CN115404024A - Low-temperature adhesive and preparation method thereof, high-molecular self-adhesive and preparation method thereof, and high-molecular waterproof roll - Google Patents
Low-temperature adhesive and preparation method thereof, high-molecular self-adhesive and preparation method thereof, and high-molecular waterproof roll Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/02—Copolymers of mineral oil hydrocarbons
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- C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
- C09J191/06—Waxes
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
- E02D31/00—Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution
- E02D31/02—Protective 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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- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
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- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
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- E—FIXED CONSTRUCTIONS
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- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D5/00—Roof covering by making use of flexible material, e.g. supplied in roll form
- E04D5/10—Roof covering by making use of flexible material, e.g. supplied in roll form by making use of compounded or laminated materials, e.g. metal foils or plastic films coated with bitumen
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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Abstract
The invention belongs to the field of waterproof coiled materials, and particularly relates to a low-temperature adhesive and a preparation method thereof, a high-molecular self-adhesive and a preparation method thereof, and a high-molecular waterproof coiled material. The preparation method of the low-temperature adhesive comprises the following steps: mixing isocyanate, metal filler and titanate coupling agent, and mixing at 85-105 ℃ to obtain the low-temperature adhesive. The raw material composition of the macromolecular self-adhesive material comprises: resin, styrene block copolymer, low-temperature adhesive, organic heat carrier and filler. The invention solves the problems of difficult construction under low temperature and substandard stripping performance under low temperature; the high-temperature performance of the coiled material is effectively improved, and the construction process conditions under the high-temperature condition are widened. The self-adhesive material formed by the provided low-temperature adhesive still has good adhesive effect at low temperature, and the adhesive strength completely meets the requirements of GB-23441-2009 or GB/T-35467.
Description
Technical Field
The invention belongs to the field of waterproof coiled materials, and particularly relates to a low-temperature adhesive and a preparation method thereof, a high-molecular self-adhesive and a preparation method thereof, and a high-molecular waterproof coiled material.
Background
With the improvement of the living standard of human beings, people have increased consciousness on environmental protection, and have subjectively pursued on the requirement of selecting waterproof materials. People are not only limited to pursuing the living standard of the materials, but also have higher improvement on the spiritual pursuit. Therefore, the environment-friendly waterproof coiled material is one of popular hot doors. The environment-friendly waterproof coiled material is suitable for civil buildings and underground waterproof engineering. The coiled material is a high molecular resin type waterproof coiled material which takes high molecular resin as a main material and is coated with a self-adhesive film.
The main defects of the existing macromolecule non-asphalt base waterproof coiled material are as follows: the environment-friendly high-molecular waterproof coiled material has obvious defects in heat resistance, low-temperature bonding and stripping performance with cement mortar, short heat-resistant time, poor low-temperature bonding and small stripping strength, and restricts the application and construction range of the environment-friendly high-molecular waterproof coiled material and the development of products under certain environment. Specifically, the existing polymer non-asphalt-based waterproof coiled material has poor low-temperature adhesion, almost has no adhesion force at low temperature (less than or equal to 5 ℃), or has small adhesion force, and cannot achieve the waterproof adhesion effect; the heat resistance time is short, the heat resistance just meets the GB-23441-2017 standard, and the stripping performance is poor.
Disclosure of Invention
The invention aims to solve the problems of the non-asphalt-based waterproof coiled material, in particular to the problem of poor low-temperature bonding, and the self-adhesive material formed by the provided low-temperature adhesive still has good bonding effect at low temperature (10-10 ℃), and the bonding strength completely meets the requirements of GB-23441-2009 or GB/T-35467; the low-temperature adhesive, the high-molecular self-adhesive material and the formed coiled material have heat resistance of up to 5h at 70 ℃, 3h at 80 ℃ and 2h at 85 ℃, and meet the requirements of GB-23441-2009 or GB/T-35467; the stripping performance of the coiled material can reach more than 2.0N/mm.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a low temperature adhesive, the method comprising:
mixing isocyanate, metal filler and titanate coupling agent, and mixing at 85-105 ℃ to obtain the low-temperature adhesive.
For the low-temperature adhesive, the reaction mechanism is that a monomolecular layer is formed by chemical adsorption or chemical substitution reaction of an-NCO group of isocyanate and alkoxy, trace carboxyl or amino in a titanate coupling agent, then ester group and carboxyl are subjected to transesterification and crosslinking to promote viscosity to rise and form thixotropy, and then long-chain entanglement groups are bent and wound with metal fillers to improve compatibility, so that the extension and tear strength is improved, and finally, the effects of strong adhesion and high adhesion are achieved through a curing reaction (mixing at 85-105 ℃).
Preferably, the adhesive comprises 15-35 parts by weight of isocyanate, 40-80 parts by weight of metal filler and 5-20 parts by weight of titanate coupling agent.
Preferably, the isocyanate is toluene diisocyanate and/or diphenylmethane diisocyanate.
Preferably, the metal filler is aluminum powder and/or iron powder.
Preferably, in the preparation method of the low-temperature adhesive, the mixing mode is as follows: heating in water bath at 85-105 deg.c for 3-5 hr.
The second aspect of the present invention provides a low-temperature adhesive prepared by the above-described method for preparing a low-temperature adhesive.
The third aspect of the present invention provides a polymer self-adhesive material, which comprises the following raw materials:
20 to 45 weight percent of resin, 2 to 17 weight percent of styrene block copolymer, 1 to 3 weight percent of low-temperature adhesive, 15 to 30 weight percent of organic heat carrier, 0 to 2 weight percent of liquid pigment, 0 to 5 weight percent of plasticizer, 15 to 40 weight percent of filler and 0.5 to 4 weight percent of heat-resistant auxiliary agent;
the low-temperature adhesive is the low-temperature adhesive.
For the macromolecular self-adhesive material, the reaction mechanism is that a chemical bond is formed by the interaction of an-NCO group of isocyanate and a carboxyl group in resin, and the coupling is carried out by the chemical action of an alkoxy group in a titanate coupling agent and the carboxyl or hydroxyl group, so that the adhesive strength is improved, and the effect of high adhesion is achieved.
As a preferred scheme, the raw material composition of the macromolecular self-adhesive material meets the following requirements:
0.1wt% to 2wt% of a liquid pigment, and/or:
1 to 5 weight percent of plasticizer.
Preferably, in the raw material composition of the polymeric self-adhesive material, the resin is at least one selected from terpene resins, petroleum resins and coumarone resins.
Preferably, the softening point of the resin is 90-110 ℃.
Preferably, in the raw material composition of the high molecular self-adhesive material, the styrene-based block copolymer is at least one selected from SIS, SSBR, SBR and SBS.
Preferably, in the raw material composition of the high molecular self-adhesive cement, the molecular weight of the styrene block copolymer is 15-25 ten thousand.
Preferably, in the raw material composition of the high molecular self-adhesive material, the organic heat carrier is at least one selected from white oil, base oil and reduced line oil.
Preferably, in the raw material composition of the high molecular self-adhesive material, the liquid pigment is at least one selected from red liquid pigment, green liquid pigment, yellow liquid pigment and blue liquid pigment.
Preferably, in the raw material composition of the polymeric self-adhesive material, the plasticizer is at least one selected from phthalic acid ester, phthalic acid ester and benzene polyacid ester.
Preferably, in the raw material composition of the high molecular self-adhesive material, the filler is at least one selected from calcium carbonate, talcum powder, heavy calcium and light calcium.
Preferably, in the raw material composition of the polymeric self-adhesive cement, the heat-resistant auxiliary is at least one selected from polyethylene wax, polypropylene wax and polypropylene.
According to the invention, whether the liquid pigment is added or not can be selected according to requirements, and the liquid pigment is beneficial to feeding and mixing besides providing corresponding colors, so that the system has no color difference.
The fourth aspect of the present invention provides a method for preparing the above polymeric self-adhesive material, wherein the method comprises:
(1) Mixing and stirring an organic heat carrier and resin, and controlling the temperature of the system to be 130-150 ℃;
(2) Adding a styrene block copolymer after the resin is completely dissolved, controlling the system temperature to be 170-190 ℃, mixing and stirring:
(3) Optionally adding liquid pigment, optionally adding plasticizer, adding filler, adding heat-resistant auxiliary agent, adding low-temperature adhesive, controlling system temperature at 160-180 ℃, mixing and stirring to obtain the macromolecular self-adhesive material.
In the present invention, "optionally" means that the operation may or may not be performed. Such as "optionally adding a liquid pigment" means that the liquid pigment may or may not be added, as desired.
In a specific embodiment, the method for preparing the polymeric self-adhesive material comprises:
s1: adding an organic heat carrier and resin into a material tank, then starting stirring, and heating to 140 ℃;
s2: adding a styrene block copolymer after the temperature is raised to 150 ℃ and the resin is completely dissolved; continuously heating to 170-190 ℃, and stirring for 3h;
s3: adding liquid pigment, plasticizer, filler, heat-resistant auxiliary agent and low-temperature adhesive; stirring at 160-180 deg.C for 30-60min to obtain the final product.
The fifth aspect of the present invention provides a high molecular self-adhesive waterproof roll, which comprises, in order: main part substrate layer, polymer self-adhesive precoat, isolation rete, if can be including setting gradually: the isolation film layer, the polymer self-adhesive glue layer, the main body base material layer, the polymer self-adhesive glue layer and the isolation film layer;
the polymer self-adhesive glue layer is formed by the polymer self-adhesive glue.
Preferably, the main substrate layer is at least one of a strong cross laminated film, a high-strength composite film and a high-strength original film in a PTE aluminum-plated composite film (PET/PP).
Preferably, the isolation film layer is at least one of a PE isolation film, a PP isolation film and a PET isolation film.
The invention has the beneficial effects that:
the invention solves the problems of difficult construction under low temperature and substandard stripping performance under low temperature; the high-temperature performance of the coiled material is effectively improved, and the construction process conditions under the high-temperature condition are widened. The self-adhesive polymer material formed by the provided low-temperature adhesive still has good adhesive effect at low temperature (10-minus 10 ℃), and the adhesive strength completely meets the regulations of GB-23441-2009 or GB/T-35467.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
The embodiment provides a low-temperature adhesive and a preparation method thereof, a high-molecular self-adhesive material and a preparation method thereof, and a high-molecular self-adhesive waterproof roll.
The preparation method of the low-temperature adhesive comprises the following steps:
25 parts by weight of isocyanate (Shanghai Yi En technology Co., ltd.) were mixed with 62 parts by weight of a metal filler (alumina powder having a particle size of less than 100 μm) and 13 parts by weight of a titanate coupling agent (Guangdong Green Wei New Material technology Co., ltd.) and heated in a water bath at 95 ℃ for 4.5 hours to obtain a low-temperature adhesive.
The macromolecular self-adhesive material comprises the following raw materials:
40wt% of tackifying petroleum resin, 15wt% of SBS, 2wt% of low-temperature adhesive, 22wt% of white oil (Zhonghai Sichuan Limited liability company), 0.1wt% of green liquid pigment (Guangdong Kedi New Material science and technology Co., ltd.), 1wt% of plasticizer phthalate (Hengshui Shengkang chemical Co., ltd.), 19wt% of 200-mesh calcium carbonate and 0.9wt% of heat-resistant assistant polypropylene wax (Honeyville corporation).
The preparation method of the macromolecular self-adhesive material comprises the following steps:
s1: adding an organic heat carrier and resin into a material tank, then starting stirring, and heating to 140 ℃;
s2: adding a styrene block copolymer after the temperature is raised to 150 ℃ and the resin is completely dissolved; continuously heating to 180 ℃, and stirring for 3 hours;
s3: adding liquid pigment, plasticizer, filler, heat-resistant auxiliary agent and low-temperature adhesive; stirring for 45min at 170 ℃ to obtain the macromolecular self-adhesive material.
The polymer self-adhesive waterproof roll comprises the following components in sequence: main part substrate layer, polymer self-adhesive precoat, isolation rete. The main body substrate layer is a powerful cross laminated film, and the isolation film layer is a PET isolation film.
Example 2
The embodiment provides a low-temperature adhesive and a preparation method thereof, a high-molecular self-adhesive material and a preparation method thereof, and a high-molecular self-adhesive waterproof roll.
The low temperature adhesive was prepared in the same manner as in example 1.
The raw material composition of the macromolecular self-adhesive material comprises:
38wt% of tackifying petroleum resin, 13wt% of SBS, 1wt% of low-temperature adhesive, 20wt% of white oil (Zhonghai Sichuan Limited liability company), 0.3wt% of green liquid pigment, 2wt% of plasticizer phthalate (Heishikang chemical industry Co., ltd.), 25wt% of 200-mesh calcium carbonate and 0.7wt% of heat-resistant assistant polypropylene wax (Honeyville corporation).
The preparation method of the polymer self-adhesive material refers to example 1.
The polymer self-adhesive waterproof roll comprises the following components in sequence: main part substrate layer, polymer self-adhesive precoat, isolation rete. The main body substrate layer is a powerful cross laminated film, and the isolation film layer is a PET isolation film.
Example 3
The embodiment provides a low-temperature adhesive and a preparation method thereof, a high-molecular self-adhesive material and a preparation method thereof, and a high-molecular self-adhesive waterproof roll.
The low temperature adhesive was prepared in the same manner as in example 1.
The raw material composition of the macromolecular self-adhesive material comprises:
35wt% of tackifying petroleum resin, 12wt% of SBS, 1.5wt% of low-temperature adhesive, 18wt% of white oil (Zhonghai Sichuan Limited liability company), 1.2wt% of green liquid pigment, 3wt% of plasticizer phthalate (Heishikang chemical industry Limited company), 27.5wt% of 200-mesh calcium carbonate and 1.8wt% of heat-resistant additive polypropylene wax (Honeyville corporation).
The preparation method of the macromolecular self-adhesive cement refers to example 1.
The polymer self-adhesion waterproofing membrane is including setting gradually: main part substrate layer, polymer self-adhesive precoat, isolation rete. The main body substrate layer is a powerful cross laminated film, and the isolation film layer is a PET isolation film.
Comparative example 1
This comparative example 1 provides a general pitch base waterproofing membrane, including the main part substrate layer, cover pitch self-adhesive precoat and the barrier film layer on the main part substrate layer. The asphalt-based self-adhesive material consists of the following components in percentage by weight: 40% of asphalt, 12% of base oil, 10% of styrene-butadiene rubber, 8% of SBS, 4% of tackifying petroleum resin, 6% of rubber powder and 20% of 200-mesh calcium carbonate.
Wherein, the main body substrate layer is a strong cross laminated film.
Comparative example 2
The comparative example provides a normal polymer self-adhesion waterproofing membrane, including main part substrate layer, polymer self-adhesion precoat and isolation rete. The macromolecular self-adhesive material comprises the following raw materials in percentage by weight: 15% of tackifying petroleum resin, 15% of SBS, 20% of white oil, 2% of pigment, 2% of self-made low-temperature adhesive, 42% of 200-mesh calcium carbonate and 4% of heat-resistant auxiliary agent polypropylene (Honeywell company).
The main body substrate base material layer is a strong cross laminated film.
Preparation of polymeric self-adhesive glue reference is made to example 1.
Comparative example 3
The difference from example 1 is 0% low temperature adhesive and 21% filler by weight.
Comparative example 4
The difference from example 2 is 0% low temperature adhesive and 26% filler by weight.
Comparative example 5
The difference from example 3 is that the heat-resistant auxiliary agent is 0% and the filler is 29.3wt%.
Performance testing
Test example 1:
the waterproof rolls provided in examples 1 to 3 and comparative examples 1 to 5 were subjected to heat resistance tests under different conditions according to the standard requirements in GB/T23457-2009 and GB/T35467-2017, and the specific test results are shown in Table 1.
TABLE 1
The comparative examples 1, 2, 3-5 are ordinary pitch-based self-adhered waterproofing membrane, ordinary polymer self-adhered waterproofing membrane and novel polymer self-adhered waterproofing membrane respectively, and the difference of its heat resistance and novel polymer self-adhered waterproofing membrane lies in the introduction of heat-resistant auxiliary agent, and it plays a remarkable effect to the heat resistance of novel self-adhered adhesive material. The heat-resistant auxiliary agent has good heat resistance, small molecular weight and small viscosity, enables materials to be dissolved after the low-temperature adhesive is added, improves the fluidity and the dispersibility of the low-temperature adhesive, and can improve the heat resistance and the low-temperature adhesiveness of the self-adhesive after the novel high-molecular self-adhesive is mixed and dispersed.
Test example 2:
according to the standard requirements in GB/T23457-2009 and GB/T35467-2017, the polymer self-adhesive materials provided by examples 1-3 and comparative examples 3, 4 and 5 and the common self-adhesive waterproof adhesive material are subjected to a coil-to-coil peeling performance test under different conditions, and the specific test results are shown in Table 2.
TABLE 2
Comparative examples 3 and 4 are not modified by low-temperature adhesive under low-temperature conditions, so that the initial viscosity of the surface is reduced, the molecular chain moves slowly, and the polarity of the surface molecules is reduced; the comparative example 5 has the peeling strength less than 1.5N/mm at the temperature of-10 to-3 ℃, the dispersibility of the low-temperature adhesive in the high-molecular self-adhesive waterproof roll is poor, and the adhesive effect can not reach mutual embedding at the low temperature.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A preparation method of a low-temperature adhesive is characterized by comprising the following steps:
mixing isocyanate, metal filler and titanate coupling agent, and mixing at 85-105 ℃ to obtain the low-temperature adhesive.
2. The method for preparing a low-temperature adhesive according to claim 1,
15-35 parts of isocyanate, 40-80 parts of metal filler and 5-20 parts of titanate coupling agent.
3. The method for producing a low-temperature adhesive according to claim 1,
the isocyanate is toluene diisocyanate and/or diphenylmethane diisocyanate;
the metal filler is aluminum powder and/or iron powder;
the mixing mode is as follows: heating the mixture in water bath at 85-105 ℃ for 3-5 h.
4. A low-temperature adhesive prepared by the method for preparing a low-temperature adhesive according to any one of claims 1 to 3.
5. The utility model provides a polymer self-adhesion adhesive material which characterized in that, polymer self-adhesion adhesive material's raw materials composition includes:
20 to 45 weight percent of resin, 2 to 17 weight percent of styrene block copolymer, 1 to 3 weight percent of low-temperature adhesive, 15 to 30 weight percent of organic heat carrier, 0 to 2 weight percent of liquid pigment, 0 to 5 weight percent of plasticizer, 15 to 40 weight percent of filler and 0.5 to 4 weight percent of heat-resistant auxiliary agent;
the low-temperature adhesive is the low-temperature adhesive according to claim 4.
6. The polymeric self-adhesive material according to claim 5, wherein the polymeric self-adhesive material has a raw material composition satisfying:
0.1wt% to 2wt% of liquid pigment, and/or:
1 to 5 weight percent of plasticizer.
7. The polymeric self-adhesive composition according to claim 5 or 6, wherein,
the resin is at least one selected from terpene resin, petroleum resin and coumarone resin;
the softening point of the resin is 90-110 ℃;
the styrene block copolymer is selected from at least one of SIS, SSBR, SBR and SBS;
the molecular weight of the styrene block copolymer is 15-25 ten thousand;
the organic heat carrier is selected from at least one of white oil, base oil and reduced line oil;
the liquid pigment is selected from at least one of red liquid pigment, green liquid pigment, yellow liquid pigment and blue liquid pigment;
the plasticizer is selected from at least one of phthalate, phthalate and benzene polyacid ester;
the filler is selected from at least one of calcium carbonate, talcum powder, heavy calcium and light calcium;
the heat-resistant assistant is at least one selected from polyethylene wax, polypropylene wax and polypropylene.
8. The method for preparing the self-adhesive polymer material according to any one of claims 5 to 7, wherein the method comprises the following steps:
(1) Mixing and stirring an organic heat carrier and resin, and controlling the system temperature to be 130-150 ℃;
(2) Adding a styrene block copolymer after the resin is completely dissolved, controlling the system temperature to be 170-190 ℃, mixing and stirring:
(3) Optionally adding liquid pigment, optionally adding plasticizer, adding filler, adding heat-resistant auxiliary agent, adding low-temperature adhesive, controlling system temperature at 160-180 ℃, mixing and stirring to obtain the macromolecular self-adhesive material.
9. The utility model provides a polymer self-adhesion waterproofing membrane, its characterized in that, this polymer waterproofing membrane is including setting gradually: the main body comprises a main body base material layer, a high polymer self-adhesive glue layer and an isolation film layer;
the polymeric self-adhesive glue layer is formed by the polymeric self-adhesive glue according to any one of claims 5 to 7.
10. The polymer waterproofing membrane according to claim 9,
the main body base material layer is at least one of a strong cross laminated film, a high-strength composite film, a PTE aluminum-plated composite film and a high-strength original film;
the isolation film layer is at least one of a PE isolation film, a PP isolation film and a PET isolation film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105017982A (en) * | 2015-07-16 | 2015-11-04 | 广东禹能建材科技股份有限公司 | Preparation method of non-asphalt multifunctional waterproof coiled material laminated adhesive |
| CN110607158A (en) * | 2018-06-14 | 2019-12-24 | 苏州市回天科技有限公司 | Preparation method of low-temperature-resistant electromagnetic shielding adhesive |
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