CN112852347A - Self-repairable enhanced TPO (thermoplastic polyolefin) waterproof coiled material, reaction glue for waterproof coiled material and preparation method of reaction glue - Google Patents
Self-repairable enhanced TPO (thermoplastic polyolefin) waterproof coiled material, reaction glue for waterproof coiled material and preparation method of reaction glue Download PDFInfo
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- CN112852347A CN112852347A CN202110261494.9A CN202110261494A CN112852347A CN 112852347 A CN112852347 A CN 112852347A CN 202110261494 A CN202110261494 A CN 202110261494A CN 112852347 A CN112852347 A CN 112852347A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of waterproof rolls, and provides a reaction adhesive for a self-repairable enhanced TPO waterproof roll, which is used for a roll and can solve the technical problems of water seepage and water leakage after the TPO waterproof roll in the prior art is damaged; a reactive glue for a self-repairable enhanced TPO waterproofing membrane comprising: liquid ethylene propylene rubber, liquid butyl rubber, polyisobutylene, terpene resin, petroleum resin, nano magnesium hydroxide, fumed silica, an antioxidant, a crosslinking accelerator, a crosslinking agent and the like; the reaction adhesive can react with carbon-carbon single bonds in a high molecular chain through the action of a peroxide vulcanizing agent to form cross-linked bonds, so that the fatigue resistance and the thermo-oxidative aging resistance of the TPO waterproof coiled material are further improved, and meanwhile, the reaction adhesive has good creep property and can automatically repair the damaged coiled material; the invention also provides a preparation method of the reaction adhesive and a self-repairable enhanced TPO waterproof coiled material prepared by applying the reaction adhesive.
Description
Technical Field
The invention relates to the technical field of waterproof rolls, in particular to a self-repairable enhanced TPO waterproof roll, a reaction adhesive for the waterproof roll and a preparation method of the reaction adhesive.
Background
The TPO waterproof coiled material has the advantages of ageing resistance, good low-temperature flexibility, welding and convenient construction, shows high elasticity of rubber at normal temperature and can be molded like plastic at high temperature. Therefore, the material has good processing performance and mechanical property, and has high-strength welding performance. And after a layer of polyester fiber fabric is additionally arranged between two layers of TPO materials, the physical property of the TPO material can be enhanced, and the breaking strength, fatigue resistance and puncture resistance of the TPO material can be improved, namely the enhanced TPO waterproof coiled material.
In practical application, the product has the comprehensive characteristics of ageing resistance, high tensile strength, large elongation, capability of being constructed on a wet roof, no need of a protective layer for exposure, convenience in construction, no pollution and the like, and is very suitable for being used as a waterproof layer of a light energy-saving roof.
Chinese patent "an enhanced TPO waterproofing membrane for mechanical fixing system" (application No. 201220094001.3, application date 2012.03.13) discloses an enhanced TPO waterproofing membrane for mechanical fixing system, which is composed of an upper surface TPO coil layer, a middle fiber fabric reinforcing layer and a lower surface TPO coil layer, wherein the middle fiber fabric reinforcing layer is a mesh cloth.
Above-mentioned enhancement mode TPO waterproofing membrane exposes the back of ageing under receiving external condition destruction or for a long time in the environment, can appear the material destruction, forms the point of leaking water, if discovery and handling in time, will have because of the condition of the property loss that the infiltration leaked water caused, consequently need improve the enhancement TPO waterproofing membrane promptly and solve this defect situation.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art, provides a reaction adhesive for a self-repairable enhanced TPO waterproof coiled material, and can solve the technical problem of water seepage and water leakage after the TPO waterproof coiled material in the prior art is damaged when being used in the coiled material.
The invention also aims to provide a preparation method of the reaction adhesive for the self-repairable enhanced TPO waterproof roll.
It is yet another object of the present invention to provide a reinforced TPO waterproofing membrane that is self-healing.
The technical scheme adopted by the invention is that the reaction adhesive for the self-repairable enhanced TPO waterproof coiled material comprises the following components in parts by weight:
in the invention, the rubber main material can provide creep deformation, elastic deformation and a crosslinking matrix, the resin material provides adhesive bonding performance, the crosslinking agent provides a vulcanization crosslinking function, the magnesium hydroxide provides a flame retardant effect, and the antioxidant improves the aging resistance of the material. The ethylene propylene rubber and the polyolefin material have similar molecular chain segment structures, are both vinyl and propenyl structures, accord with the similar compatibility principle of high polymer materials, and have better compatibility; the arrangement of lateral methyl groups in a butyl rubber molecular chain is dense, so that the thermal activity of polymer molecules is limited, the air permeability is low, the air tightness is good, and the two types of the methyl groups exist simultaneously to improve the internal structure of the waterproof roll and stabilize the waterproof performance; the terpene resin and the petroleum resin can provide better viscosity for the coiled material, and the combination of the terpene resin and the petroleum resin further promotes the viscosity of the coiled material; the polyisobutylene can improve the plasticity and the creep property of the coiled material, and the terpene resin, the petroleum resin and the polyisobutylene can improve the self-healing efficiency of the coiled material. Partial vulcanization reaction is carried out between the self-repairing reaction glue and polyolefin in the TPO waterproof coiled material, wherein cross-linking bonds are formed between carbon-carbon single bonds of a high molecular chain after reaction through the action of a peroxide vulcanizing agent; when the TPO waterproof coiled material is damaged, the TPO waterproof coiled material cannot be repaired in time in rainy days, and at the moment, the damaged adhesive layer is self-healed under the action of creep property, so that water leakage can be delayed to avoid loss.
Furthermore, the particle size of the nano magnesium hydroxide is less than or equal to 1500 meshes.
Within the particle size range, the magnesium hydroxide has better dispersibility and better flame retardant effect in the coiled material.
Further, the specific surface area of the fumed silica is more than or equal to 200m2/g。
The method for measuring the specific surface area is the BET method. The larger the specific surface area, the better the dispersibility in rubber processing, and a certain reinforcing effect can be achieved.
Further, the liquid ethylene propylene rubber is selected from at least one of T65, T66, T76 and T77 in lion chemical; the liquid butyl rubber is selected from at least one of Kalene1300 of Royal Elastomers, LIIR268 and LIIR301 of JSR; the polyisobutylene is selected from one or two of PB1300 and PB900 of Korean Dalin; the terpene resin is at least one of T-105, T-115 and T-110 of DRT; the petroleum resin is at least one selected from C-110R, C-110W, C-115W of Istman; the fumed silica is at least one of H300, M-5 and LM-150 of cabot; the antioxidant is at least one selected from 1010, 168 and B225 of BASF.
Further, the crosslinking accelerator is selected from at least one of dithiotetramethylthiuram, zinc dibutyldithiocarbamate, and N-cyclohexyl-2-benzothiazylsulfenamide.
Further, the crosslinking agent is selected from at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide and dicumyl peroxide.
The crosslinking promoter is used in the crosslinking reaction of macromolecule and has high crosslinking reaction efficiency.
The preparation method of the reaction adhesive for the self-repairable enhanced TPO waterproof coiled material comprises the steps of placing liquid ethylene propylene rubber and liquid butyl rubber into a heating stirring kettle for mixing and processing, setting the rotating speed to be 50-60 r/min, heating to 150-160 ℃ within 20-40 min, adding polyisobutylene, terpene resin, petroleum resin, nano magnesium hydroxide, fumed silica and an antioxidant for 2-4 times, stirring and mixing until no particle exists on naked eyes, cooling to 90-110 ℃, adding a crosslinking accelerator and a crosslinking agent, stirring and mixing again, and obtaining no particle impurities after 20-40 min.
The utility model provides an enhancement mode TPO waterproofing membrane that can selfheal, includes TPO resin layer, reinforcing fabric and TPO resin layer down, reinforcing fabric surface coating has the one deck as above reaction glue.
The coiled material formed by the upper TPO resin layer, the reinforced fabric and the lower TPO resin layer has better breaking strength, fatigue resistance and puncture resistance, and the reinforced fabric is coated with a layer of the reaction adhesive, so that the performances of breaking strength, fatigue resistance, puncture resistance and the like can be further improved, and the coiled material also has self-repairing capability; the reaction glue and the upper and lower TPO resin layers have partial vulcanization reaction, the carbon-carbon single bonds of the polymer chains react through the action of the peroxide vulcanizing agent to form cross-linked bonds, and the creep property of the reaction glue enables the coiled material to have better self-repairing capability, so that the coiled material can be self-repaired in time when the coiled material is damaged, and the loss caused by water leakage is avoided.
Further, the reinforced fabric is PET polyester mesh cloth.
Furthermore, the tensile force of the waterproof coiled material is greater than or equal to 365N/cm, and the tearing strength is greater than or equal to 754N.
Further, the thickness of the upper TPO resin layer is 0.4-2 mm, the thickness of the reinforced fabric is 0.05-0.1 mm, and the thickness of the lower TPO resin layer is 0.5-3 mm.
Further, the reinforced fabric is subjected to gum dipping treatment and then is subjected to hot-press composite molding with the upper TPO resin layer and the lower TPO resin layer.
The reinforced fabric is dried for 30min at the temperature of 60 ℃ after being impregnated, and then is subjected to hot-pressing composite molding with the upper TPO resin layer and the lower TPO resin layer
Compared with the prior art, the invention has the beneficial effects that:
1) the reaction glue can react with carbon-carbon single bonds in a high molecular chain through the action of a peroxide vulcanizing agent to form cross-linked bonds, so that the fatigue resistance, heat resistance and ageing resistance of the TPO waterproof coiled material are further improved, and meanwhile, the reaction glue has good creep property and can automatically repair the damaged coiled material.
2) The resin combination of terpene resin and petroleum resin in the reaction glue can provide better viscosity for the coiled material;
3) the combination of the terpene resin, the petroleum resin and the polyisobutylene greatly improves the self-healing efficiency of the damaged coiled material.
Drawings
FIG. 1 is a structural view of a self-repairable reinforced TPO waterproof roll of the present invention.
Detailed Description
The examples of the present invention are provided for illustrative purposes only and are not to be construed as limiting the invention.
Example 1
This example provides a reaction glue for a self-repairable reinforced TPO waterproof roll, wherein the reaction glue comprises 25 parts by weight of liquid ethylene propylene rubber (lion chemical T65), 20 parts by weight of liquid butyl rubber (royaltomers Kalene1300), 10 parts by weight of polyisobutylene (PB 1300 of korea forest), 2 parts by weight of terpene resin (DRT T-110), 5 parts by weight of petroleum resin (eastman C-110R), 5 parts by weight of nano magnesium hydroxide, 5 parts by weight of fumed silica (cabot H300), 0.5 part by weight of antioxidant (BASF 1010), 0.12 part by weight of crosslinking accelerator (dithiotetramethyl thiuram), and 0.3 part by weight of crosslinking agent (2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane).
The preparation method comprises the following steps: mixing liquid ethylene propylene rubber (lion chemical T65) and liquid butyl rubber (Royal Elastomers Kalene1300) in a heating and stirring kettle at 50r/min for 20min to 150 deg.C, then adding polyisobutylene (PB 1300 of Dalin Korea), terpene resin (DRT T-110), petroleum resin (Ishmann C-110R), nano magnesium hydroxide, fumed silica (Cambot H300) and antioxidant (BASF 1010) for 2 times, stirring and mixing for the first time until the mixture is uniformly mixed and no particles appear under the eyes, and then cooling to 90 ℃, adding a crosslinking accelerator (dithiotetramethyl thiuram) and a crosslinking agent (2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane) to stir and mix for the second time, and obtaining the self-repairing reaction glue without granular impurities after 20 min.
Example 2
The embodiment provides a reaction glue for a self-repairable enhanced TPO waterproof coiled material, wherein 40 parts by weight of liquid ethylene propylene rubber (lion chemical T66), 35 parts by weight of liquid butyl rubber (Japanese JSR LIIR268), 45 parts by weight of polyisobutylene (Korean Dalin PB900), 6 parts by weight of terpene resin (DRT-105), 9 parts by weight of petroleum resin (Istman C-110W), 18 parts by weight of nano magnesium hydroxide, 12 parts by weight of fumed silica (Cambot M-5), 0.7 part by weight of antioxidant (BASF168), 0.15 part by weight of crosslinking accelerator (zinc dibutyldithiocarbamate) and 0.35 part by weight of crosslinking agent (2, 4-dichlorobenzoyl peroxide).
The preparation method comprises the following steps: putting liquid ethylene propylene rubber (lion chemical T66) and liquid butyl rubber (Japanese JSR LIIR268) glue into a heating stirring kettle for mixing and processing, setting the rotating speed to be 55r/min, heating to 157 ℃ within 23min, then adding polyisobutylene (Korean forest PB900), terpene resin (DRT T-105), petroleum resin (Istman C-110W), nano magnesium hydroxide, fumed silica (Cambot M-5) and antioxidant (BASF168) for 3 times, stirring and mixing for the first time until the mixture is uniform and no particles are seen by naked eyes, then cooling to 100 ℃, adding crosslinking accelerator (zinc dibutyldithiocarbamate) and crosslinking agent (2, 4-dichlorobenzoyl) for stirring and mixing for the second time, and obtaining the self-repairing reaction glue after 25min without particle impurities.
Example 3
The embodiment provides a reaction glue for a self-repairable enhanced TPO waterproof coiled material, wherein the reaction glue comprises 60 parts by weight of liquid ethylene propylene rubber (lion chemical T76), 55 parts by weight of liquid butyl rubber (Japanese JSR LIIR301), 50 parts by weight of polyisobutylene (Korean Dalling PB1300), 10 parts by weight of terpene resin (DRT T-115), 15 parts by weight of petroleum resin (Istman C-115W), 32 parts by weight of nano magnesium hydroxide, 25 parts by weight of fumed silica (Cambot LM-150), 1.2 parts by weight of antioxidant (BASF B225), 0.18 part by weight of crosslinking accelerator (N-cyclohexyl-2-benzothiazyl sulfenamide) and 0.4 part by weight of crosslinking agent (dicumyl peroxide).
The preparation method comprises the following steps: putting liquid ethylene propylene rubber (lion chemical T76) and liquid butyl rubber (Japanese JSR LIIR301) into a heating stirring kettle, mixing and processing, setting the rotating speed at 60r/min, heating to 160 ℃ within 40min, then adding polyisobutylene (Korean forest PB1300), terpene resin (DRT T-115), petroleum resin (Istman C-115W), nano magnesium hydroxide, fumed silica (Cambot LM-150) and antioxidant (BASF B225) for 4 times, stirring and mixing for the first time until the mixture is uniform and no particles are seen by naked eyes, then cooling to 110 ℃, adding crosslinking accelerator (N-cyclohexyl-2-benzothiazyl sulfenamide) and crosslinking agent (dicumyl peroxide), stirring and mixing for the second time, and obtaining the self-repairing reaction rubber without particle impurities after 40 min.
The inner reinforced fabric is respectively soaked in the reaction glue prepared in the embodiments 1 to 3, after the gum dipping treatment is completed, the inner reinforced fabric and the thermoplastic polyolefin sheet extruded by the extruder are subjected to hot-pressing composite forming, and the reinforced TPO waterproof roll with the self-repairing function is formed by hot-pressing composite through a three-roll calender, as shown in FIG. 1.
Comparative example 1
The difference between the comparative example 1 and the example 1 is that the inner reinforced fabric of the comparative example 1 is not treated by dipping, and the material and the preparation method of the reinforced TPO waterproof coiled material are the same as those of the example 1.
The unbroken coil and the broken coil of examples 1-3 and comparative example 1 were each tested using the national standard GB 27789-.
The properties of the unbroken coils of examples 1-3 and comparative example 1 are shown in table 1:
TABLE 1 comparison of the Properties of the unbroken coils of examples 1-3 and comparative example 1
As can be seen from Table 1, the waterproof coiled material of comparative example 1 only reaches the national standard in water impermeability, while the waterproof coiled materials of examples 1-3 of the invention can obviously keep water tightness for a longer time under the same water pressure; and if at the same time, it is apparent that it can be maintained watertight under a greater water pressure, thus showing that the waterproofing membrane of the present invention has a better water pressure resistant duration and water pressure resistant pressure, and further, the waterproofing membrane of the present invention has better tensile and tear strengths than those of comparative example 1.
The coils of examples 1 to 3 and comparative example 1 were subjected to a self-repairing force test after breakage, the coils of examples 1 to 3 and comparative example 1 were selected to be broken to the same extent, and the test was performed after leaving for 10min, and the results are shown in table 2:
TABLE 2 self-healing after coil failure test comparison of examples 1-3 and comparative example 1
As can be seen from table 2, the waterproof roll of the present invention has a certain self-repairing capability after being damaged, while the waterproof roll of comparative example 1 has no self-repairing capability.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. The reaction glue for the self-repairable enhanced TPO waterproof coiled material is characterized by comprising the following components in parts by weight:
2. the reaction adhesive for the self-repairable enhanced TPO waterproof roll according to claim 1, characterized in that the grain size of the nano magnesium hydroxide is less than or equal to 1500 meshes.
3. The reaction adhesive for the self-repairable enhanced TPO waterproof roll according to claim 1, characterized in that the specific surface area of the fumed silica is more than or equal to 200m2/g。
4. The reactive glue for self-healing reinforced TPO waterproofing membranes according to claim 1 wherein the crosslinking accelerator is selected from at least one of tetramethylthiuram dithionate, zinc dibutyldithiocarbamate, N-cyclohexyl-2-benzothiazylsulfenamide.
5. The reactive glue for self-healing reinforced TPO waterproofing membrane according to claim 1, characterized in that said cross-linking agent is selected from at least one of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide and dicumyl peroxide.
6. A preparation method of the reaction adhesive for the self-repairable enhanced TPO waterproof coiled material as claimed in any one of claims 1 to 5, characterized in that liquid ethylene propylene rubber and liquid butyl rubber are placed in a heating stirring kettle to be mixed and processed, the rotating speed is set to be 50-60 r/min, the temperature is raised to 150-160 ℃ within 20-40 min, then polyisobutylene, terpene resin, petroleum resin, nano calcium carbonate, fumed silica and antioxidant are added for 2-4 times, the mixture is stirred and mixed until no particle exists in naked eyes, then the temperature is lowered to 90-110 ℃, a crosslinking accelerator and a crosslinking agent are added, the mixture is stirred and mixed again, and no particle impurities are obtained after 20-40 min.
7. A self-repairable reinforced TPO waterproof coiled material comprises an upper TPO resin layer, a reinforced fabric and a lower TPO resin layer, wherein the surface of the reinforced fabric is wrapped with a layer of the reaction glue as described in any one of claims 1 to 5.
8. The self-healing reinforced TPO waterproofing membrane according to claim 7 wherein the waterproofing membrane has a tensile force greater than or equal to 365N/cm and a tear strength greater than or equal to 754N.
9. A self-repairable enhanced TPO waterproof coiled material as claimed in claim 7, wherein the thickness of the upper TPO resin layer is 0.4-2 mm, the thickness of the enhanced fabric is 0.05-0.1 mm, and the thickness of the lower TPO resin layer is 0.5-3 mm.
10. A self-repairable enhanced TPO waterproofing membrane according to any one of claims 7 to 9, wherein the enhanced fabric is subjected to a gum dipping treatment and then is subjected to a hot-press composite molding with an upper TPO resin layer and a lower TPO resin layer.
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| CN202110261494.9A CN112852347A (en) | 2021-03-10 | 2021-03-10 | Self-repairable enhanced TPO (thermoplastic polyolefin) waterproof coiled material, reaction glue for waterproof coiled material and preparation method of reaction glue |
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| CN202110261494.9A CN112852347A (en) | 2021-03-10 | 2021-03-10 | Self-repairable enhanced TPO (thermoplastic polyolefin) waterproof coiled material, reaction glue for waterproof coiled material and preparation method of reaction glue |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202467012U (en) * | 2012-03-13 | 2012-10-03 | 北京东方雨虹防水技术股份有限公司 | Enhanced TPO (thermoplastic olefin) waterproof coiled material for machine fixing system |
| CN105585978A (en) * | 2016-03-14 | 2016-05-18 | 王辉 | Waterproof self-adhesive coiled material prepared from butyl rubber and preparation method of coiled material |
| CN109370068A (en) * | 2018-09-25 | 2019-02-22 | 青岛东方雨虹建筑材料有限公司 | A kind of low temperature resistant TPO self-adhesive layer and preparation method thereof and low temperature resistant TPO waterproof roll |
-
2021
- 2021-03-10 CN CN202110261494.9A patent/CN112852347A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202467012U (en) * | 2012-03-13 | 2012-10-03 | 北京东方雨虹防水技术股份有限公司 | Enhanced TPO (thermoplastic olefin) waterproof coiled material for machine fixing system |
| CN105585978A (en) * | 2016-03-14 | 2016-05-18 | 王辉 | Waterproof self-adhesive coiled material prepared from butyl rubber and preparation method of coiled material |
| CN109370068A (en) * | 2018-09-25 | 2019-02-22 | 青岛东方雨虹建筑材料有限公司 | A kind of low temperature resistant TPO self-adhesive layer and preparation method thereof and low temperature resistant TPO waterproof roll |
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| 阮桂海: "《丁基橡胶应用工艺》", 31 July 1980, 化学工业出版社 * |
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Application publication date: 20210528 |