CN115074048A

CN115074048A - Thermosensitive discoloring body reverse-adhesion type TPO (thermoplastic polyolefin) macromolecular waterproof coiled material and preparation method thereof

Info

Publication number: CN115074048A
Application number: CN202210881861.XA
Authority: CN
Inventors: 江玉民; 闵建彬; 刘乃林; 邢宇菲
Original assignee: China Building Materials Suzhou Waterproofing Research Institute Co ltd
Current assignee: China National Building Materials Innovation and Technology Research Institute Co Ltd
Priority date: 2022-07-26
Filing date: 2022-07-26
Publication date: 2022-09-20
Anticipated expiration: 2042-07-26
Also published as: CN115074048B

Abstract

The invention discloses a reverse-adhesion type TPO (thermoplastic polyolefin) high-molecular waterproof coiled material of a thermochromic body, which comprises a multilayer composite structure, wherein the multilayer composite structure at least comprises a thermosensitive color development layer, a TPO high-molecular main material layer and a reverse adhesion layer from top to bottom; the thermosensitive color development layer, the TPO polymer main material layer and the anti-adhesion layer comprise the same elastomer material, and the elastomer material is TPO resin; the anti-adhesive layer has a cavity with a large number of active bonding sites inside. By adopting the technical scheme of the invention, two effects of a cold roof and a hot roof are provided, and energy conservation and emission reduction are realized through the color change of the surface of the coiled material; simultaneously, adopt the anti-adhesive layer of inviscid, the inside cavity of anti-adhesive layer is filled to unset cement, forms tenon fourth of the twelve earthly branches structure, reaches the effect of firm bonding, need not to use isolation material or secondary heating sand-lined process, can directly use, has reduced the production and has synthesized the energy consumption.

Description

Thermosensitive discoloring body reverse-adhesion type TPO (thermoplastic polyolefin) macromolecular waterproof coiled material and preparation method thereof

Technical Field

The invention relates to the technical field of high-molecular waterproof rolls, in particular to a thermosensitive discoloring body reverse-adhesion type TPO high-molecular waterproof roll and a preparation method thereof.

Background

With the implementation of the policy of energy conservation and emission reduction, the market share of the polymer waterproof roll material is larger and larger. The self-adhesive type TPO waterproof coiled material occupies a large share due to the construction convenience, and particularly in underground engineering and roofing engineering, the self-adhesive type TPO waterproof coiled material is in the list of preferred products due to the excellent aging resistance.

TPO waterproofing membrane, the polyolefin waterproofing membrane of thermoplasticity, has high weatherability and corrosion resistance, does not contain the plasticizer simultaneously, directly exposes the use and has overlength ageing resistance. The market of the self-adhesive TPO waterproof coiled material is the largest. However, the service life of the self-adhesive TPO waterproof coiled material is greatly influenced by the weather aging of the exposed environment and the damp-heat aging of underground engineering. At present, the phenomenon of insufficient durability generally exists in self-adhesive TPO waterproof coiled materials. On the other hand, most of the traditional roof TPO waterproof coiled materials are white, have the effect of energy-saving and heat-insulating 'cold roofs', but have the problem of 'light pollution'. In addition, in winter, buildings need the effect of 'hot roofing' instead to improve the indoor temperature. Along with the increasing of energy-conserving building demand, present monochromatic TPO waterproofing membrane can't satisfy people's demand, but color-changing TPO waterproofing membrane's market demand is growing day by day.

At present, a large amount of hot-melt pressure-sensitive adhesive is used as an adhesive layer for the self-adhesive high-molecular waterproof coiled material, the hot-melt pressure-sensitive adhesive uses a large amount of petroleum resin and plasticizer in production, the low-temperature resistance and the aging resistance of the hot-melt pressure-sensitive adhesive are far lower than those of a TPO waterproof coiled material body, a wooden barrel effect is caused in the whole life cycle, and the service life of the TPO waterproof coiled material is seriously shortened. Meanwhile, in the pre-paved anti-sticking product, in order to prevent the bonding layer from influencing the construction, the surface of the bonding layer is also required to be covered with a layer of isolation sand, the weight of the isolation sand accounts for more than 60% of the weight of the main polymer material, and the transportation cost is directly increased. Meanwhile, the production energy consumption, the transportation energy consumption and the heat energy consumption in the sand covering process of the isolation sand directly increase the comprehensive production energy consumption of the pre-paved anti-sticking type product, and are not beneficial to energy conservation and emission reduction.

For example, the invention patent CN114635297A in China provides a SBS modified asphalt waterproof coiled material capable of self-adhesive construction and a preparation method thereof, wherein the SBS modified asphalt waterproof coiled material comprises 80-100 parts of ethylene-vinyl acetate copolymer, 20-30 parts of halogenated butyl rubber, 15-25 parts of tackifying resin, 3-5 parts of styrene-isoprene-styrene block copolymer, 50-100 parts of polyisobutylene, 5-10 parts of plasticizer, 10-20 parts of filler, 2-3 parts of vulcanization aid, 1-2 parts of vulcanization accelerator, 1-2 parts of odor remover and 3-5 parts of anti-aging agent. According to the invention, the viscosity of the coiled material is enhanced by adding a large proportion of tackifying resin, so that the problem of poor compatibility of the non-asphalt-based self-adhesive material and the SBS coating material is mainly solved, but the waterproof coiled material is easy to age and poor in weather resistance due to the introduction of a large proportion of oily tackifying resin. Chinese invention patent CN113388336A provides a TPO thermoplastic polyolefin polymer non-asphalt based self-adhesive membrane waterproof roll and a preparation method thereof, the waterproof roll comprises a polyester fabric base, a TPO thermoplastic polyolefin polymer base and a non-asphalt based self-adhesive, the TPO thermoplastic polyolefin polymer base comprises polypropylene, ethylene propylene rubber, a light stabilizer, a flame retardant and an antioxidant, the non-asphalt based self-adhesive comprises styrene butadiene rubber SBR, styrene butadiene rubber SBS, polyhydroxy polymer, a tackifier and an anti-ultraviolet agent, the invention adds appropriate proportion of polyhydroxy polymer into the non-asphalt based adhesive membrane to play the effects of tackification, volume expansion and plasticization, greatly improves the creep property and self-healing property of the waterproof roll, and can also improve the adhesive property, however, the physical mortise and tenon formed between the waterproof roll and concrete is only through plane-plane combination, the adhesive property is not a mortise and tenon structure in the traditional sense, the adhesive strength is not enough to support the waterproof roll to be firmly combined with concrete for a long time, so that the adhesive property must be improved by adding a tackifier, or the waterproof roll is easy to fall off. In addition, a layer of isolating film or isolating material needs to be attached to the surface of the non-asphalt-based self-adhesive, and the isolating film or isolating material is removed before use and then laid on the surface layer of the concrete.

In summary, in the waterproof roll in the prior art, a large amount of plasticizer, oily tackifying resin or tackifier is usually introduced to form an anti-adhesion layer on the surface layer of the waterproof roll, and an isolation material or a viscosity reduction material (isolation sand) needs to be attached to the anti-adhesion layer, which increases the cost and energy consumption additionally for both the isolation film and the isolation sand, and is easy to cause environmental pollution. And the tackifying resin is easy to age, so that the service life of the waterproof material is influenced. On the other hand, the waterproof coiled material is generally added with a plasticizer according to needs to increase the plasticizing performance and flexibility of the coiled material, but the plasticizer is easy to migrate and diffuse, so that the coiled material is easy to age and become brittle.

Disclosure of Invention

The TPO macromolecular waterproof roll prepared has a cavity with active bonding sites, can directly form a firm mortise and tenon structure with unset cement or concrete, does not need to add tackifying resin and plasticizer, does not need to cover an isolation material on the surface layer of the waterproof roll, can be directly paved on the surface layer of the concrete or cement, and is convenient to use; and the surface is additionally provided with a heat-sensitive color development layer, different colors can be displayed in different seasons, and the double effects of cold and hot roofs are met, so that the energy is saved, and the environment is protected and high efficiency is achieved.

In order to achieve the purpose, the invention provides a thermosensitive discoloring body reverse-adhesion type TPO high-molecular waterproof roll which comprises a multilayer composite structure, wherein the multilayer composite structure at least comprises a thermosensitive color development layer, a TPO high-molecular main material layer and a reverse adhesion layer from top to bottom; the thermosensitive color development layer, the TPO polymer main material layer and the anti-adhesion layer comprise the same elastomer material, and the elastomer material is TPO resin; the anti-adhesion layer comprises TPO resin, EVA resin, ordinary portland cement, a foaming agent and a surfactant, and a large number of cavities with active bonding sites are formed inside the anti-adhesion layer after melt blending.

Further, the heat-sensitive color development layer comprises 94-97% of TPO resin, 0.3-0.6% of light stabilizer, 2-5% of temperature-sensitive pigment capsule and 0.5-1% of antioxidant by mass percent;

the TPO polymer main material layer comprises 30-58% of TPO resin, 20-40% of calcium carbonate, 20-40% of magnesium hydroxide, 0.2-0.6% of antioxidant, 0.3-0.6% of light stabilizer, 0.5-3% of titanium dioxide and 1-5% of anhydrous copper sulfate;

the anti-adhesion layer comprises 40-55% of TPO resin, 10-20% of EVA resin, 20-30% of ordinary portland cement, 5-10% of brominated butyl rubber, 5-8% of hydrogenated styrene-butadiene rubber, 1-5% of surfactant, 0.3-1% of foaming agent and 0.1-0.3% of co-foaming agent.

Wherein the antioxidant is at least one of Basf 1010, 168 and 1076. The light stabilizer is at least one of basf 2020, 770 and 944.

The temperature-variable pigment capsule is Fuxin sunlight 3-10 micron microcapsule powder. Add the heat-sensitive color development layer on TPO polymer waterproofing membrane's top layer, realize the colour under different seasons, different temperature conditions and change, present white or other light colours summer, with the infrared part in the sunlight during reflection back to the atmosphere to the temperature of coiled material when reducing the insolate also can reach "cold roofing" effect simultaneously, reduces indoor air conditioning and consumes. In winter, the film is black or other dark colors, and absorbs infrared part in sunlight, thereby improving the temperature of the coiled material, achieving the effect of 'hot roofing' and reducing indoor heat supply consumption. And finally, the waterproof function requirement, the color design requirement and the energy-saving and emission-reducing requirements are met at the same time.

Particularly, the moisture display reagent anhydrous copper sulfate is added into the TPO polymer main material layer, so that the purpose that after the waterproof roll is damaged, the damaged point is actively displayed through color change is achieved, and the maintenance convenience is greatly improved.

Further, the surfactant is any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent; the foaming agent is any one or more of calcium carbonate, magnesium carbonate, sodium bicarbonate, azodicarbonamide, barium azodicarboxylate, diethyl azodicarboxylate and N, N-dinitrosopentamethylenetetramine; the auxiliary foaming agent is any one or more of urea derivatives, zinc oxide, stearic acid and salicylic acid. The addition of the surfactant can enhance the waterproof performance of the self-adhesive waterproof roll on one hand; on the other hand, the viscosity of the bonding layer can be enhanced, so that the peeling strength of the self-adhesive waterproof roll is increased.

Furthermore, the thickness of the anti-adhesion layer is 0.3-0.5 mm, the thickness of the TPO high polymer main material layer is 0.5-2.0 mm, and the thickness of the thermosensitive color development layer is 0.1-0.2 mm.

In the TPO polymer main material layer, the calcium carbonate is heavy calcium carbonate with the grain diameter of 600 meshes, and the magnesium hydroxide has the grain diameter of 1500 meshes.

Further, the TPO resin is selected from at least one of CA10A, CA02A, 6102.

Further, the TPO polymer main material layer is of a multilayer structure and comprises a first TPO polymer main material layer, a reinforcing layer and a second TPO polymer main material layer; the reinforced layer is coated between the first TPO polymer main body material layer and the second TPO polymer main body material layer; the TPO main polymer material layer is formed by compounding the first TPO main polymer material layer, the reinforcing layer and the second TPO main polymer material layer.

Further, the material of the reinforced layer is glass fiber fabric.

By adopting the technical scheme, a large amount of gas can be generated in the anti-adhesion layer by adding the foaming agent and the surfactant into the formula of the anti-adhesion layer, so that a large amount of cavities with active bonding sites on the surface of the anti-adhesion layer are generated; the exposed brominated butyl rubber and hydrogenated styrene butadiene rubber in the cavity can enhance the adhesion performance with cement or concrete.

After the cement or the concrete which is not solidified is contacted, the cement or the concrete which is not solidified can be reversely filled into the cavity inside the anti-bonding layer, and when the tenon-and-mortise structure is formed, the cement or the concrete is combined with the active bonding sites in the cavity, so that the bonding effect is further enhanced, and the cement or the concrete is firmer. And the surface of the anti-bonding layer is different from that in the prior art, the surface does not have the bonding performance, and an isolation material does not need to be attached to the surface, and the anti-bonding layer is directly paved on the surface of concrete or cement when in use, and the unset concrete or cement enters the cavity inside the anti-bonding layer.

The thermochromic local anti-adhesion TPO macromolecular waterproof roll material obtained by adopting the technical scheme has the exposed service life of 25 years and no crack at the roll material at minus 40 ℃, and the peel strength of post-poured cement mortar or concrete is not reduced after the roll material is subjected to heat aging at 115 ℃ for 672 hours. Can adjust different color variation according to the operation requirement to reach the reduction sunshine in summer and absorb, increase the absorptive effect of sunshine in winter, work as this waterproofing membrane local damaged back simultaneously, can show the damage point through the color variation of the inside moisture detection reagent of waterproofing membrane, easily maintenance.

In order to realize another purpose, the invention also provides a preparation method of the thermosensitive discoloring body reverse adhesion type TPO high-molecular waterproof roll, which specifically comprises the following steps:

s1 melting and plasticizing: weighing the raw materials of the anti-adhesion layer, the TPO polymer main material layer and the thermosensitive color development layer according to the proportion, respectively adding the raw materials into a high-speed stirrer to be uniformly mixed, respectively conveying the raw materials into a double-screw extruder to be melted and plasticized, and respectively obtaining an anti-adhesion layer mixed material, a TPO polymer main material layer mixed material and a thermosensitive color development layer mixed material.

S2 hot press forming for the first time: respectively and synchronously extruding the TPO polymer main material layer mixed material and the thermosensitive color-developing layer mixed material into a first rolling mill, and carrying out hot-pressing compounding and cooling sizing through a one-step forming process to form a surface layer composite hot-pressing material layer; extruding the anti-adhesion layer mixed material to obtain an anti-adhesion layer; the surface layer composite hot-pressing material layer comprises a TPO high-molecular main material layer and a thermosensitive color development layer.

S3, second hot-press forming: and conveying the surface layer composite hot-pressing material layer and the anti-sticking layer to a second roller calender for hot-pressing compounding and cooling and shaping to form the TPO high-molecular waterproof coiled material.

S4 cooling and rolling: and cooling, trimming and rolling the TPO high-molecular waterproof roll obtained in the step S3.

The TPO polymer waterproof roll sequentially comprises a thermosensitive color development layer, a TPO polymer main material layer and an anti-adhesion layer from top to bottom.

The thermosensitive discoloration body inverse adhesion type TPO high-molecular waterproof roll prepared by adopting the technical scheme is of a three-layer structure and sequentially comprises an inverse adhesion layer, a TPO high-molecular main material layer and a thermosensitive color development layer from inside to outside.

In order to improve the strength and the supporting performance of the thermosensitive discoloring body inverse-sticky TPO high-molecular waterproof roll, the invention also provides another technical scheme of the preparation method of the thermosensitive discoloring body inverse-sticky TPO high-molecular waterproof roll, which comprises the following specific steps of:

s1 melting and plasticizing: the raw materials of the anti-adhesive layer, the first TPO polymer main material layer, the second TPO polymer main material layer and the thermosensitive color development layer are weighed according to the proportion and then added into a high-speed stirrer to be uniformly mixed, and then are respectively conveyed into a double-screw extruder to be melted and plasticized to obtain an anti-adhesive layer mixed material, a first TPO polymer main material layer mixed material, a second TPO polymer main material layer mixed material and a thermosensitive color development layer mixed material.

S2 hot press forming for the first time: synchronously extruding the first TPO polymer main material layer mixed material, the second TPO polymer main material layer mixed material and the thermosensitive color development layer mixed material; the first TPO polymer main material layer mixed material and the second TPO polymer main material layer mixed material are extruded, meanwhile, an enhancement layer is wrapped between the two layers, and finally, the enhancement layer and the thermosensitive color development layer mixed material are simultaneously conveyed into a first rolling calender, and are subjected to hot-pressing compounding and cooling sizing through a one-step forming process to form a surface layer composite hot-pressing material layer; and extruding the anti-adhesion layer mixed material to obtain the anti-adhesion layer.

The first TPO polymer main material layer mixed material, the enhancement layer and the second TPO polymer main material layer mixed material are extruded by the first roller calender and then are integrally formed to form the TPO polymer main material layer; the surface layer composite hot-pressing material layer comprises a first TPO polymer main material layer, an enhancement layer, a second TPO polymer main material layer and a thermosensitive color development layer.

S3, second hot-press forming: and conveying the surface layer composite hot-pressing material layer and the anti-adhesion layer to a second three-roll calender for hot-pressing compounding, and carrying out hot pressing and cooling setting on the anti-adhesion layer to form the TPO high-molecular waterproof roll.

S4 cooling and rolling: and cooling, trimming and winding the TPO high-molecular waterproof roll obtained in the step S3.

The reverse-adhesion type TPO high-molecular waterproof roll of the thermochromic body prepared by adopting the technical scheme is of a five-layer structure and sequentially comprises a thermosensitive color development layer, a second TPO high-molecular main material layer, an enhancement layer, a first TPO high-molecular main material layer and a reverse adhesion layer from top to bottom. Hot pressing one deck enhancement layer, integrated into one piece between TPO polymer main material layer to reinforcing TPO polymer waterproofing membrane's intensity improves support strength, increase of service life.

According to the invention, each layer is made of TPO resin which is an elastomer material, so that on one hand, the layers can be well fused in a hot-pressing compounding process, the adhesion performance between the layers is enhanced, and the peeling strength is improved. On the other hand, the weather resistance and the elastic strength of the waterproof roll are improved, and the service life of the waterproof roll is greatly prolonged.

Through the application of the technical scheme, compared with the prior art, the invention has the following advantages:

1. by adopting the technical scheme of the invention, the surface of the waterproof roll is provided with the thermosensitive color-developing layer, the super-weather-resistant thermochromic capsules are added into TPO resin, and the TPO resin is white or other light colors in summer, and reflects the infrared part in sunlight back to the atmosphere, so that the temperature of the roll is reduced during insolation, and meanwhile, the cold roof effect can be achieved, and the indoor cold air consumption is reduced; the coiled material is black or other dark colors in winter, and absorbs infrared parts in sunlight, so that the temperature of the coiled material is increased, the effect of 'hot roofing' is achieved, and indoor heat supply consumption is reduced; finally, the waterproof function requirement, the color design requirement and the energy conservation and emission reduction requirement are met at the same time.

2. By adopting the technical scheme of the invention, a large number of cavities with active bonding sites on the surface can be formed in the anti-bonding layer by adding the foaming agent and the surfactant into the formula of the anti-bonding layer, and after the anti-bonding layer is contacted with unset cement, the unset cement can fill the cavities in the anti-bonding layer, so that a mortise and tenon structure is formed, and the effect of firm bonding is achieved. On the one hand, use same elastomer TPO resin through anti-adhesion layer and TPO polymer main material layer, and all do not use the plasticizer, avoided the problem of plasticizer migration diffusion, solved present self-adhesion type polymer waterproofing membrane "vat effect" and leaded to the problem that life seriously shortens. On the other hand, because the anti-adhesion layer body has no viscosity, an isolation material is not needed, a secondary heating sand covering process is not needed, and the anti-adhesion layer can be directly used, so that the use of isolation sand is reduced, the comprehensive energy consumption of production is reduced, and meanwhile, the energy consumption is reduced by about 40% in transportation.

3. According to the technical scheme, the moisture display reagent anhydrous copper sulfate is added into the TPO high-molecular main material layer, so that the purpose that after the waterproof roll is damaged, the damaged point is actively displayed through color change is achieved, and the maintenance convenience is greatly improved.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the specific contents of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a reverse-adhesion type TPO (thermoplastic polyolefin) high-molecular waterproof coiled material of a thermochromic body, which comprises a multilayer composite structure, wherein the multilayer composite structure at least comprises a thermosensitive color development layer, a TPO high-molecular main material layer and a reverse adhesion layer from top to bottom; the thermosensitive color development layer, the TPO high-molecular main material layer and the anti-adhesion layer comprise the same elastomer material, and the elastomer material is TPO resin; the anti-adhesion layer comprises TPO resin, EVA resin, ordinary portland cement, a foaming agent and a surfactant, and a large number of cavities with active bonding sites are formed inside the anti-adhesion layer after melt blending.

Wherein, the thermosensitive color development layer comprises 94-97% of TPO resin, 0.3-0.6% of light stabilizer, 2-5% of temperature-sensitive pigment capsule and 0.5-1% of antioxidant by mass percentage; the TPO polymer main material layer comprises 30-58% of TPO resin, 20-40% of calcium carbonate, 20-40% of magnesium hydroxide, 0.2-0.6% of antioxidant, 0.3-0.6% of light stabilizer, 0.4-3% of titanium dioxide and 1-5% of anhydrous copper sulfate; the anti-sticking layer comprises 40-55% of TPO resin, 10-20% of EVA resin, 20-30% of ordinary portland cement, 5-10% of brominated butyl rubber, 5-8% of hydrogenated styrene-butadiene rubber, 1-5% of surfactant, 0.3-1% of foaming agent and 0.1-0.3% of co-foaming agent.

Preferably, the TPO polymer main body material layer may have a multilayer structure, the multilayer structure includes a first TPO polymer main body material layer, a reinforcing layer, and a second TPO polymer main body material layer, the reinforcing layer is wrapped between the first TPO polymer main body material layer and the second TPO polymer main body material layer, and the first TPO polymer main body material layer and the second TPO polymer main body material layer are integrally formed by hot pressing.

Preferably, the thickness of the anti-adhesion layer is 0.3-0.5 mm, the thickness of the TPO polymer main material layer is 0.5-2.0 mm, and the thickness of the heat-sensitive color development layer is 0.1-0.2 mm.

Wherein the TPO resin is RiandBarssel Hifax series resin, and is at least one selected from CA10A, CA02A and 6102. The surfactant is any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent; the silane coupling agent can be KH550, KH560, KH570, KH792, etc.; the titanate coupling agent can be NDZ201, NDZ401 and the like; the aluminate coupling agent may be LS60, LS821, etc.

The foaming agent is any one of carbonate, azo foaming agent and nitroso compound foaming agent, and specifically, any one of calcium carbonate, magnesium carbonate, sodium bicarbonate, azodicarbonamide, barium azodicarboxylate, diethyl azodicarboxylate and N, N-dinitrosopentamethylenetetramine; the assistant foaming agent is one of urea derivatives, zinc oxide, stearic acid and salicylic acid.

The calcium carbonate is heavy calcium carbonate with the grain size of 600 meshes, and the magnesium hydroxide has the grain size of 1500 meshes. The temperature-variable microcapsule powder can be Fuxin sunlight 3-10 μm microcapsule powder. The antioxidant is at least one of Basff 1010, 168 and 1076. The light stabilizer is at least one of basf 2020, 770 and 944.

The above raw materials can be purchased from the market.

The performance of the thermochromic body reverse-adhesion type TPO high-molecular waterproof roll material with the multilayer structure is detected according to the P-type index of GB 27789-.

TABLE 1 detection basis and index for high-molecular waterproof coiled material

The technical solution of the present invention will be described in further detail below with reference to specific examples.

Example 1

In this embodiment, the multilayer composite structure includes, from top to bottom, a thermosensitive color development layer, a TPO polymer host material layer, and an anti-adhesive layer, where the thermosensitive color development layer includes, by mass, 94% of TPO resin, 0.5% of a light stabilizer, 5% of a temperature-sensitive pigment capsule, and 0.5% of an antioxidant; the TPO polymer main material layer comprises 45% of TPO resin, 25% of calcium carbonate, 25% of magnesium hydroxide, 10100.6% of basf, 20200.4% of basf, 3% of titanium dioxide and 1% of anhydrous copper sulfate; the anti-adhesion layer comprises 45.9% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 10% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 1% of calcium carbonate and 0.1% of stearic acid.

In this example, the TPO resins are CA10A and CA02A, and the mass ratio of CA10A to CA02A is 9: 1.

and respectively putting the raw materials of each layer into a high-speed stirrer to be uniformly mixed, and respectively conveying the raw materials into a double-screw extruder A, a double-screw extruder B and a double-screw extruder C to be melted and plasticized to respectively obtain a molten anti-adhesion layer mixed material, a TPO (thermoplastic polyolefin) polymer main material layer mixed material and a thermosensitive color-developing layer mixed material. And synchronously extruding the molten mixed material TPO high-molecular main material layer mixed material, the enhancement layer and the thermosensitive color-developing layer mixed material into a first rolling calender, and cooling and shaping to form the surface layer composite hot-pressing material layer through a one-step forming process. The surface layer composite hot-pressing material layer comprises a TPO high-molecular main material layer and a thermosensitive color development layer.

And extruding the anti-adhesion layer mixed material to obtain the anti-adhesion layer.

And conveying the surface layer composite hot-pressing material layer and the anti-sticking layer to a second roller calender for hot-pressing compounding and cooling and shaping to form the TPO high-molecular waterproof roll. Thus forming the thermosensitive color-changing body reverse-adhesion type TPO high-molecular waterproof roll with a multilayer structure of a thermosensitive color-developing layer, a TPO high-molecular main material layer and a reverse-adhesion layer.

TPO polymer waterproofing membrane includes thermosensitive color development layer-TPO polymer main material layer-anti-adhesive layer three layer construction from top to bottom in proper order.

Wherein the thickness of the thermosensitive color development layer is 0.1-0.2 mm; the thickness of the TPO high-molecular main material layer is 0.5-2.0 mm; the thickness of the anti-adhesion layer is 0.3-0.5 mm.

Carry out physical properties to the anti-type TPO polymer waterproofing membrane that glues of the thermochromic body of this embodiment and detect. The detection result is that the maximum tension is 300N/cm; elongation at maximum tensile force 16%; elongation at break of the film is 600%; the heat resistance is 120 ℃, and no slippage, flowing or dripping exists for 2 hours; low-temperature bendability: the main material has no crack at 40 ℃ below zero; low-temperature flexibility: the anti-adhesion layer has no crack at-40 ℃; and the peel strength with post-cast concrete: 2.0N/mm of non-treatment and 2.0N/mm of heat treatment; low temperature flexibility after heat aging: 672 hours at 115 ℃ and no crack at-40 ℃; artificial climate accelerated aging: the low-temperature bending property of the alloy is 5000 hours, and no crack exists at 40 ℃ below zero.

The results show that the detection items all meet the requirement of the P index.

Color rendering performance detection was also performed for this embodiment. The thermosensitive color-developing layer is white when the thermosensitive color-developing body reverse-adhesion type TPO macromolecular waterproof coiled material is placed at the temperature of more than 30 ℃; the thermosensitive color development layer is gray under the condition of 0-30 ℃; the <0 ℃ heat-sensitive color development layer appears black.

The thermosensitive color developing layer is damaged, and the TPO high polymer main material layer is blue when meeting water. Because add the anhydrous copper sulfate of moisture display reagent in TPO polymer host material layer, when waterproofing membrane damaged back, through the colour change, can discover damaged point, easy maintenance very easily.

Example 2

This example differs from example 1 in the difference of the components in the anti-adhesive layer. Specifically, the anti-adhesive layer comprises 46.6% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 10% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 0.3% of calcium carbonate and 0.1% of stearic acid.

The anti-adhesion layer in the embodiment has low-temperature flexibility and no crack at-40 ℃ through detection. Other detection items all meet the requirement of the P index.

Example 3

This example differs from example 1 in the composition of the anti-adhesive layer. Specifically, the anti-adhesion layer comprises 45.7% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 10% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 1% of calcium carbonate and 0.3% of stearic acid.

Example 4

This example differs from example 1 in the composition of the anti-adhesive layer. Specifically, the anti-adhesive layer comprises 50.7% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 5% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 1% of calcium carbonate and 0.3% of stearic acid.

And after detection, the peel strength with post-cast concrete is as follows: no treatment 2.0N/mm, heat treatment 1.8N/mm. Other detection items all meet the requirement of the P index.

Example 5

This example differs from example 1 in the composition of the anti-adhesive layer. Specifically, the anti-adhesive layer comprises 51.1% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 5% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 0.6% of azodicarbonamide and 0.3% of zinc oxide.

The anti-adhesion layer in the embodiment has low-temperature flexibility and no crack at-40 ℃ through detection.

And the peel strength with post-cast concrete: no treatment 1.9N/mm, heat treatment 1.8N/mm.

Other detection items all meet the requirement of the P index.

Example 6

This example differs from example 1 in the composition of the anti-adhesive layer. Specifically, the anti-adhesive layer comprises 51.7% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 5% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 0.2% of azodicarbonamide and 0.1% of zinc oxide.

And the peel strength with post-cast concrete: no treatment 2.0N/mm, heat treatment 1.8N/mm.

Other detection items all meet the requirement of the P index.

Example 7

This example differs from example 1 in the composition of the anti-adhesive layer. Specifically, the anti-adhesion layer comprises 40.7% of TPO resin, 10% of EVA resin, 30% of ordinary portland cement, 5% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 1% of calcium carbonate and 0.3% of stearic acid.

And (3) detecting, wherein the peel strength with post-cast concrete is as follows: no treatment 1.9N/mm, heat treatment 1.7N/mm. Other detection items all meet the requirement of the P index.

Example 8

This example differs from example 1 in the difference of the components in the anti-adhesive layer. Specifically, the anti-adhesion layer comprises 45.7% of TPO resin, 10% of EVA resin, 25% of ordinary portland cement, 5% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of KH (silane coupling agent), 1% of calcium carbonate and 0.3% of stearic acid.

And after detection, the peel strength with post-cast concrete is as follows: no treatment 2.0N/mm, heat treatment 1.9N/mm. Other detection items all meet the requirement of the P index.

Example 9

The present example differs from example 1 in the difference of the components in the thermosensitive color-developing layer. The thermosensitive color development layer comprises 97% of TPO resin, 0.5% of light stabilizer, 2% of temperature-sensitive pigment capsule and 0.5% of antioxidant by mass percent.

And meanwhile, color rendering performance detection is carried out. The thermosensitive color-developing layer is white when the thermosensitive color-developing body reverse-adhesion type TPO macromolecular waterproof coiled material is placed at the temperature of more than 30 ℃; the thermosensitive color development layer is gray under the condition of 0-30 ℃; the <0 ℃ heat-sensitive color development layer appears black.

Example 10

The present example is different from example 1 in that, in the host material TPO resin in each layer structure, the mass ratio of CA10A and CA02A is 1: 1.

carry out physical properties to the anti-type TPO polymer waterproofing membrane that glues of the thermochromic body of this embodiment and detect. The detection result is the maximum tension of 310N/cm; elongation at maximum tensile force of 18%; elongation at break of the film is 550%; the heat resistance is 120 ℃, and the sliding, flowing and dripping are avoided after 2 hours; low-temperature bendability: the main material has no crack at 40 ℃ below zero; low-temperature flexibility: the anti-adhesion layer has no crack at-40 ℃; and the peel strength with post-cast concrete: 2.0N/mm of non-treatment and 2.0N/mm of heat treatment; low temperature flexibility after heat aging: 680 hours at 115 ℃ and no crack at-40 ℃; artificial climate accelerated aging: the low-temperature bending property of the alloy is 5000 hours, and no crack exists at 40 ℃ below zero.

Example 11

The difference between the present embodiment and embodiment 1 is that the main material TPO resin in each layer structure includes CA10A and 6102, and the mass ratio of CA10A and 6102 is 1: 1.

carry out physical properties to the anti-type TPO polymer waterproofing membrane that glues of the thermochromic body of this embodiment and detect. The detection result is that the maximum tension is 280N/cm; elongation at maximum tensile force of 15%; elongation at break of the film is 500%; the heat resistance is 120 ℃, and no slippage, flowing or dripping exists for 2 hours; low-temperature bendability: the main material has no crack at 40 ℃ below zero; low-temperature flexibility: the anti-adhesion layer has no crack at-40 ℃; and the peel strength with post-cast concrete: 2.0N/mm of non-treatment and 2.0N/mm of heat treatment; low temperature flexibility after heat aging: 670 hours at 115 ℃ and no crack at-40 ℃; artificial climate accelerated aging: the bending property at low temperature of 5000 hours is-40 ℃ without cracks.

Example 12

The difference between this example and example 1 is the difference of the main material layer of TPO polymer.

The TPO polymer main material layer is a multilayer structure comprising a first TPO polymer main material layer, an enhancement layer and a second TPO polymer main material layer.

First TPO polymer body material layer and second TPO polymer body material layer constitution are the same, and the material of enhancement layer is glass fiber fabric.

The first TPO main polymer material layer and the second TPO main polymer material layer comprise 45% of TPO resin, 25% of calcium carbonate, 25% of magnesium hydroxide, 10100.6% of basf, 20200.4% of basf, 3% of titanium dioxide and 1% of anhydrous copper sulfate;

in this embodiment, the raw materials of the anti-adhesion layer, the first TPO polymer body material layer, the second TPO polymer body material layer, and the thermosensitive color development layer are weighed according to a ratio and then respectively put into a high-speed mixer to be uniformly mixed, and then respectively conveyed to the twin-screw extruder a, the twin-screw extruder B, the twin-screw extruder C, and the twin-screw extruder D to be melted and plasticized, so as to respectively obtain the molten anti-adhesion layer mixture, the first TPO polymer body material layer mixture, the second TPO polymer body material layer mixture, and the thermosensitive color development layer mixture.

And synchronously extruding the molten first TPO polymer main material layer mixed material, the enhancement layer, the second TPO polymer main material layer mixed material and the thermosensitive color-developing layer mixed material into a first rolling and polishing machine for first hot-press shaping, extruding by a one-step forming process, and cooling and qualifying to form a surface layer composite hot-press material layer after hot-press compounding. Wherein, in first TPO polymer main part material layer misce bene, enhancement layer, the second TPO polymer main part material layer misce bene passed through first roll calender, integrated into one piece formed TPO polymer main part material layer.

The surface layer composite hot-pressing material layer comprises a four-layer structure of a first TPO polymer main body material layer, an enhancement layer, a second TPO polymer main body material layer and a thermosensitive color development layer.

And conveying the surface layer composite hot-pressing material layer and the anti-sticking layer to a second roller calender for hot-pressing compounding and cooling and shaping to form the TPO high-molecular waterproof roll.

The thermochromic body reverse-adhesion type TPO high-molecular waterproof roll with the five-layer structure comprises a thermosensitive color development layer, a second TPO high-molecular main material layer, an enhancement layer, a first TPO high-molecular main material layer and a reverse adhesion layer from top to bottom in sequence.

Wherein the thickness of the thermosensitive color development layer is 0.1-0.2 mm; the thickness of the TPO high polymer main material layer is 0.5-2.0 mm; the thickness of the anti-adhesion layer is 0.3-0.5 mm.

Carry out physical properties to the anti-type TPO polymer waterproofing membrane that glues of the thermochromic body of this embodiment and detect. The detection result is that the maximum tension is 350N/cm; elongation at maximum tensile force of 18%; film elongation at break 680%; the heat resistance is 120 ℃, and no slippage, flowing or dripping exists for 2 hours; low-temperature bendability: the main material has no crack at 40 ℃ below zero; low-temperature flexibility: the anti-adhesion layer has no crack at-40 ℃; and the peel strength with post-cast concrete: 2.0N/mm of non-treatment and 2.0N/mm of heat treatment; low temperature flexibility after heat aging: 672 hours at 115 ℃ and has no crack at-40 ℃; artificial climate accelerated aging: the low-temperature bending property of 5100 hours is-40 ℃ without cracks.

Comparative example 1

The present comparative example differs from example 1 in the difference of the components in the anti-adhesive layer. In the comparative example, the anti-adhesive layer comprises 45.9% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 18% of brominated butyl rubber, 7925% of silane coupling agent KH, 1% of calcium carbonate and 0.1% of stearic acid.

The low-temperature flexibility of the anti-adhesion layer in the comparative example is-40 ℃ and has no crack through detection.

And the peel strength with post-cast concrete: no treatment 1.4N/mm, heat treatment 1.0N/mm.

Comparative example 2

The present comparative example differs from example 1 in the difference of the components in the anti-adhesive layer. The anti-adhesion layer in the comparative example comprises 45.9% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 18% of hydrogenated styrene-butadiene rubber, 7925% of KH 792% of silane coupling agent, 1% of calcium carbonate and 0.1% of stearic acid.

And the peel strength of post-cast concrete: no treatment 1.3N/mm, heat treatment 1.0N/mm.

Comparative example 3

The present comparative example differs from example 1 in the difference of the components in the anti-adhesive layer. In the comparative example, the anti-adhesive layer comprises 45.9% of TPO resin, 10% of EVA resin, 20% of ordinary portland cement, 10% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 7925% of silane coupling agent KH, 2% of calcium carbonate and 0.1% of stearic acid.

Comparative example 4

The present comparative example differs from example 1 in the difference of the components in the anti-adhesive layer. In the comparative example, the anti-adhesive layer comprises 46.7% of TPO resin, 10% of EVA resin, 25% of ordinary portland cement, 10% of brominated butyl rubber, 8% of hydrogenated styrene-butadiene rubber, 0.2% of calcium carbonate and 0.1% of stearic acid.

And the peel strength with post-cast concrete: no treatment 1.2N/mm, heat treatment 0.9N/mm.

Through the analysis of the embodiment and the comparison example, the thermochromic body reverse-adhesion type TPO high-molecular waterproof roll material prepared by the technical scheme of the invention displays different colors by exposing the roll material at different temperatures, so that the double effects of a cold roof and a hot roof are realized, and the waterproof function requirement, the color design requirement and the energy-saving and emission-reducing requirements are met. And because all adopt the TPO material as the host material in each layer, improve its waterproofing membrane's weatherability on the one hand, on the other hand, the same TPO material has good compatibility in the melt hot pressing process, has improved the bonding effect between the layer.

Meanwhile, the surface of the anti-sticking layer is not sticky, an isolation material is not needed for isolation, and a secondary heating sand covering procedure is not needed before use, so that the use of isolation sand is reduced, the comprehensive energy consumption of production is reduced, and the energy consumption in transportation is reduced by about 40%.

The moisture indicator is added into the main material layer, so that when the thermosensitive color-developing layer is damaged, the damaged point can be found visually, and the maintenance is convenient.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A thermosensitive allochroic body reverse-adhesion type TPO high-molecular waterproof coiled material is characterized by comprising a multilayer composite structure, wherein the multilayer composite structure at least comprises a thermosensitive color development layer, a TPO high-molecular main material layer and a reverse adhesion layer from top to bottom; the thermosensitive color development layer, the TPO polymer main material layer and the anti-adhesion layer comprise the same elastomer material, and the elastomer material is TPO resin;

the anti-adhesion layer comprises TPO resin, EVA resin, ordinary portland cement, a foaming agent and a surfactant, and a large number of cavities with active bonding sites are formed inside the anti-adhesion layer after melt blending.

2. The thermochromic body reverse-adhesion type TPO polymer waterproof coiled material as claimed in claim 1, wherein the thermochromic layer comprises 94-97% by mass of TPO resin, 0.3-0.6% by mass of light stabilizer, 2-5% by mass of temperature-sensitive pigment capsules, and 0.5-1% by mass of antioxidant;

3. The thermochromic body reverse-adhesion type TPO polymer waterproof roll material as claimed in claim 2, wherein the surfactant is any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent;

the foaming agent is any one of carbonate, azo compound or nitroso compound foaming agent;

the auxiliary foaming agent is one of urea derivatives, zinc oxide, stearic acid and salicylic acid.

4. The thermochromic body reverse adhesion type TPO polymer waterproof roll as claimed in claim 2, wherein the thickness of the reverse adhesion layer is 0.3-0.5 mm, the thickness of the TPO polymer main material layer is 0.5-2.0 mm, and the thickness of the thermochromic layer is 0.1-0.2 mm.

5. The thermochromic body reverse-adhesion type TPO polymer waterproof roll as claimed in claim 2, wherein in the TPO polymer main material layer, calcium carbonate is heavy calcium carbonate with a particle size of 600 meshes, and magnesium hydroxide with a particle size of 1500 meshes.

6. The thermochromic bulk reverse adhesion type TPO waterproof polymer roll according to any one of claims 1 to 5, wherein the TPO resin is at least one selected from CA10A, CA02A and 6102.

7. The thermochromic body reverse-adhesion type TPO polymer waterproof roll according to any one of claims 1 to 5, wherein the TPO polymer main material layer is a multilayer structure and comprises a first TPO polymer main material layer, a reinforcing layer and a second TPO polymer main material layer;

the reinforced layer is coated between the first TPO polymer main body material layer and the second TPO polymer main body material layer;

the TPO main polymer material layer is formed by compounding the first TPO main polymer material layer, the reinforcing layer and the second TPO main polymer material layer.

8. The thermochromic bulk reverse-adhesion type TPO polymeric waterproofing membrane according to claim 7, wherein the reinforcement layer is a glass fiber fabric.

9. The preparation method of the thermochromic body reverse-adhesion type TPO polymer waterproof roll as claimed in any one of claims 1 to 8, comprising the following specific steps:

s1, melting and plasticizing: weighing the raw materials of the anti-adhesion layer, the TPO polymer main material layer and the thermosensitive color-developing layer according to the proportion, respectively adding the weighed raw materials into a high-speed stirrer to be uniformly mixed, and respectively conveying the raw materials into three double-screw extruders to be melted and plasticized to obtain a molten state anti-adhesion layer mixed material, a TPO polymer main material layer mixed material and a thermosensitive color-developing layer mixed material;

s2, first hot-press forming: respectively and synchronously extruding the TPO polymer main material layer mixed material and the thermosensitive color-developing layer mixed material into a first rolling mill, and carrying out hot-pressing compounding and cooling sizing through a one-step forming process to form a surface layer composite hot-pressing material layer; extruding the anti-adhesion layer mixed material to obtain an anti-adhesion layer;

s3, hot press forming for the second time: simultaneously conveying the surface layer composite hot-pressing material layer and the anti-adhesion layer to a second roller calender for hot-pressing compounding and cooling and shaping to form the TPO high-molecular waterproof coiled material;

s4, cooling and rolling: and cooling, trimming and winding the TPO high-molecular waterproof roll obtained in the step S3.

10. The preparation method of the thermochromic body reverse-adhesion type TPO polymer waterproof roll as claimed in any one of claims 1 to 8, comprising the following specific steps:

s1, melting and plasticizing: weighing the raw materials of the anti-adhesive layer, the first TPO polymer main material layer, the second TPO polymer main material layer and the thermosensitive color-developing layer according to the proportion, adding the weighed raw materials into a high-speed stirrer, uniformly mixing, and respectively conveying the raw materials into a double-screw extruder for melting and plasticizing to obtain an anti-adhesive layer mixed material, a first TPO polymer main material layer mixed material, a second TPO polymer main material layer mixed material and a thermosensitive color-developing layer mixed material;

s2, first hot-press forming: synchronously extruding the first TPO polymer main material layer mixed material, the second TPO polymer main material layer mixed material and the thermosensitive color development layer mixed material; coating an enhancement layer between the first TPO polymer main material layer mixed material and the second TPO polymer main material layer mixed material while extruding, and finally conveying the enhancement layer and the thermosensitive color development layer mixed material to a first rolling calender simultaneously, and performing hot-pressing compounding and cooling sizing through a one-step forming process to form a surface layer composite hot-pressing material layer; extruding the anti-adhesion layer mixed material to obtain an anti-adhesion layer;

s3, hot-press forming for the second time: conveying the surface layer composite hot-pressing material layer and the anti-adhesion layer to a second roller calender for hot-pressing compounding, and forming a TPO high-molecular waterproof coiled material after hot pressing, cooling and shaping the anti-adhesion layer;