by mechanical desulfurization also has the influence of the dissolution-supporting oil, which leads to the obvious increase of the oil permeability of the self-adhesive coiled material, because the dissolution-supporting oil is a small molecule with lower molecular weight, the molecular thermal motion capability is stronger, and the probability of migration is higher;

in the embodiment 53 and the comparative examples D5 and D6, the influence of the rubbers with different desulfurization degrees on the comprehensive physical properties of the self-adhesive coiled material is shown, and in fact, the modifiers adopted in the D5 and D6 have fewer uncrosslinked components, lower contents of linearized macromolecules and gradient micromolecules and higher content of crosslinked particles. The micro-crosslinked network is shown on the self-adhesive coiled material, and the formed micro-crosslinked network has poor cohesive force due to the damage of a large number of stress concentration points of granular rubber, so that the comprehensive physical properties of the self-adhesive coiled material are influenced.

In addition, after the modifier is applied, the heat aging resistance of the self-adhesive coiled material is more excellent, because the combined carbon black and the physical/chemical anti-aging agent existing in the rubber are partially separated and dissolved in the self-adhesive coiled material in the desulfurization and de-crosslinking processes, and the free carbon black and the physical/chemical anti-aging agent have larger contribution to resisting heat-oxygen aging. The devulcanized reclaimed rubber of comparative examples D5 and D6 did not undergo carbon black/physical chemical antioxidant precipitation, and thus had a weaker resistance to thermal oxidative aging.

In addition, in order to verify the initial adhesiveness of the present embodiment, a GB/T4852-2002 pressure-sensitive adhesive bonding initial adhesiveness test method (rolling ball method) was used as a test method for verifying the excellent initial adhesiveness of the self-adhesive roll material of the present invention, and the test results are shown in table 5.

TABLE 5

At present, the initial viscosity test of the self-adhesive asphalt waterproof coiled material at present on the market is generally between 8-20# balls, and after the modifier is added, the initial viscosity of the self-adhesive coiled material is far higher than that of the common self-adhesive coiled material on the market. Moreover, it can be seen from the above examples that the higher the content of the gradient small molecule is, the better the initial viscosity is, but the too high content of the gradient small molecule in the linearized active rubber affects the cohesion of the micro-crosslinked network of the system; in addition, after the modifier is added, the initial viscosity of the self-adhesive coiled material is not greatly attenuated due to the action of thermal oxidation aging, except for the contribution of an anti-aging auxiliary agent in a system, the tail end of a molecular chain of gradient micromolecules in the modifier can form a part of polar active functional groups in the de-crosslinking process, and the functional groups have good affinity with a base layer and the coiled material, so that more excellent initial viscosity is reflected.

Examples 64 to 69 comparative example 7

Self-adhesive rolls were prepared in examples 64 to 69 and comparative example 7(D7), all using the following materials: the asphalt is alkyl petroleum asphalt, Qinhuang island No. 90 asphalt, and the penetration degree is as follows: 90, respectively; the modifier was the modifier prepared in example 32 above; elastomeric polymer: SBS (Yueyang petrochemical 791-H); filling: talc powder, mesh number: is larger than 500 meshes; the difference lies in the dosage ratio among the raw materials of asphalt, modifier, elastomer polymer, etc., which is detailed in table 6:

the self-adhesive web was prepared according to the same procedure as in example 43.

TABLE 6

Examples	Asphalt	Modifying agent	Elastomeric polymers	Filler material
					64	55	25	0	20
65	40	50	0	10
					66	37	38	0	25
67	43	40	7	10
					68	49.5	40	0.5	10
69	48	40	2	10
					D7	70	20	0	10

The properties of the self-adhesive webs prepared in the above examples were characterized and are shown in table 7:

TABLE 7

From the above cases, it is known that, as the amount of the self-adhesive modifier (64/65/66/D7) is increased, the comprehensive physical properties of the self-adhesive coiled material are better improved, and the design requirements of GB23441-2009 can be met, because the self-adhesive modifier is proper in amount, the content of linearized macromolecules in the self-adhesive modifier is enough to form a relatively stable micro-crosslinked network, and then the self-adhesive coiled material shows better comprehensive physical properties; and if the addition amount of the self-adhesive modifier is too small (D7), the linear macromolecular content in the modification system is too small to form a stable micro-crosslinked network, and the aspects of poor heat resistance, low temperature, peel strength, adhesiveness and the like are further shown. With the addition of a small amount of high molecular polymer (example 67/68/69), the comprehensive physical properties of the self-adhesive coiled material are greatly improved, because the additional high molecular polymer and the linearized macromolecules in the system can form a more compact micro-crosslinked network, the cohesion of the system is enhanced, and then the more excellent comprehensive physical properties are shown.

Example 70

The raw materials and preparation process used in this example are the same as those in example 69, except that the asphalt is selected from alkyl petroleum asphalt, qilu petrochemical No. 50 asphalt, penetration: 50. the characterization results are shown in Table 8.

Example 71

The raw materials and preparation process used in this example are the same as those in example 69, except that the asphalt is alkyl petroleum asphalt, Liaohe petrochemical No. 200 asphalt, penetration: 200. the characterization results are shown in Table 8.

Example 72

The raw materials and preparation process used in this example were the same as in example 69, except that the elastomeric polymer was selected from SIS (table rubber 4111A). The characterization results are shown in Table 8.

Example 73

The raw materials and preparation process used in this example were the same as in example 69, except that the elastomeric polymer was selected from SEBS (ba lin petrochemical 503). The characterization results are shown in Table 8.

Example 74

The raw materials and preparation process used in this example were the same as in example 69, except that the elastomeric polymer was selected from SBR (gillin petrochemical 1502). The characterization results are shown in Table 8.

TABLE 8

In addition to the above examples, the present invention also includes other embodiments, for example, other types or combinations of talc powder, heavy calcium carbonate, light calcium carbonate and diatomite are selected as fillers, and other types or combinations of DCP, TMTM, DM, H, and bromomethyl p-tert butyl phenol formaldehyde resins are selected as rubber crosslinking aids, which can achieve good technical effects, and obtain self-adhesive rolls with excellent performance, and for saving space, the details are not repeated here.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The self-adhesive polymer modified asphalt waterproof coiled material is characterized by comprising, by weight, 37-55 parts of asphalt, 25-50 parts of a modifier and 10-25 parts of a first filler, wherein the modifier comprises linearized active rubber, a second filler and a rubber crosslinking aid, the linearized active rubber is obtained by desulfurization treatment of waste rubber powder, and the weight percentage content of linearized molecules in the linearized active rubber is more than or equal to 75%; the linearized molecules in the linearized active rubber comprise gradient micromolecules and macromolecular polymers, the molecular weight of the gradient micromolecules is 500-10000, and the molecular weight of the macromolecular polymers is more than 10000; in the linearized molecules, the weight percentage content of the gradient small molecules is 10-20%, and the weight percentage content of the macromolecular polymer is 80-90%; the linearized active rubber is prepared by the following method: in supercritical carbon dioxide, placing a mixture of waste rubber powder and a photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber; in the modifier, the weight ratio of the linearized active rubber, the second filler and the rubber crosslinking assistant is 100: 20-60: 0.05 to 2.

2. The self-adhesive polymer modified asphalt waterproofing membrane according to claim 1, wherein the asphalt is alkyl petroleum asphalt.

3. The self-adhesive polymer modified asphalt waterproof roll material as claimed in claim 1, wherein the penetration of asphalt at 25 ℃ is 50-200 mm^-1。

4. The coiled material of claim 1, wherein the first filler and the second filler are each independently selected from one or more of talc, heavy calcium carbonate, light calcium carbonate and diatomaceous earth.

5. The roll of self-adhesive polymer-modified asphalt waterproofing material according to claim 1, wherein the mesh number of the first filler and the second filler is greater than 300 mesh.

6. The self-adhesive polymer modified asphalt waterproofing membrane according to claim 1, wherein the rubber crosslinking assistant is one or more of DCP, TMTM, DM, H and bromomethyl p-tert butyl phenol formaldehyde resin.

7. The self-adhesive polymer modified asphalt waterproof roll material as claimed in claim 1, wherein the raw material of the roll material further comprises 0.5-7 parts by weight of an elastomeric polymer.

8. The self-adhesive polymer modified asphalt waterproof roll material as claimed in claim 7, wherein the raw material of the roll material further comprises 0.5-2 parts by weight of the elastomer polymer.

9. The roll of self-adhesive polymer-modified asphalt waterproofing material according to claim 7, wherein the elastomeric polymer is one or more of SBS, SIS, SEBS and SBR.

10. A method for preparing a self-adhesive polymer modified asphalt waterproofing membrane according to any one of claims 1 to 9, characterized in that the preparation method comprises the following steps:

mixing and dispersing asphalt, a modifier and a first filler to obtain a rubber material; and

and (3) dipping or coating the rubber material on the surface of the felt, and pressing the felt for forming to obtain the coiled material.

11. The method according to claim 10, wherein an elastomeric polymer is added simultaneously with the mixing and dispersing of the asphalt, the modifier and the first filler.

12. The method of claim 11, wherein the step of preparing the compound comprises:

mixing and swelling the bitumen and the elastomeric polymer to obtain a first mixture;

mixing and swelling the first mixture with the modifier to obtain a second mixture;

grinding the second mixture to obtain a secondary homogenized material;

and stirring and dispersing the secondary homogenized material and the first filler to obtain the rubber material.

13. The production method according to claim 12,

the step of preparing the first mixture comprises: and heating the asphalt to 130-160 ℃, then adding the elastomer polymer into the asphalt, and carrying out first heat preservation swelling under the stirring condition to obtain the first mixture.

14. The preparation method of claim 13, wherein the stirring speed of the first heat-preservation swelling process is 200-600 rpm, the heat-preservation temperature is 130-160 ℃, and the swelling time is 30-90 min.

15. The method of claim 12, wherein the step of preparing the second mixture comprises: and adding the modifier into the first mixture, and carrying out second heat preservation swelling under the stirring condition to obtain a second mixture.

16. The preparation method of claim 15, wherein the stirring speed of the second heat-preservation swelling process is 200-600 rpm, the heat-preservation temperature is 130-160 ℃, and the swelling time is 15-45 min.

17. The method of claim 12, wherein the step of preparing the secondary homogenate comprises: and grinding the second mixture for 15-30 min by adopting a colloid mill at the temperature of 130-160 ℃ to obtain the secondary homogenized material.

18. The method of claim 12, wherein the step of preparing the compound comprises: and dispersing the secondary homogenized material and the first filler for 20-60 min under the conditions of a stirring speed of 200-600 rpm and a temperature of 130-160 ℃ to obtain the rubber material.

19. The method of claim 12, wherein prior to the step of mixing and swelling the first mixture with a modifier, the method further comprises the step of preparing the modifier by:

carrying out banburying mixing on the linearized active rubber, the second filler and the rubber crosslinking assistant to obtain a mixture; and

and extruding and molding the mixture to obtain the modifier.

20. The method of claim 10, wherein the linearized active rubber is prepared by the following method: and (2) in supercritical carbon dioxide, placing the mixture of the waste rubber powder and the photocatalyst under ultraviolet light for photocatalytic desulfurization reaction to obtain the linearized active rubber.

21. The production method according to claim 20, wherein the photocatalyst is a composite inorganic photocatalyst.

22. The method of claim 20, wherein the photocatalyst is selected from Co-doped TiO₂、ZrO₂/ZnO composite and ZrO₂/TiO₂One or more of the complexes.

23. The method according to claim 20, wherein the photocatalyst is used in an amount of 0.5 to 3% by weight based on the waste rubber powder.