CN113502132A

CN113502132A - Pre-laid high-polymer waterproof coiled material and preparation method thereof

Info

Publication number: CN113502132A
Application number: CN202110801752.8A
Authority: CN
Inventors: 胡伟华; 龚兴宇; 杨小育; 刘勤
Original assignee: Weinan Keshun New Material Co ltd
Current assignee: Weinan Keshun New Material Co ltd
Priority date: 2021-07-15
Filing date: 2021-07-15
Publication date: 2021-10-15
Anticipated expiration: 2041-07-15
Also published as: CN113502132B

Abstract

The invention relates to the technical field of building waterproofing, and discloses a pre-paved high-molecular waterproof coiled material and a preparation method thereof. The pre-paved high-molecular waterproof coiled material comprises a carrier, an adhesive layer loaded on the carrier and a protective layer loaded on the adhesive layer; the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.05-0.20; the protective layer is a water-based fluorocarbon coating, and the water-based fluorocarbon coating contains more than two tert-fluoro emulsions, water, a filler, a pH regulator, a defoaming agent, a thickening agent and a dispersing agent which are stored in a mixed manner or independently. The weather resistance and the ageing resistance of the pre-paved high-polymer waterproof coiled material provided by the invention are obviously improved.

Description

Pre-laid high-polymer waterproof coiled material and preparation method thereof

Technical Field

The invention relates to the technical field of building waterproofing, in particular to a pre-paved high-molecular waterproof coiled material and a preparation method thereof.

Background

The waterproof roll is mainly used for building walls, roofs, tunnels, highways, refuse landfills and the like, can be curled into a roll-shaped flexible building material product for resisting external rainwater and underground water leakage, is used as an engineering foundation for realizing water seepage-free connection among buildings, is a waterproof first barrier of the whole engineering, and plays a vital role in the whole engineering.

The prior pre-laid waterproofing membrane generally comprises a substrate layer, an adhesive layer on the substrate layer and a sand grain anti-sticking layer on the adhesive layer. The product is mainly isolated by adopting a sand-coating mode, can be solidified together with cast-in-place concrete through chemical crosslinking reaction and physical mortise and tenon joint, can completely prevent water from permeating into a gap between the waterproof coiled material and the structure, is not influenced by displacement of a basal layer, and fundamentally avoids the defect of water channeling.

However, after the roll is laid on a construction site in an empty state, the sand-coated surface is directly exposed to ultraviolet rays, and gaps among sand grains can cause the aging of the hot melt adhesive or butyl rubber, so that the service life of the waterproof roll is reduced.

Disclosure of Invention

The invention aims to overcome the defects of poor weather resistance and easy aging of the pre-paved high-molecular waterproof roll in the prior art.

As described in the background art, the existing pre-paved waterproof roll is isolated in a sand-lined manner, and the sand-lined surface is directly exposed to ultraviolet rays, so that the adhesive layer is aged, and the service life of the waterproof roll is reduced. In the research process, the inventor of the invention finds that on one hand, the water-based fluorocarbon coating containing a specific amount of tertiary fluorine emulsion is used as a protective layer, so that the skin-type full adhesion can be formed with post-pouring concrete, the possibility of water channeling is effectively reduced, and the bonding strength between a coiled material and the concrete is improved; on the other hand, the protective layer is matched with the carrier and the adhesive layer in a specific thickness proportion, so that the waterproof roll can effectively resist the erosion of outdoor ultraviolet rays, high temperature, sand and stone and rainwater, and the pre-paved high-polymer waterproof roll with excellent weather resistance and ageing resistance can be obtained. Based on the foregoing, the inventors provide a solution to the present invention.

In order to achieve the above object, a first aspect of the present invention provides a pre-paved polymer waterproof roll, including a carrier, an adhesive layer loaded on the carrier, and a protective layer loaded on the adhesive layer; the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.05-0.20;

the protective layer is a water-based fluorocarbon coating, and the water-based fluorocarbon coating contains more than two tert-fluoro emulsions, water, a filler, a pH regulator, a defoaming agent, a thickening agent and a dispersing agent which are stored in a mixed manner or independently;

based on the total weight of the aqueous fluorocarbon coating, the content of the tertiary fluorine emulsion is 20-60 wt%, the content of water is 2-40 wt%, the content of the filler is 10-30 wt%, the content of the pH regulator is 0.05-5.0 wt%, the content of the defoaming agent is 0.05-5.0 wt%, the content of the thickening agent is 0.05-5.0 wt%, and the content of the dispersing agent is 0.05-5.0 wt%;

the concentration of the tertiary fluorine emulsion is 45-55 wt%.

The second aspect of the present invention provides a method for preparing the pre-spread polymer waterproof roll material of the first aspect, which comprises: and sequentially loading an adhesive layer and a protective layer on the carrier, and curing the obtained product.

The pre-paved high-molecular waterproof coiled material formed by taking the aqueous fluorocarbon coating containing a specific amount of the tertiary fluorine emulsion as a protective layer and matching with the carrier and the adhesive layer in a specific thickness proportion can effectively resist the erosion of outdoor ultraviolet rays, high temperature, sand and rain without obvious attenuation of performance.

The inventor also finds that the pre-paved high-molecular waterproof coiled material provided by the invention not only can reduce the utilization rate of sand and improve the environmental protection, but also can enhance the full adhesion effect with post-poured concrete; meanwhile, the water-based fluorocarbon coating is used as a protective layer, has no stickiness and no exposed glue points, can effectively isolate a glue layer, and does not cause a foot sticking phenomenon.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, unless otherwise specified, the room temperature or room temperature is 25. + -. 2 ℃.

As described above, the first aspect of the present invention provides a pre-spread polymer waterproof roll, which includes a carrier, an adhesive layer loaded on the carrier, and a protective layer loaded on the adhesive layer; the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.05-0.20;

the concentration of the tertiary fluorine emulsion is 45-55 wt%.

Preferably, the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.08-0.12. The inventors have found that, according to the preferred embodiment, a pre-laid polymer waterproof roll having more excellent weather resistance and aging resistance can be obtained.

Preferably, the concentration of the tertiary fluorine emulsion is 50-55 wt%. The inventors have found that, according to the preferred embodiment, a protective layer having a high adhesion to cement, metal, or the like can be obtained, and the bonding strength between the waterproofing membrane and the post-cast concrete can be effectively improved.

The invention has no special requirement on the source of the tertiary fluorine emulsion, and the tertiary fluorine emulsion can be prepared by the existing method or obtained commercially, and is exemplarily obtained by polymerizing fluorine-containing acrylic ester and vinyl versatate.

Preferably, the tertiary fluorine emulsion is obtained by a preparation method comprising the following steps:

(1) in the presence of a solvent I, carrying out contact mixing I on ethylene versatate, fluorine-containing acrylate, a first part of polyoxyethylene octyl phenol ether-10 and a first part of allyloxy hydroxypropyl sodium sulfonate to obtain a first mixed solution;

(2) in the presence of a solvent II, carrying out contact mixing on the rest of polyoxyethylene octyl phenol ether-10, the rest of sodium allyloxy hydroxypropyl sulfonate and a part of the first mixed solution II to obtain a second mixed solution;

(3) contacting and mixing the second mixed solution, the initiator and the rest part of the first mixed solution III to obtain a third mixed solution;

(4) and (3) carrying out contact mixing IV on the third mixed solution, tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate to obtain a fourth mixed solution, and adjusting the pH value of the fourth mixed solution to 7-8.

Preferably, the solvent I and the solvent II are both deionized water.

Preferably, in step (1), the first portion of polyoxyethylene octylphenol ether-10 is 30-35 wt% of the total amount of polyoxyethylene octylphenol ether-10, and the first portion of sodium allyloxy hydroxypropyl sulfonate is 30-35 wt% of the total amount of sodium allyloxy hydroxypropyl sulfonate.

Preferably, in step (1), the conditions of contacting and mixing I at least comprise: the stirring speed is 100-200rpm, the temperature is 5-35 ℃, and the time is 5-20 min.

Preferably, in step (2), a part of the first mixed solution accounts for 1-5 wt% of the total weight of the first mixed solution.

Preferably, in step (2), the conditions of contacting and mixing II include at least: the stirring speed is 300-500rpm, the temperature is 75-90 ℃, and the time is 180-600 min.

Preferably, in step (3), the initiator is selected from at least one of ammonium persulfate and sodium bicarbonate.

Preferably, in step (3), the conditions for contacting mixture III include at least: the stirring speed is 300-500rpm, the temperature is 75-90 ℃, and the time is 300-600 min.

Preferably, in step (4), the conditions for contacting the mixture IV include at least: the stirring speed is 300-500rpm, the temperature is 60-75 ℃, and the time is 60-120 min.

According to a particularly preferred embodiment, in the above preparation method, based on the total amount of all raw materials, the deionized water is used in an amount of 20 to 40 wt%, the vinyl versatate is used in an amount of 20 to 50 wt%, the fluorine-containing acrylate is used in an amount of 5 to 30 wt%, the polyoxyethylene octylphenol ether-10 is used in an amount of 1 to 2 wt%, the sodium allyloxy hydroxypropyl sulfonate is used in an amount of 1 to 2 wt%, the initiator is used in an amount of 0.05 to 1.0 wt%, the tert-butyl hydroperoxide is used in an amount of 0.05 to 0.5 wt%, and the sodium formaldehyde sulfoxylate is used in an amount of 0.05 to 0.5 wt%.

Preferably, based on the total weight of the aqueous fluorocarbon coating, the content of the tertiary fluorine emulsion is 30-50 wt%, the content of the water is 10-35 wt%, the content of the filler is 20-30 wt%, the content of the pH regulator is 0.5-1.5 wt%, the content of the defoaming agent is 0.5-1.5 wt%, the content of the thickening agent is 0.5-1.5 wt%, and the content of the dispersing agent is 0.5-1.5 wt%.

Preferably, the carrier is selected from at least one of high density polyethylene, thermoplastic polyolefin and ethylene propylene diene monomer.

Preferably, the adhesive layer is selected from at least one of pressure-sensitive hot melt adhesive, butyl rubber and acrylate adhesive.

Preferably, the filler is selected from at least one of talc, heavy calcium, light calcium and kaolin.

Preferably, the pH adjuster is at least one selected from the group consisting of acetic acid, formic acid, hydrochloric acid, ammonia water, aqueous monomethylamine solution, and aqueous dimethylamine solution.

According to a particularly preferred embodiment, in the pH regulator, the concentrations of the acetic acid, the formic acid and the hydrochloric acid are all from 1 to 5 wt%, and the concentrations of the aqueous ammonia, the aqueous dimethylamine solution and the aqueous monomethylamine solution are all from 3 to 10 wt%.

Preferably, the defoamer is selected from silicone based defoamers.

According to a particularly preferred embodiment, the antifoaming agent is selected from at least one of dow AFE1410, middle federal B313, middle federal B314, middle federal B315.

Preferably, the thickening agent is selected from cellulose ether-based thickening agents.

According to a particularly preferred embodiment, the thickener is chosen from at least one of basf C040, dow ASE60, sublong HHBR 250.

Preferably, the dispersant is selected from at least one of Basff 4010, Fule DS-193, Nippon research S-100.

As described above, the second aspect of the present invention is a method for producing a roll of pre-applied polymer waterproof sheet according to the first aspect, the method comprising: and sequentially loading an adhesive layer and a protective layer on the carrier, and curing the obtained product.

In the present invention, there is no particular requirement on the operation steps of sequentially loading the adhesive layer and the protective layer on the carrier, and the loading may be performed by a method conventional in the art, and for example, the adhesive layer and the protective layer may be sequentially loaded on the carrier by spray gun spraying, knife coating, or roll coating.

Preferably, the method further comprises: before the protective layer is loaded, the components in the water-based fluorocarbon coating are mixed.

The invention has no special requirements on the preparation method of the water-based fluorocarbon coating, can be prepared by adopting the existing method, and exemplarily provides a particularly preferred preparation method of the water-based fluorocarbon coating, which comprises the following steps:

(I) first mixing water and a thickening agent to obtain a first mixture;

(II) second mixing the first mixture with a pH regulator to obtain a second mixture;

(III) carrying out third mixing on the second mixture, the tertiary fluorine emulsion, the filler and the defoaming agent to obtain a third mixture;

(IV) fourth mixing the third mixture with a dispersant.

According to a particularly preferred embodiment, in step (I), the conditions of the first mixing are at least such that: the stirring speed is 100-200rpm, the temperature is 5-35 ℃, and the time is 5-10 min.

According to a particularly preferred embodiment, in step (II), the conditions of the second mixing are at least such that: the stirring speed is 100-300rpm, the temperature is 5-35 ℃, and the time is 5-10 min.

According to a particularly preferred embodiment, in step (III), the conditions of the third mixing are at least such that: the stirring speed is 500-1000rpm, the temperature is 5-35 ℃, and the time is 10-20 min.

According to a particularly preferred embodiment, in step (IV), the fourth mixing conditions at least satisfy: the stirring speed is 500-1000rpm, the temperature is 5-35 ℃, and the time is 10-20 min.

Preferably, the curing conditions at least satisfy: the temperature is 90-110 deg.C, and the time is 2-5 min.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials and instruments used are commercially available unless otherwise specified.

Tertiary fluorine emulsion: stirring 100g of ethylene versatate, 50g of fluorine-containing acrylate, 100g of deionized water, 5g of polyoxyethylene octyl phenol ether-10 and 5g of sodium allyloxy hydroxypropyl sulfonate at 150rpm for 15min at room temperature to obtain a first mixed solution;

at room temperature, fully dissolving 1g of ammonium persulfate by using 100g of deionized water to obtain 101mL of ammonium persulfate solution for later use;

stirring 100g of deionized water, 10g of polyoxyethylene octylphenol ether-10, 10g of sodium allyloxy hydroxypropyl sulfonate and 2 wt% of first mixed solution at 400rpm for 180min at 80 ℃ to obtain second mixed solution, adding 11mL of ammonium persulfate solution into the second mixed solution at an interval of 10min, reacting for 20min, then dropwise adding mixed solution formed by 90mL of ammonium persulfate solution and the rest of the first mixed solution, timing by dropwise adding the first drop of mixed solution, finishing dropwise adding after 3h, and preserving heat for 2h to obtain third mixed solution;

adding 0.5g of tert-butyl hydroperoxide and 0.5g of sodium formaldehyde sulfoxylate into the third mixed solution at 60 ℃, stirring for 80min at 500rpm to obtain a fourth mixed solution, and adjusting the pH value of the fourth mixed solution to 7 by using ammonia water to obtain a tert-fluoro emulsion;

acrylic emulsion: the brand is 328K, purchased from Barde Fukulture Co., Ltd;

aqueous SBS emulsion: the trademark is T-138 and is purchased from Shanghai Guangfu chemical Co., Ltd;

filling: talc having an average particle size of 1250 mesh and available from Hebeixin Xu mineral products Co., Ltd;

filling: light calcium carbonate, model No. SF-NM35, available from samba fine chemicals, inc, su;

filling: coarse whiting, with an average particle size of 1250 mesh, was purchased from Shijiazhuan Xin liter mineral products, Inc.;

pH regulator: monomethylamine, purchased from Changzhou gather-abundance chemical;

pH regulator: dimethylamine, available from changzhou polyconcentration chemical;

defoaming agent: model AFE1410, available from dow, usa;

thickening agent: brand C040, available from basf shares company;

thickening agent: trade designation ASE60, purchased from dow, usa;

dispersing agent: under the trademark 4010, available from basf shares, inc;

carrier: low-pressure polyethylene with the trademark of 001, Shenzhen, Hongxingyuan plastic products Limited;

carrier: polyolefin thermoplastic elastomer, trade name YHGT-009, Shandong silver waterproof materials Ltd;

carrier: ethylene Propylene Diene Monomer (EPDM) with the trademark of OS-2329, Hebei European Plastic products Co., Ltd;

glue layer: the hot-melt pressure-sensitive adhesive is provided by Koshun waterproof science and technology Co.Ltd, and has the model of CKS-101;

glue layer: pressure-sensitive acrylate adhesive, available from Changzhou spring adhesive products science and technology Limited under the designation 4045;

glue layer: butyl rubber, brand 1675N, shanghai duo kang realities ltd;

in the following examples, the concentration of the aqueous monomethylamine solution was 5 wt%, and the concentration of the aqueous dimethylamine solution was 5 wt%.

Preparation example 1

The preparation examples are provided to illustrate that the waterborne fluorocarbon coating of the present invention is prepared according to the formula and process parameters shown in table 1 and by the following method.

The method for preparing the water-based fluorocarbon coating comprises the following steps:

(1) stirring water and a thickening agent at 150rpm for 8min at normal temperature to obtain a first mixture;

(2) stirring the obtained first mixture and a pH regulator at the normal temperature for 8min at 150rpm to obtain a second mixture;

(3) stirring the obtained second mixture, the tertiary fluorine emulsion, the filler and the defoaming agent at the normal temperature for 15min at 800rpm to obtain a third mixture;

(4) and stirring the third mixture and the dispersant at 800rpm for 15min at normal temperature to obtain the water-based fluorocarbon coating S1.

The remaining preparation examples, unless otherwise specified, were carried out using the same procedure as in preparation example 1, except that the aqueous fluorocarbon coating formulations and process parameters used were different, as specified in table 1.

TABLE 1

Example 1

The embodiment provides a preparation method of a pre-paved high-molecular waterproof roll, which comprises the steps of taking low-pressure polyethylene as a carrier, coating hot-melt pressure-sensitive adhesive on the carrier to form an adhesive layer, spraying the water-based fluorocarbon coating prepared in the preparation example 1 on the adhesive layer to form a protective layer, and baking at 100 ℃ for 3min to solidify the protective layer to obtain a pre-paved high-molecular waterproof roll A1;

wherein the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3: 0.12; the thickness of the protective layer is 1.2 mm.

Example 2

The embodiment provides a preparation method of a pre-paved high-molecular waterproof roll, which comprises the steps of taking a polyolefin thermoplastic elastomer as a carrier, coating a pressure-sensitive acrylic adhesive on the carrier to form an adhesive layer, spraying the water-based fluorocarbon coating prepared in the preparation example 2 on the adhesive layer to form a protective layer, and baking at 110 ℃ for 2min to solidify the protective layer to obtain a pre-paved high-molecular waterproof roll A2;

wherein the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.35: 0.08; the thickness of the protective layer is 1.2 mm.

Example 3

The embodiment provides a preparation method of a pre-paved high-molecular waterproof roll, which comprises the steps of taking ethylene propylene diene monomer as a carrier, coating butyl rubber on the carrier to form a glue layer, spraying the water-based fluorocarbon coating prepared in the preparation example 3 on the glue layer to form a protective layer, and baking at 90 ℃ for 4min to solidify the protective layer to obtain a pre-paved high-molecular waterproof roll A3;

wherein the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3: 0.1; the thickness of the protective layer is 1.2 mm.

Example 4

A pre-paved polymer waterproof roll was prepared according to the method of example 1, except that the aqueous fluorocarbon coating prepared in preparation example 4 was sprayed on the adhesive layer to form a protective layer.

Example 5

The pre-paved polymer waterproof roll is prepared according to the method of example 1, except that the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3: 0.2; and the thickness of the protective layer was the same as that of example 1.

Example 6

A pre-applied polymer waterproofing membrane was prepared according to the method of example 1, except that the concentration of the tertiary fluorine emulsion in the protective layer aqueous fluorocarbon coating was 45 wt%.

Comparative example 1

The comparative example prepares a pre-paved polymer waterproof roll according to the method of example 1, except that the protective layer with the same thickness is formed by spraying the aqueous fluorocarbon coating prepared in comparative example 1 on the adhesive layer.

Comparative example 2

This comparative example prepares a pre-paved polymer waterproofing membrane according to the method of example 1, except that the protective layer having the same thickness is formed by spraying the aqueous fluorocarbon coating prepared in comparative example 2 on the adhesive layer.

Comparative example 3

The pre-paved polymer waterproof roll is prepared according to the method of example 1, except that the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.4: 0.3 and the thickness of the protective layer was the same as that of example 1.

Comparative example 4

A pre-applied polymer waterproofing membrane was prepared according to the method of example 1, except that the concentration of the tertiary fluorine emulsion in the protective layer aqueous fluorocarbon coating was 58 wt%.

Test example

The pre-paved polymer waterproof coiled material prepared in the examples and the comparative examples is subjected to performance detection, and the peel strength of the pre-paved polymer waterproof coiled material and post-cast concrete before and after aging is detected according to the national standard GB/T23457-2017.

TABLE 2

As can be seen from Table 1, the peel strength of the pre-paved waterproof polymer coil and post-cast concrete provided by the invention is higher than that of GB/T23457-2017, and particularly, after xenon lamp aging, the peel strength is higher than that before treatment, so that the pre-paved waterproof polymer coil provided by the invention has excellent weather resistance and ageing resistance.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A pre-paved high-molecular waterproof coiled material is characterized by comprising a carrier, an adhesive layer loaded on the carrier and a protective layer loaded on the adhesive layer; the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.05-0.20;

the concentration of the tertiary fluorine emulsion is 45-55 wt%.

2. The pre-paved polymer waterproof roll as claimed in claim 1, wherein the thickness ratio of the carrier, the adhesive layer and the protective layer is 1: 0.3-0.35: 0.08-0.12.

3. The roll of pre-applied polymer waterproofing membrane according to claim 1 or 2, wherein the concentration of the tertiary fluorine emulsion is 50 to 55 wt%.

4. The roll of pre-applied polymer waterproofing membrane according to any of claims 1 to 3, wherein the tertiary fluorine emulsion is obtained by polymerization of a fluorine-containing acrylate and vinyl versatate.

5. The pre-paved polymer waterproof roll according to any one of claims 1-4, wherein the content of the tertiary fluorine emulsion is 30-50 wt%, the content of the water is 10-35 wt%, the content of the filler is 20-30 wt%, the content of the pH regulator is 0.5-1.5 wt%, the content of the defoamer is 0.5-1.5 wt%, the content of the thickener is 0.5-1.5 wt%, and the content of the dispersant is 0.5-1.5 wt%, based on the total weight of the aqueous fluorocarbon coating.

6. The pre-paved polymer waterproof coiled material according to any one of claims 1 to 5, wherein the carrier is at least one selected from high-density polyethylene, thermoplastic polyolefin and ethylene propylene diene monomer;

preferably, the adhesive layer is at least one selected from hot melt pressure sensitive adhesive, butyl rubber and acrylate adhesive.

7. The pre-paved polymer waterproof roll according to any one of claims 1-6, wherein the filler is at least one selected from talc, heavy calcium carbonate, light calcium carbonate and kaolin;

8. A method for preparing a pre-spread polymer waterproof roll material according to any one of claims 1 to 7, which comprises the following steps: and sequentially loading an adhesive layer and a protective layer on the carrier, and curing the obtained product.

9. The method of claim 8, wherein the method further comprises: before the protective layer is loaded, the components in the water-based fluorocarbon coating are mixed.

10. The method of claim 8, wherein the curing conditions are at least: the temperature is 90-110 deg.C, and the time is 2-5 min.