CN110820810A - Thermoplastic polyolefin pre-laid waterproof coiled material and preparation method thereof - Google Patents

Thermoplastic polyolefin pre-laid waterproof coiled material and preparation method thereof Download PDF

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CN110820810A
CN110820810A CN201911228094.7A CN201911228094A CN110820810A CN 110820810 A CN110820810 A CN 110820810A CN 201911228094 A CN201911228094 A CN 201911228094A CN 110820810 A CN110820810 A CN 110820810A
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thermoplastic polyolefin
adhesive
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melt pressure
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CN110820810B (en
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张广彬
孙艳芳
李延霞
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DYANMIC NEW TYPE WATERPROOF BUILDING MATERIALS Co Ltd SHENGLI OIL FIELD
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DYANMIC NEW TYPE WATERPROOF BUILDING MATERIALS Co Ltd SHENGLI OIL FIELD
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    • EFIXED CONSTRUCTIONS
    • E02HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02DFOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D31/00Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution
    • E02D31/02Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution against ground humidity or ground water
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J157/00Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09J157/02Copolymers of mineral oil hydrocarbons
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
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    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
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    • C08K2003/265Calcium, strontium or barium carbonate

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Abstract

The invention relates to a thermoplastic polyolefin pre-paved waterproof coiled material and a preparation method thereof. The technical scheme is as follows: the upper portion of the thermoplastic polyolefin waterproof main body layer forms a butyl modified SIS hot-melt pressure-sensitive self-adhesive layer, a construction welding overlapping region is reserved on one side edge portion of the thermoplastic polyolefin waterproof main body layer, a weather-resistant mineral particle functional layer with cement reaction activity is coated on the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer, an anti-sticking isolation edge film is arranged on one side edge portion of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer, and a construction self-adhesive overlapping region is arranged below the anti-sticking isolation edge film. The beneficial effects are as follows: the internal stress of the thermoplastic polyolefin waterproof sheet is obviously reduced, and the dimensional stability is greatly improved; the high-temperature cohesion of the pressure-sensitive adhesive is improved through the optimized design of the butyl modified SIS hot-melt pressure-sensitive self-adhesive formula; and ingenious composite overlap edge structural design, the effective combination of the three makes the product have excellent performance of preventing the edge from being warped.

Description

Thermoplastic polyolefin pre-laid waterproof coiled material and preparation method thereof
Technical Field
The invention relates to a non-asphalt-based pre-paved waterproof building coil, in particular to a thermoplastic polyolefin pre-paved waterproof coil and a preparation method thereof.
Background
One of the difficulties which plague the industry for decades in underground waterproofing is the waterproofing quality of the bottom plate and the side wall without the construction space. The main reason is leakage of blow-by water. Traditional waterproof materials adopt outer waterproof and inner waterproof, and waterproof coiled materials are only adhered to a base layer, but not adhered to structural concrete. Once the coil is damaged, groundwater can flow between the waterproofing layer and the structural concrete, from the concrete cracks into the interior of the building. Another reason is sedimentation effects. When the traditional waterproof material is bonded with the base layer, once foundation settlement occurs, the base layer is easy to deform and settle, the waterproof layer is easy to distort and deform along with the foundation settlement, the waterproof layer is easy to separate from the bonded base layer, the waterproof layer cannot be completely sealed, and the bottom plate is exposed in underground water. Therefore, it becomes a challenge how to provide direct full-bonding waterproof protection for the structural concrete at the side wall part without the construction space of the bottom plate and the side wall.
The U.S. Grace corporation invented a pre-paved waterproof roll system and a construction technology in 1992, and the high-molecular self-adhesive film waterproof roll is adopted to realize full adhesion between the structural concrete and the side wall part without the construction space of the bottom plate and the side wall in the world for the first time, so that the optimal waterproof effect is obtained. The waterproof coiled material is a novel waterproof coiled material developed after 90 years in the 20 th century, has the advantages of good low-temperature and waterproof performances, high tension and elongation, self-adhesion and the like, is deeply favored by the building waterproof industry, particularly by construction units, and is rapidly developed domestically in recent years. However, the self-adhesive adopted by the waterproof coiled materials in China still mainly adopts modified asphalt, so that the technical defects of poor aging resistance, need of arranging a cement mortar protective layer in the pre-paving construction process and the like exist, and further the construction efficiency is low and potential engineering risks are caused. The core for solving the problems is to increase the research on the production and application of the polymer self-adhesive and replace the modified asphalt self-adhesive currently used in China. Some published documents in recent years report solutions, such as:
the invention discloses a non-uncovering type macromolecule self-adhesive waterproof coiled material and a preparation method thereof, wherein the patent application number of the Chinese patent is 201310297231.9, the patent name is 'a non-uncovering type macromolecule self-adhesive waterproof coiled material', the invention comprises a plastic base material, the two sides of the upper surface of the plastic base material are lapping areas, the middle part of the upper surface of the plastic base material is a bonding area with structural concrete, and a self-adhesive layer and an isolating layer are thermally coated on the upper surface of the plastic base material. Wherein the self-adhesive layer in the structure of the uncovering-free type macromolecule self-adhesive waterproof coiled material consists of SBS resin, SIS resin, plasticizer, tackifier, light absorbent and filler; the self-adhesive layer is provided with an isolating layer which is composed of active inorganic particles and can generate hydration reaction with the freshly mixed cement-based material. When the self-adhesive waterproof coiled material with the structure is used, concrete is directly poured without removing an isolation layer material on the surface of the self-adhesive waterproof coiled material, and a firm connection interface is formed. Therefore, the method has the advantages of simpler construction, reduction of resource waste, more stable and reliable bonding performance with concrete and the like.
In document 2, chinese patent application No. 201420307428.6, the patent name "a high polymer pre-paved waterproof roll" is that the technical scheme of the patent is: the upper surface of the modified polyethylene plastic waterproof main body layer is an SIS hot-melt pressure-sensitive self-adhesive layer, and a weather-resistant mineral particle functional layer with cement reaction activity and a heat-reflection type anti-sticking isolation edge film positioned on one side edge of the coiled material are covered on the upper surface of the SIS hot-melt pressure-sensitive self-adhesive layer; the beneficial effects are that: the heat-reflection type anti-sticking isolation edge film can obviously reduce the surface temperature of the SIS hot-melt pressure-sensitive self-adhesive layer at the lapping edge part of the high-molecular pre-paved waterproof coiled material exposed to the sun outdoors, so that the thermal creep property of the SIS hot-melt pressure-sensitive self-adhesive is reduced, and the removal of the anti-sticking isolation edge film in the construction process is facilitated; the setting of the weather-resistant mineral particle functional layer enables the coiled material to have the concrete mortar bonding construction characteristic, effectively prevents the problem of ultraviolet ray aging caused by long-term exposure of self-adhesive glue in the air, and provides a non-sticky pedestrian surface for construction operation, thereby avoiding the setting of a cement mortar protective layer and reducing the construction cost.
The technical scheme reported in the above-mentioned published documents adopts macromolecule self-adhesive to replace modified asphalt self-adhesive, and basically solves the technical defects of poor ageing resistance and the need of setting cement mortar protective layer in the pre-laying construction process of the domestic existing products. However, the document 1 has technical defects of poor water resistance and ultraviolet aging performance of the cement-based particle isolation layer, and has potential engineering hidden troubles. Although the technical defects are solved by the arrangement of the weather-resistant mineral particle functional layer in the document 2, the fatal technical defects still exist, namely, after the polyethylene plastic waterproof main body layer is constructed, the lap joint part of the coiled material is easy to deform and tilt or even separate under the dual actions of swelling of the SIS hot-melt pressure-sensitive self-adhesive and the internal stress of the polyethylene plastic waterproof main body layer after the polyethylene plastic waterproof main body layer is exposed to the sun, and the engineering quality is seriously influenced.
Disclosure of Invention
The invention aims to provide a thermoplastic polyolefin pre-paved waterproof coiled material and a preparation method thereof aiming at the defects in the prior art, the coiled material has excellent performance of preventing edge warping, and the technical defect that the overlapping edge is easy to warp and release in the prior art is effectively overcome.
The invention provides a thermoplastic polyolefin pre-paved waterproof coiled material, which has the technical scheme that: comprises a thermoplastic polyolefin waterproof main body layer (1), a butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), a weather-resistant mineral particle functional layer (3), an anti-sticking isolation side film (4), a construction welding overlapping area (5) and a construction self-adhesive overlapping area (6), a butyl modified SIS hot melt pressure sensitive self-adhesive layer (2) is formed on the upper part of the thermoplastic polyolefin waterproof main body layer (1), a construction welding overlapping area (5) is reserved at one side edge part of the thermoplastic polyolefin waterproof main body layer (1), and a weather-resistant mineral particle functional layer (3) with cement reaction activity is coated on the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), an anti-sticking isolating edge film (4) is arranged on one side edge part of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), and a construction self-adhesive lap joint area (6) is arranged below the anti-sticking isolation side film (4), and a composite lap joint side structure is formed by the construction self-adhesive lap joint area (6) and the construction welding lap joint area (5).
Preferably, the weather-resistant mineral particle functional layer (3) is composed of synthetic sand.
Preferably, the construction welding overlapping area (5) and the construction self-adhesion overlapping area (6) are adjacently arranged on the same side of the coiled material to form a composite overlapping edge structure.
Preferably, the width of the construction welding overlapping area (5) is 5-6 cm, and the width of the construction self-adhesion overlapping area (6) is 3-4 cm.
Preferably, the method for producing the thermoplastic polyolefin waterproof main body layer (1) is as follows:
firstly, adding a reinforcing material, an antioxidant, titanium dioxide and thermoplastic polyolefin elastomer resin into a mixer, mixing and stirring for 5-20 minutes, and then preparing a reinforcing master batch by adopting a double-screw granulator; then adding the thermoplastic polyolefin resin, the reinforced master batch and the filling material into a double-screw molding extruder with the length-diameter ratio larger than 30 through weight loss metering equipment, and extruding and molding the thermoplastic polyolefin waterproof main body layer (1) with the thickness of 0.5-1.5 mm;
wherein, by weight, 40-75 parts of thermoplastic polyolefin resin; 25-60 parts of thermoplastic polyolefin elastomer resin; 0.5-10 parts of a reinforcing material; 10-50 parts of a filling material; 0-2 parts of an antioxidant; 1-3 parts of titanium dioxide.
Preferably, the preparation method of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2) is as follows:
firstly, sequentially adding polyisobutylene and brominated butyl rubber into an internal mixer, carrying out back mixing and internal mixing for 7-8 minutes at the temperature of 130-140 ℃, then carrying out rubber discharge and filtration, then packaging the mixed masterbatch by using an open mill, carrying out thin-passing on the mixed masterbatch for 2-3 times respectively, and cutting the mixed masterbatch into blocks for later use; firstly adding naphthenic white oil, petroleum resin and an antioxidant into a reaction kettle with a stirring device, stirring and heating to 120-130 ℃, adding SIS thermoplastic rubber after materials are fully melted, then stirring and heating to 180-190 ℃ under the protection of nitrogen, then adding a formula amount of prefabricated mixing master batch, stirring for more than 30min at a heat preservation time until no visible particles exist, then adding a coupling agent, cooling and stirring to 145-155 ℃, and then coating a hot-melt pressure-sensitive self-adhesive with the thickness of 0.3-0.5 mm on a thermoplastic polyolefin waterproof main body layer by using a hot-melt pressure-sensitive adhesive coating machine to form a pressure-sensitive self-adhesive layer;
the composite material comprises, by weight, 25-40 parts of SIS thermoplastic rubber, 2-10 parts of a modifier, 20-35 parts of naphthenic oil, 35-60 parts of petroleum resin, 5-10 parts of polyisobutylene, 0.5-2 parts of an antioxidant and 0-2 parts of a coupling agent.
Preferably, the surface of the reinforcing material is treated by a coupling agent to form ultrafine reinforcing inorganic fibers, the average diameter of the fibers is 10-13 um, and the average diameter of the fibers is 70-150 um.
Preferably, the filling material is calcium carbonate, and the titanium dioxide is high-weather-resistance rutile type titanium dioxide.
Preferably, the SIS thermoplastic rubber is a styrene-isoprene-styrene block copolymer, and the technical parameters are as follows according to parts by mass: 15 parts of combined styrene, 5-65 parts of diblock SI, 4-10 g/10min of melt mass flow rate at 200 ℃/5 kg.
Preferably, the modifier is brominated butyl rubber, the antioxidant is a composite antioxidant prepared by compounding an antioxidant 1010 and an antioxidant 168 in any ratio, and the coupling agent is a silane coupling agent.
The preparation method of the thermoplastic polyolefin pre-paved waterproof roll material comprises the following steps:
adding the prepared butyl modified SIS hot-melt pressure-sensitive self-adhesive into a hot-melt pressure-sensitive adhesive coating machine, coating the 0.3-0.5 mm butyl modified hot-melt pressure-sensitive self-adhesive on a 0.5-1.5 mm thick thermoplastic polyolefin waterproof main body layer through the hot-melt pressure-sensitive adhesive coating machine, and not coating adhesive in an area which is 5-6 cm inward from one side edge of the thermoplastic polyolefin waterproof main body layer during coating to serve as a reserved construction welding lap joint area; then covering an anti-adhesion isolation edge film in an area which is 3-4 cm away from the inner side of the construction welding overlapping area to serve as a construction self-adhesion overlapping area, and then synchronously covering the rest pressure-sensitive self-adhesive layers with a weather-resistant mineral particle functional layer with cement reaction activity by adopting a sand-blasting machine; and then the thermoplastic polyolefin pre-paved waterproof coiled material product with the thickness of 1.2-1.8 mm is prepared by traction compaction, cooling and shaping, reeling, metering and cutting.
The invention is realized by adopting a one-step method, so that the production efficiency and the quality stability of the product are greatly improved, and the product has obvious cost advantage.
Compared with the prior art, the invention has the following beneficial effects:
the internal stress of the thermoplastic polyolefin waterproof sheet is remarkably reduced, and the dimensional stability is greatly improved; by the optimized design of the butyl modified SIS hot-melt pressure-sensitive self-adhesive formula, the high-temperature (generally 40-50 ℃) cohesion of the pressure-sensitive adhesive is obviously improved under the condition that the adhesive property of the SIS hot-melt pressure-sensitive self-adhesive is not influenced; the product has excellent performance of preventing the edge from being warped due to the effective combination of the three components, thereby effectively solving the technical defect that the position of the overlapping edge is easy to warp and release in the prior art;
the technical defect that in the prior art, a lap joint edge is easy to warp and release is effectively overcome by a combined scheme of a Thermoplastic Polyolefin (TPO) waterproof sheet based on an 'anti-warping edge' design, a butyl modified SIS hot-melt pressure-sensitive self-adhesive and a composite lap joint edge structure design;
secondly, a brand-new wet bonding technology is adopted, the coiled material and the structural layer concrete form permanent organic combination, and the hidden trouble of water channeling in the middle is avoided; even if the local damage of the coiled material occurs, the water is limited in a very small range, and the reliability of the waterproof layer is completely improved;
thirdly, the shock resistance and the puncture resistance are excellent, the construction load directly acting on the reinforced concrete pouring device and the impact of the steel reinforcement framework can be borne, and the reinforced concrete pouring can be directly implemented;
the construction is convenient, a leveling layer is not needed, the requirement on the base layer is low, the influence of weather and base layer humidity is avoided, the construction in rainy season and the construction period reaching project have unique and obvious advantages, and a cement mortar protective layer which consumes time and money is not needed;
fifthly, the SIS hot-melt pressure-sensitive self-adhesive has strong self-healing property and unique self-healing capability for slight construction damage;
and sixthly, the waterproof coiled material is laid on the base layer in the air, is convenient and quick, and is not influenced by the sedimentation deformation of the base layer.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic representation of coil overlap prior to construction;
FIG. 3 is a schematic diagram of a coil after hot melting and rolling;
in the upper diagram: the waterproof building block comprises a thermoplastic polyolefin waterproof main body layer 1, a butyl modified SIS hot-melt pressure-sensitive self-adhesive layer 2, a weather-resistant mineral particle functional layer 3, an anti-sticking isolation edge film 4, a construction welding overlapping area 5 and a construction self-adhesive overlapping area 6.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
The invention provides a thermoplastic polyolefin pre-paved waterproof coiled material, which has the technical scheme that: comprises a thermoplastic polyolefin waterproof main body layer (1), a butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), a weather-resistant mineral particle functional layer (3), an anti-sticking isolation side film (4), a construction welding overlapping area (5) and a construction self-adhesive overlapping area (6), a butyl modified SIS hot melt pressure sensitive self-adhesive layer (2) is formed on the upper part of the thermoplastic polyolefin waterproof main body layer (1), a construction welding overlapping area (5) is reserved at one side edge part of the thermoplastic polyolefin waterproof main body layer (1), and a weather-resistant mineral particle functional layer (3) with cement reaction activity is coated on the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), an anti-sticking isolating edge film (4) is arranged on one side edge part of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), and a construction self-adhesive lap joint area (6) is arranged below the anti-sticking isolation side film (4), and a composite lap joint side structure is formed by the construction self-adhesive lap joint area (6) and the construction welding lap joint area (5).
Foretell construction welding overlap joint district (5) and construction self-adhesion overlap joint district (6) are adjacent to be set up in the homonymy of coiled material, constitute compound overlap edge structure, and the width of construction welding overlap joint district (5) is 5 ~ 6cm, and the width of construction self-adhesion overlap joint district (6) is 3 ~ 4 cm.
The weather-resistant mineral particle functional layer (3) is composed of synthetic sand, preferably the synthetic sand made of white cement, high-activity superfine slag powder, natural mineral particles and the like, and the size range of the synthetic sand is 30-70 meshes of continuous grading.
The weather-resistant mineral particle functional layer has the following technical characteristics: one is irregular flat polygonal, has proper continuous gradation, can effectively improve the contact surface with the hot-melt pressure-sensitive self-adhesive, thereby improving the adhesion firmness and simultaneously putting an end to the puncture damage of the sharp particles to the thermoplastic polyolefin waterproof main body layer; the self-adhesive has excellent weather resistance and water resistance, and can effectively prevent the problem of ultraviolet aging and the like caused by long-term exposure of the self-adhesive in the air under the protection of the self-adhesive; thirdly, the cement has cement reactivity and plays a role in reaction and combination in the solidification process of concrete; and the fourth step is to have the anti-sticking function, which plays the role of anti-sticking in production and transportation, and makes the coiled material resist trampling of human in the construction process.
In addition, the manufacturing method of the thermoplastic polyolefin waterproof main body layer (1) comprises the following steps:
firstly, adding a reinforcing material, an antioxidant, titanium dioxide and thermoplastic polyolefin elastomer resin into a mixer, mixing and stirring for 5-20 minutes, and then preparing a reinforcing master batch by adopting a double-screw granulator; then adding the thermoplastic polyolefin resin, the reinforced master batch and the filling material into a double-screw molding extruder with the length-diameter ratio larger than 30 through weight loss metering equipment, and extruding and molding the thermoplastic polyolefin waterproof main body layer (1) with the thickness of 0.5-1.5 mm;
wherein, by weight, 40-75 parts of thermoplastic polyolefin resin; 25-60 parts of thermoplastic polyolefin elastomer resin; 0.5-10 parts of a reinforcing material; 10-50 parts of a filling material; 0-2 parts of an antioxidant; 1-3 parts of titanium dioxide.
The thermoplastic polyolefin resin has a melt mass flow rate of 0.5-0.8 g/10min (230 ℃/2.16 kg) and an ethylene content (mass fraction) of 45-50%.
The melt mass flow rate of the thermoplastic polyolefin elastomer resin is 1.0-1.5 g/10min (190 ℃/2.16 kg).
The reinforced material is selected from superfine reinforced inorganic fibers with the surfaces treated by a coupling agent, the average diameter of the fibers is 10-13 um, and the average diameter of the fibers is 70-150 um. Preferably the aspect ratio is greater than 7.
The filling material is 425-mesh active light calcium carbonate.
The antioxidant is a compound antioxidant which is compounded by an antioxidant 1010 and an antioxidant 168 according to any ratio.
The titanium dioxide is high weather resistance rutile type titanium dioxide.
In addition, the preparation method of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2) comprises the following steps:
firstly, sequentially adding polyisobutylene and brominated butyl rubber into an internal mixer, carrying out back mixing and internal mixing for 7-8 minutes at the temperature of 130-140 ℃, then carrying out rubber discharge and filtration, then packaging the mixed masterbatch by using an open mill, carrying out thin-passing on the mixed masterbatch for 2-3 times respectively, and cutting the mixed masterbatch into blocks for later use; firstly adding naphthenic white oil, petroleum resin and an antioxidant into a reaction kettle with a stirring device, stirring and heating to 120-130 ℃, adding SIS thermoplastic rubber after materials are fully melted, then stirring and heating to 180-190 ℃ under the protection of nitrogen, then adding a formula amount of prefabricated mixing master batch, stirring for more than 30min at a heat preservation time until no visible particles exist, then adding a coupling agent, cooling and stirring to 145-155 ℃, and then coating a hot-melt pressure-sensitive self-adhesive with the thickness of 0.3-0.5 mm on a thermoplastic polyolefin waterproof main body layer by using a hot-melt pressure-sensitive adhesive coating machine to form a pressure-sensitive self-adhesive layer;
the composite material comprises, by weight, 25-40 parts of SIS thermoplastic rubber, 2-10 parts of a modifier, 20-35 parts of naphthenic oil, 35-60 parts of petroleum resin, 5-10 parts of polyisobutylene, 0.5-2 parts of an antioxidant and 0-2 parts of a coupling agent.
The SIS thermoplastic rubber is a styrene-isoprene-styrene block copolymer, and the preferable technical parameters are as follows: the combined styrene content (mass fraction) is 15%, the diblock (SI) content (mass fraction) is 5-65%, and the melt mass flow rate is 4-10 g/10min (200 ℃/5 kg).
The modifier is brominated butyl rubber, and the preferred technical parameters are as follows: mooney viscosity of 28-36 ML (1 + 8) at 125 ℃ and bromine content (mass fraction) of 1.6-2.2%.
The naphthenic oil is naphthenic white oil, and the preferred technical indexes are as follows: the open flash point is more than or equal to 210 ℃, the pour point is less than or equal to-15 ℃, the content (mass fraction) of saturated hydrocarbon is more than or equal to 93 percent, the aniline point is more than or equal to 105 ℃, and the carbon-type structure is that Ca is less than or equal to 1 percent, Cn is more than or equal to 47 percent and Cp is more than or equal to 50 percent.
The petroleum resin is hydrogenated petroleum resin, and the preferable technical parameters are as follows: the softening point is more than or equal to 105 ℃, the melt rotational viscosity (190 ℃) is more than or equal to 130mPa.s, and the Yellow Index (YI) is less than or equal to 3.
The technical parameters of the polyisobutylene are that the open flash point is more than or equal to 220 ℃, the pour point is less than or equal to 15 ℃, the average molecular weight (Mn) is 1500-2500, and the kinematic viscosity (100 ℃) is 700-4000 mm2/s。
The antioxidant is a compound antioxidant which is compounded by an antioxidant 1010 and an antioxidant 168 according to any ratio.
The coupling agent is a silane coupling agent, preferably an epoxy silane coupling agent.
The multilayer composite structure of the Thermoplastic Polyolefin (TPO) pre-paved waterproof coiled material of the invention enables the TPO pre-paved waterproof coiled material to have the function of pre-paving and anti-sticking, and the technical principle is as follows: during construction, the coiled material is pre-laid in a hollow way or temporarily fixed on the surface of concrete or a compacted sand cushion layer meeting the requirements; then, under the condition of not laying a cement mortar protective layer, directly binding reinforcing steel bars, erecting templates and other procedures on the coiled material, then directly pouring concrete on the weather-resistant mineral particle functional layer of the pre-laid waterproof coiled material, wherein active functional groups on the surface of the weather-resistant mineral particles can form chemical bonding force with silicate groups in cement in the process of curing portland cement in the concrete pouring process, so that stronger chemical and mechanical riveting force is formed between the special weather-resistant mineral particles and the concrete. Meanwhile, the butyl modified SIS hot-melt pressure-sensitive adhesive and the cement paste automatically fill micro-capillary pores on an adhesion interface under the dual actions of pressure and thermal creep, and van der Waals attraction is formed on the adhesion interface. Therefore, after the cement is cured, an adhesive force is formed by the resultant forces of van der Waals attraction force, chemical bonding force, mechanical riveting and the like on the adhesive interface, and further, a continuous permanent strong adhesive is formed after the concrete is cured. The water channeling channel is completely eliminated, a skin-type waterproof system is formed, and even if the waterproof layer is locally damaged, external water cannot flow between the waterproof layer and the structural concrete. And the waterproof performance is obviously improved.
Example 1: the invention provides a preparation method of a thermoplastic polyolefin pre-paved waterproof coiled material, which comprises the following steps:
1. preparation method of Thermoplastic Polyolefin (TPO) waterproof main body layer
Firstly, adding raw materials such as 1 part of reinforcing material, 0.5 part of antioxidant, 2 parts of titanium dioxide, 25 parts of thermoplastic polyolefin elastomer resin and the like into a mixer, mixing and stirring for 10 minutes, and then preparing a reinforcing master batch by adopting a double-screw granulator; then, 75 parts of thermoplastic polyolefin resin, 28.5 parts of reinforced master batch and 10 parts of filling material are respectively added into a double-screw molding extruder with the length-diameter ratio larger than 30 through weightlessness metering equipment, and a Thermoplastic Polyolefin (TPO) waterproof main layer membrane with the thickness of 0.7mm is extruded and molded. The operating process parameters are that the screw temperature is 140-195 ℃, the die temperature is 195-205 ℃ and the three-roller temperature is 50-60 ℃;
the surface of the reinforcing material is treated by a coupling agent to form superfine reinforcing inorganic fibers, the average diameter of the fibers is 10-13 mu m, the average diameter of the fibers is 70-150 mu m, and the length-diameter ratio is 8; the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1: 1; titanium dioxide of the high weather resistance rutile type; the filling material adopts 425-mesh active light calcium carbonate.
2. Preparation method of butyl modified SIS hot-melt pressure-sensitive self-adhesive
Firstly, sequentially adding 5 parts of polyisobutylene and 2 parts of brominated butyl rubber into an internal mixer, back mixing and internally mixing for 7 minutes at the temperature of 130 ℃, then discharging and filtering, then packaging the mixed masterbatch by using an open mill, thinly passing through the mixed masterbatch for 3 times respectively, and cutting the mixed masterbatch into blocks for later use; firstly, adding 30 parts of naphthenic white oil, 50 parts of petroleum resin and 1 part of antioxidant into a reaction kettle with a stirring device, stirring and heating to 130 ℃, adding 40 parts of SIS thermoplastic rubber after the materials are fully melted, then stirring and heating to 190 ℃ under the protection of nitrogen, adding the prepared mixing master batch with the formula amount, stirring for more than 30min under heat preservation until no visible particles exist, then adding 0.5 part of coupling agent, cooling and stirring to 155 ℃ for later use;
the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1:1, and the coupling agent is an epoxy silane coupling agent.
3. Composite forming preparation method of coiled material
Adding the prepared butyl modified SIS hot-melt pressure-sensitive self-adhesive into a hot-melt pressure-sensitive adhesive coating machine, coating the 0.5mm butyl modified hot-melt pressure-sensitive self-adhesive on a 0.7mm thick Thermoplastic Polyolefin (TPO) waterproof main body layer through the hot-melt pressure-sensitive adhesive coating machine, and not coating the adhesive in an inward 5-6 cm area on one side edge of the Thermoplastic Polyolefin (TPO) waterproof main body layer during coating to serve as a reserved construction welding overlapping area. And then covering an anti-adhesion isolation edge film in an area which is 3-4 cm away from the inner side of the construction welding overlapping area to serve as a construction self-adhesion overlapping area, and then synchronously covering the rest pressure-sensitive self-adhesive layers with a weather-resistant mineral particle functional layer with cement reaction activity by adopting a sand-blasting machine. Then the Thermoplastic Polyolefin (TPO) pre-paved waterproof coiled material product with the thickness of 1.2mm is prepared through the working procedures of traction compaction, cooling and shaping, coiling, metering, cutting, packaging and the like.
The product performance was tested according to the standards of "Thermoplastic Polyolefin (TPO) Pre-spread coil (T/CBMF 43-2019)" of China Association of building materials, and the relevant data are shown in Table 1.
Referring to fig. 2 and 3, the process of the present invention is as follows:
remove in the work progress behind the antiseized isolation boundary film (4) of lower coiled material and make its construction self-adhesion overlap area (6) expose, adopt construction welding overlap area (5) of welder welding lower coiled material and Thermoplastic Polyolefin (TPO) waterproof main part layer (1) of upper coiled material to realize body welding (construction welding overlap area is the component part of waterproof main part layer, its material composition is identical completely, so call body welding) overlap joint, welder's waste heat makes the overlap area clearance of two coiled materials of automatic filling after construction self-adhesion overlap area (6) fully melting realize seamless full adhesion, part hot melt pressure sensitive self-adhesive takes place to warp after the compression roller roll-in simultaneously, the avris of being extruded upper coiled material links to each other with butyl modification SIS hot melt pressure sensitive self-adhesive layer (2) of upper coiled material and realizes body bonding (its material composition is identical completely, so call body bonding). So that the composite overlap edge forms a "nip" (shown in more detail in the schematic) to lock the edges of the upper web of material after construction. The composite overlap edge after construction realizes the composite structure combination of 'body welding overlap joint of the welding overlap joint region' + 'seamless full adhesion of the self-adhesive overlap joint region' + 'jaw locking edge of the hot melt pressure sensitive self-adhesive layer', thereby obviously improving the overlap joint reliability and the overlap joint strength and finally solving the technical defect of edge part buckling and releasing of the upper coiled material.
Example 2: the invention provides a preparation method of a thermoplastic polyolefin pre-paved waterproof coiled material, which comprises the following steps:
1. preparation method of Thermoplastic Polyolefin (TPO) waterproof main body layer
Firstly, adding raw materials of 10 parts of reinforcing material, 1.5 parts of antioxidant, 3 parts of titanium dioxide, 60 parts of thermoplastic polyolefin elastomer resin and the like into a mixer, mixing and stirring for 20 minutes, and then preparing into a reinforced master batch by adopting a double-screw granulator; then, 40 parts of thermoplastic polyolefin resin, 74.5 parts of reinforced master batch and 50 parts of filling material are respectively added into a double-screw molding extruder with the length-diameter ratio larger than 30 through weightlessness metering equipment, and a Thermoplastic Polyolefin (TPO) waterproof main body layer membrane with the thickness of 1.5mm is extruded and molded. The operating process parameters are that the screw temperature is 140-185 ℃, the die temperature is 185-195 ℃ and the three-roller temperature is 40-50 ℃;
the surface of the reinforcing material is treated by a coupling agent to form superfine reinforcing inorganic fibers, the average diameter of the fibers is 10-13 mu m, the average diameter of the fibers is 70-150 mu m, and the length-diameter ratio is 9; the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 2: 1; titanium dioxide of the high weather resistance rutile type; the filling material adopts 425-mesh active light calcium carbonate.
2. Preparation method of butyl modified SIS hot-melt pressure-sensitive self-adhesive
Firstly, sequentially adding 10 parts of polyisobutylene and 5 parts of brominated butyl rubber into an internal mixer, back mixing and internally mixing for 8 minutes at the temperature of 140 ℃, then discharging and filtering, then packaging the mixed masterbatch by using an open mill, thinly passing through the mixed masterbatch for 3 times respectively, and cutting the mixed masterbatch into blocks for later use; then adding 20 parts of naphthenic white oil, 35 parts of petroleum resin and 0.5 part of antioxidant into a reaction kettle with a stirring device, stirring and heating to 120 ℃, adding 25 parts of SIS thermoplastic rubber after the materials are fully melted, then stirring and heating to 180 ℃ under the protection of nitrogen, adding the prepared mixing masterbatch with the formula amount, keeping the temperature and stirring for more than 30min until no visible particles exist, then adding 2 parts of coupling agent, cooling and stirring to 145 ℃ for later use;
the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 2:1, and the coupling agent is an epoxy silane coupling agent.
3. Composite forming preparation method of coiled material
Adding the prepared butyl modified SIS hot-melt pressure-sensitive self-adhesive into a hot-melt pressure-sensitive adhesive coating machine, coating the 0.3mm butyl modified hot-melt pressure-sensitive self-adhesive on a 1.5 mm-thick Thermoplastic Polyolefin (TPO) waterproof main body layer through the hot-melt pressure-sensitive adhesive coating machine, and not coating the adhesive in an inward 5-6 cm area on one side edge of the Thermoplastic Polyolefin (TPO) waterproof main body layer during coating to serve as a reserved construction welding overlapping area. And then covering an anti-adhesion isolation edge film in an area which is 3-4 cm away from the inner side of the construction welding overlapping area to serve as a construction self-adhesion overlapping area, and then synchronously covering the rest pressure-sensitive self-adhesive layers with a weather-resistant mineral particle functional layer with cement reaction activity by adopting a sand-blasting machine. Then the Thermoplastic Polyolefin (TPO) pre-paved waterproof coiled material product with the thickness of 1.8mm is prepared through the working procedures of traction compaction, cooling and shaping, coiling, metering, cutting, packaging and the like.
The product performance was tested according to the standards of "Thermoplastic Polyolefin (TPO) Pre-spread coil (T/CBMF 43-2019)" of China Association of building materials, and the relevant data are shown in Table 1.
TABLE 1 physical Properties of the products
Figure DEST_PATH_IMAGE001
The results show that the product has excellent physical properties, and meets or exceeds the product performance requirements of Thermoplastic Polyolefin (TPO) pre-laid coiled materials (T/CBMF 43-2019) in the standards of China Association of building materials.
Example 3: the invention provides a preparation method of a thermoplastic polyolefin pre-paved waterproof coiled material, which comprises the following steps:
1. preparation method of Thermoplastic Polyolefin (TPO) waterproof main body layer
Firstly, adding raw materials such as 5 parts of reinforcing material, 1.0 part of antioxidant, 2 parts of titanium dioxide, 50 parts of thermoplastic polyolefin elastomer resin and the like into a mixer, mixing and stirring for 15 minutes, and then preparing into a reinforced master batch by adopting a double-screw granulator; then 50 parts of thermoplastic polyolefin resin, 58 parts of reinforced master batch and 25 parts of filling material are respectively added into a double-screw molding extruder with the length-diameter ratio larger than 30 through weightlessness metering equipment, and a Thermoplastic Polyolefin (TPO) waterproof main body layer membrane with the thickness of 0.9mm is extruded and molded. The operating process parameters are that the screw temperature is 140-190 ℃, the die temperature is 190-200 ℃ and the three-roller temperature is 40-50 ℃;
the surface of the reinforcing material is treated by a coupling agent to form superfine reinforcing inorganic fibers, the average diameter of the fibers is 10-13 mu m, the average diameter of the fibers is 70-150 mu m, and the length-diameter ratio is 9; the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1: 2; titanium dioxide of the high weather resistance rutile type; the filling material adopts 425-mesh active light calcium carbonate.
2. Preparation method of butyl modified SIS hot-melt pressure-sensitive self-adhesive
Firstly, sequentially adding 5 parts of polyisobutylene and 2 parts of brominated butyl rubber into an internal mixer, back mixing and internally mixing for 7 minutes at the temperature of 130 ℃, then discharging and filtering, then packaging the mixed masterbatch by using an open mill, thinly passing through the mixed masterbatch for 3 times respectively, and cutting the mixed masterbatch into blocks for later use; firstly, adding 20 parts of naphthenic base white oil, 45 parts of petroleum resin and 0.5 part of antioxidant into a reaction kettle with a stirring device, stirring and heating to 130 ℃, adding 35 parts of SIS thermoplastic rubber after the materials are fully melted, then stirring and heating to 185 ℃ under the protection of nitrogen, then adding the prepared mixing masterbatch with the formula amount, preserving heat and stirring for more than 30min until no visible particles exist, then adding 1 part of coupling agent, cooling and stirring to 150 ℃ for later use;
the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1:2, and the coupling agent is an epoxy silane coupling agent.
3. Composite forming preparation method of coiled material
Adding the prepared butyl modified SIS hot-melt pressure-sensitive self-adhesive into a hot-melt pressure-sensitive adhesive coating machine, coating the 0.3mm butyl modified hot-melt pressure-sensitive self-adhesive on a 0.9mm thick Thermoplastic Polyolefin (TPO) waterproof main body layer through the hot-melt pressure-sensitive adhesive coating machine, and not coating the adhesive in an inward 5-6 cm area on one side edge of the Thermoplastic Polyolefin (TPO) waterproof main body layer during coating to serve as a reserved construction welding overlapping area. And then covering an anti-adhesion isolation edge film in an area which is 3-4 cm away from the inner side of the construction welding overlapping area to serve as a construction self-adhesion overlapping area, and then synchronously covering the rest pressure-sensitive self-adhesive layers with a weather-resistant mineral particle functional layer with cement reaction activity by adopting a sand-blasting machine. Then the Thermoplastic Polyolefin (TPO) pre-paved waterproof coiled material product with the thickness of 1.2mm is prepared through the working procedures of traction compaction, cooling and shaping, coiling, metering, cutting, packaging and the like.
The above description is only a few of the preferred embodiments of the present invention, and any person skilled in the art may modify the above-described embodiments or modify them into equivalent ones. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.

Claims (10)

1. A thermoplastic polyolefin pre-paved waterproof coiled material is characterized in that: comprises a thermoplastic polyolefin waterproof main body layer (1), a butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), a weather-resistant mineral particle functional layer (3), an anti-sticking isolation side film (4), a construction welding overlapping area (5) and a construction self-adhesive overlapping area (6), a butyl modified SIS hot melt pressure sensitive self-adhesive layer (2) is formed on the upper part of the thermoplastic polyolefin waterproof main body layer (1), a construction welding overlapping area (5) is reserved at one side edge part of the thermoplastic polyolefin waterproof main body layer (1), and a weather-resistant mineral particle functional layer (3) with cement reaction activity is coated on the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), an anti-sticking isolating edge film (4) is arranged on one side edge part of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2), and a construction self-adhesive lap joint area (6) is arranged below the anti-sticking isolation side film (4), and a composite lap joint side structure is formed by the construction self-adhesive lap joint area (6) and the construction welding lap joint area (5).
2. The roll of thermoplastic polyolefin pre-laid waterproofing material according to claim 1, characterized in that: the weather-resistant mineral particle functional layer (3) is composed of synthetic sand.
3. The roll of thermoplastic polyolefin pre-laid waterproofing material according to claim 1, characterized in that: the construction welding overlapping area (5) and the construction self-adhesion overlapping area (6) are adjacently arranged at the same side of the coiled material to form a composite overlapping edge structure.
4. The roll of thermoplastic polyolefin pre-laid waterproofing membrane according to claim 3, characterized in that: the width of the construction welding overlapping area (5) is 5-6 cm, and the width of the construction self-adhesion overlapping area (6) is 3-4 cm.
5. The roll of thermoplastic polyolefin pre-laid waterproofing material according to claim 1, characterized in that: the manufacturing method of the thermoplastic polyolefin waterproof main body layer (1) comprises the following steps:
firstly, adding a reinforcing material, an antioxidant, titanium dioxide and thermoplastic polyolefin elastomer resin into a mixer, mixing and stirring for 5-20 minutes, and then preparing a reinforcing master batch by adopting a double-screw granulator; then adding the thermoplastic polyolefin resin, the reinforced master batch and the filling material into a double-screw molding extruder with the length-diameter ratio larger than 30 through weight loss metering equipment, and extruding and molding the thermoplastic polyolefin waterproof main body layer (1) with the thickness of 0.5-1.5 mm;
wherein, by weight, 40-75 parts of thermoplastic polyolefin resin; 25-60 parts of thermoplastic polyolefin elastomer resin; 0.5-10 parts of a reinforcing material; 10-50 parts of a filling material; 0-2 parts of an antioxidant; 1-3 parts of titanium dioxide.
6. The roll of thermoplastic polyolefin pre-laid waterproofing membrane according to claim 5, characterized in that: the preparation method of the butyl modified SIS hot-melt pressure-sensitive self-adhesive layer (2) comprises the following steps:
firstly, sequentially adding polyisobutylene and brominated butyl rubber into an internal mixer, carrying out back mixing and internal mixing for 7-8 minutes at the temperature of 130-140 ℃, then carrying out rubber discharge and filtration, then packaging the mixed masterbatch by using an open mill, carrying out thin-passing on the mixed masterbatch for 2-3 times respectively, and cutting the mixed masterbatch into blocks for later use; firstly adding naphthenic white oil, petroleum resin and an antioxidant into a reaction kettle with a stirring device, stirring and heating to 120-130 ℃, adding SIS thermoplastic rubber after materials are fully melted, then stirring and heating to 180-190 ℃ under the protection of nitrogen, then adding a formula amount of prefabricated mixing master batch, stirring for more than 30min at a heat preservation time until no visible particles exist, then adding a coupling agent, cooling and stirring to 145-155 ℃, and then coating a hot-melt pressure-sensitive self-adhesive with the thickness of 0.3-0.5 mm on a thermoplastic polyolefin waterproof main body layer by using a hot-melt pressure-sensitive adhesive coating machine to form a pressure-sensitive self-adhesive layer;
the composite material comprises, by weight, 25-40 parts of SIS thermoplastic rubber, 2-10 parts of a modifier, 20-35 parts of naphthenic oil, 35-60 parts of petroleum resin, 5-10 parts of polyisobutylene, 0.5-2 parts of an antioxidant and 0-2 parts of a coupling agent.
7. The roll of thermoplastic polyolefin pre-laid waterproofing membrane according to claim 5, characterized in that: the reinforced material is selected from superfine reinforced inorganic fibers with the surfaces treated by a coupling agent, the average diameter of the fibers is 10-13 um, and the average diameter of the fibers is 70-150 um.
8. The roll of thermoplastic polyolefin pre-laid waterproofing membrane according to claim 5, characterized in that: the filling material is calcium carbonate, and the titanium dioxide is high weather resistance rutile type titanium dioxide.
9. The roll of thermoplastic polyolefin pre-laid waterproofing according to claim 5 or 6, characterized in that: the SIS thermoplastic rubber is a styrene-isoprene-styrene block copolymer; the modifier is brominated butyl rubber, the antioxidant is a composite antioxidant which is compounded by an antioxidant 1010 and an antioxidant 168 in any ratio, and the coupling agent is a silane coupling agent.
10. The method for preparing thermoplastic polyolefin pre-spread waterproof coiled material according to any one of the claims 1 to 8, characterized by comprising the following processes:
adding the prepared butyl modified SIS hot-melt pressure-sensitive self-adhesive into a hot-melt pressure-sensitive adhesive coating machine, coating the 0.3-0.5 mm butyl modified hot-melt pressure-sensitive self-adhesive on a 0.5-1.5 mm thick thermoplastic polyolefin waterproof main body layer through the hot-melt pressure-sensitive adhesive coating machine, and not coating adhesive in an area which is 5-6 cm inward from one side edge of the thermoplastic polyolefin waterproof main body layer during coating to serve as a reserved construction welding lap joint area; then covering an anti-adhesion isolation edge film in an area which is 3-4 cm away from the inner side of the construction welding overlapping area to serve as a construction self-adhesion overlapping area, and then synchronously covering the rest pressure-sensitive self-adhesive layers with a weather-resistant mineral particle functional layer with cement reaction activity by adopting a sand-blasting machine; and then the thermoplastic polyolefin pre-paved waterproof coiled material product with the thickness of 1.2-1.8 mm is prepared by traction compaction, cooling and shaping, reeling, metering and cutting.
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