阅读说明：本技术 一种复合防水卷材及其制备方法 (Composite waterproof coiled material and preparation method thereof ) 是由 陈明进 杨杰 全敦华 刁雪锋 申应军 刘曙光 于 2021-07-28 设计创作，主要内容包括：本发明涉及新材料技术领域,特别涉及一种复合防水卷材及其制备方法,该复合防水卷材包括上表层、中间层以及下表层；按重量份计,所述上表层、中间层和下表层分别包括以下原料组分：上表层和下表层：LLDPE100份,HDPE10～30份,茂金属聚乙烯10～30份,PE粘接树脂10～30份,稳定剂0.5～1份；中间层：EVA100份,LLDPE100～110份,HDPE10～30份,茂金属聚乙烯10～30份,交联剂0.1～1份,稳定剂0.5～1份。本发明提供的复合防水卷材,具有耐高温、耐低温、易焊接等优异性能,解决现有防水板的耐热性、耐低温性能不足的问题。(The invention relates to the technical field of new materials, in particular to a composite waterproof roll and a preparation method thereof, wherein the composite waterproof roll comprises an upper surface layer, a middle layer and a lower surface layer; the upper surface layer, the middle layer and the lower surface layer respectively comprise the following raw material components in parts by weight: upper and lower skins: 100 parts of LLDPE, 10-30 parts of HDPE, 10-30 parts of metallocene polyethylene, 10-30 parts of PE bonding resin and 0.5-1 part of stabilizer; an intermediate layer: 100 parts of EVA, 100-110 parts of LLDPE, 10-30 parts of HDPE, 10-30 parts of metallocene polyethylene, 0.1-1 part of cross-linking agent and 0.5-1 part of stabilizer. The composite waterproof coiled material provided by the invention has excellent performances of high temperature resistance, low temperature resistance, easy welding and the like, and solves the problem that the heat resistance and the low temperature resistance of the existing waterproof board are insufficient.)

1. The composite waterproof roll is characterized by comprising an upper surface layer, a middle layer and a lower surface layer; the upper surface layer, the middle layer and the lower surface layer respectively comprise the following raw material components in parts by weight:

upper and lower skins:

an intermediate layer:

2. the composite waterproof roll according to claim 1, wherein the thickness ratio of the upper surface layer, the middle layer and the lower surface layer is (0.5-1.5): (6.5-8.5): (0.5 to 1.5).

3. The composite waterproofing membrane according to claim 1, wherein the thickness ratio of the upper surface layer, the middle layer and the lower surface layer is 1: 8: 1.

4. the composite waterproof roll material according to claim 1, wherein the melt flow rate of the EVA is 0.5-2 g/10min, and the mass content of the vinyl acetate in the EVA is 10-30%.

5. The composite waterproof roll material as claimed in claim 1, wherein the LLDPE has a melt flow rate of 0.5-2 g/10 min.

6. The composite waterproof roll material as claimed in claim 1, wherein the melt flow rate of the HDPE is 0.5-2 g/10 min.

7. The composite waterproof roll material according to claim 1, wherein the melt flow rate of the metallocene polyethylene is 0.5 to 2g/10 min.

8. The composite waterproof roll material according to claim 1, wherein the crosslinking agent is one or more of TMPTA, DEGDA and TPGDA.

9. The composite waterproof roll material according to claim 1, wherein the melt flow rate of the PE bonding resin is 1-7 g/10 min.

10. A method for preparing a composite waterproofing membrane according to any one of claims 2 to 9, characterized by comprising the following steps:

s100: preparing materials of an upper surface layer, a lower surface layer and a middle layer: weighing and uniformly mixing the raw material components of the upper surface layer, the lower surface layer and the middle layer according to a formula, and then respectively putting the raw material components into a double-screw extruder for extrusion granulation to obtain upper surface layer granules, lower surface layer granules and middle layer granules;

s200, casting the prepared upper-layer granules, lower-layer granules and middle-layer granules into a composite waterproof board through a three-layer casting machine;

and S300, crosslinking the composite waterproof sheet material prepared in the S200 through ultraviolet radiation to obtain the composite waterproof roll material.

Technical Field

The invention relates to the technical field of new materials, in particular to a composite waterproof coiled material and a preparation method thereof.

Background

Since the 70 s in the 20 th century, the railway construction technology in China has been greatly improved, the number of remote mountain railways and urban rail transit lines is increased year by year, and the requirements on the construction standard are higher and higher along with the development of railway traffic. In railway construction planning, in order to save a large amount of traffic time and create an optimal railway route, tunnels are often selected to be constructed when mountain roadblocks are met, and therefore the number of the tunnels is increased.

At present, the relatively common problem that meets in the railway tunnel construction process lies in the tunnel percolating water, can use the waterproof board in order to solve the percolating water problem in the tunnel usually. However, there are some problems to be solved, one being that some tunnels pass geothermal water, where the geothermal water is heated up to 80 ℃; secondly, in some northern cold regions, the environmental temperature is very low, especially in cold winter, the temperature is below zero, and the performance of the existing waterproof board material, such as waterproofness, long service time and the like, can be adversely affected by both over-high temperature and over-low temperature. Therefore, higher performance requirements are placed on the tunnel flashing used in railway tunnel construction: high temperature resistance and low temperature resistance, and simultaneously, good hot-melt welding performance of the alloy is required to be ensured.

The application number is CN201610517519.6, Chinese invention patent with 2016, 11, 16 discloses an EVA waterproof board, which comprises the following components: 10-30 parts of high-density polyethylene, 10-30 parts of metallocene-catalyzed linear low-density polyethylene, 20-30 parts of ethylene-vinyl acetate copolymer, 20-60 parts of linear low-density polyethylene and 0.3-1.5 parts of antioxidant. The EVA waterproof board effectively ensures the flexibility and the hot-melt welding performance of the waterproof board, has the tensile strength of more than 18MPa, the elongation of more than 650 percent and the tearing strength of more than 100KN/m, has excellent mechanical properties, but cannot meet the environment of high terrestrial heat.

Disclosure of Invention

To solve the problems mentioned in the background art: the existing waterproof board material cannot meet the requirements of high temperature resistance and low temperature resistance in the practical application process. The invention provides a composite waterproof coiled material, which comprises an upper surface layer, a middle layer and a lower surface layer; the upper surface layer, the middle layer and the lower surface layer respectively comprise the following raw material components in parts by weight:

upper and lower skins:

an intermediate layer:

the invention provides a radiation cross-linked polyethylene material as an intermediate layer, wherein the radiation cross-linked polyethylene material remarkably improves the Tg value (glass transition temperature) through radiation cross-linking, so that the heat resistance is remarkably improved; the irradiation cross-linked polyethylene material is used as the intermediate layer material of the composite waterproof coiled material, so that the heat resistance of the composite waterproof coiled material is obviously improved. But the thermal welding performance and the peeling force of the crosslinked middle layer material are reduced, and the upper surface layer and the lower surface layer added with the PE bonding resin are arranged, so that the heat resistance of the composite waterproof coiled material can be effectively maintained, and the thermal welding performance of the composite waterproof coiled material is remarkably improved.

Further, in one embodiment, the thickness ratio of the upper surface layer, the middle layer and the lower surface layer is (0.5-1.5): (6.5-8.5): (0.5 to 1.5).

Further, in one embodiment, the thickness ratio of the upper surface layer, the middle layer and the lower surface layer is 1: 8: 1.

further, in one embodiment, the melt flow rate of the EVA is 0.5-2 g/10min, and the mass content of vinyl acetate in the EVA is 10% -30%.

Further, in one embodiment, the LLDPE has a melt flow rate of 0.5-2 g/10 min.

Further, in one embodiment, the HDPE has a melt flow rate of 0.5 to 2g/10 min.

Further, in one embodiment, the metallocene polyethylene has a melt flow rate of 0.5 to 2g/10 min.

Further, in one embodiment, the cross-linking agent is one or more of TMPTA, DEGDA, TPGDA.

Further, in one embodiment, the melt flow rate of the PE bonding resin is 1-7 g/10 min.

The invention also provides a preparation method of the composite waterproof roll, which comprises the following steps: s100: preparing materials of an upper surface layer, a lower surface layer and a middle layer: weighing and uniformly mixing the raw material components of the upper surface layer, the lower surface layer and the middle layer according to a formula, and then respectively putting the raw material components into a double-screw extruder for extrusion granulation to obtain upper surface layer granules, lower surface layer granules and middle layer granules; s200, casting the prepared upper-layer granules, lower-layer granules and middle-layer granules into a composite waterproof board through a three-layer casting machine; and S300, crosslinking the composite waterproof sheet material prepared in the S200 through ultraviolet radiation to obtain the composite waterproof roll material.

Compared with the prior art, the invention has the following technical effects:

the composite waterproof coiled material provided by the invention has excellent performances of high temperature resistance, low temperature resistance, easy welding and the like, and solves the problem that the heat resistance and the low temperature resistance of the existing waterproof board are insufficient.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention also provides the following examples and comparative examples:

the formulations (unit: parts by weight) of the examples and comparative examples provided by the present invention are shown in table 1 below:

TABLE 1

Wherein, the raw material component species selection in the examples and comparative examples shown in Table 1 are consistent, the EVA is selected from the EVA of the mark V5110J of the petrochemical production of the winnowing, the melt flow rate of the EVA is 1.0g/10min (190 ℃, 2.16kg), and the mass content of the vinyl acetate in the EVA is 19%; the LLDPE is selected from LLDPE of Fujian co-production brand DFDA7042, and the melt flow rate is 1.8g/10min (190 ℃, 2.16 kg); the HDPE produced by Taiwan plastic is the HDPE with the mark 8010, and the melt flow rate is 1g/10min (190 ℃, 2.16 kg); the metallocene polyethylene is selected from 1018MF metallocene polyethylene produced by Exxon Mobil, and the melt flow rate is 1.0g/10min (190 deg.C, 2.16 kg); the stabilizer is a compound composition of 1010 (also known as tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) and 168 (also known as tri [2, 4-di-tert-butylphenyl ] phosphite); TMPTA is selected as the cross-linking agent; the PE bonding resin is produced by a new material of Jin\26104, Xiamen, and the melt flow rate is 7g/10min (190 ℃, 2.16 kg).

In addition to the practical options presented in the specific examples above, the cross-linking agent may preferably be one or a combination of more of TMPTA (trimethylolpropane triacrylate), DEGDA (diethylene glycol diacrylate), TPGDA (tripropylene glycol diacrylate); preferably, the parameters of the EVA selected may be: the melt flow rate is 0.5-2 g/10min (190 ℃ C. 2.16kg), the mass content of the vinyl acetate is 10-30%, and the parameters can be within the range, including but not limited to the practical choices embodied by the above embodiments; preferably, the parameters of the EVA selected may be: the melt flow rate is 0.5-2 g/10min (190 ℃, 2.16kg), and the parameters can be within the range, including but not limited to the practical choices embodied in the above embodiments; preferably, the parameter of the EVA selected may be a melt flow rate of 0.5-2 g/10min (190 ℃, 2.16kg), and the parameter may be within this range, including but not limited to the actual choice embodied in the above embodiments; preferably, the parameters of the metallocene polyethylene selected for use may be: the melt flow rate is 0.5-2 g/10min (190 ℃, 2.16kg), and the parameters can be within the range, including but not limited to the practical choices embodied in the above embodiments; preferably, the parameters of the PE bonding resin selected may be: the melt flow rate is 1-7 g/10min, and the parameters thereof can be within the range, including but not limited to the practical choices embodied in the above embodiments, specifically, in some embodiments, the PE bonding resin can also be a PE bonding resin produced by commercially available guangzhou deer mountain new material ltd, shanghai bang high molecular material ltd, or a PE bonding resin of brand number E3200 produced by commercially available gold Yang (mansion) new material technology ltd selected in embodiments 1-4 as a preferred choice; preferably, the parameters of the HDPE chosen may be: the melt flow rate is 0.5-2 g/10min (190 ℃, 2.16kg), and the parameters can be within the range, including but not limited to the practical choices embodied in the above examples.

In addition to the practical choices embodied in the above specific examples, the stabilizer may be one or more combinations of sterically hindered phenolic stabilizers, sterically hindered amine stabilizers, phosphate stabilizers, thioester stabilizers, and phosphites, preferably a combination of 1010 (also known as pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and 168 (also known as tris [2, 4-di-tert-butylphenyl ] phosphite) as used in examples 1-4.

The composite waterproof roll is prepared according to the formula in the table 1, and the preparation method comprises the following steps:

s100: preparing materials of an upper surface layer, a lower surface layer and a middle layer: s110, preparing granules of an upper surface layer and a lower surface layer: weighing and uniformly mixing the raw material components of the upper surface layer and the lower surface layer according to the formula in the table 1, and then putting the raw material components into a double-screw extruder for extrusion, cooling and granulation to obtain upper surface layer granules and lower surface layer granules; wherein the length-diameter ratio of the screw of the double-screw extruder is 40:1, the temperature of each zone of the double-screw extruder is 50 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃ in sequence from the zone 1 to the zone 10, the head temperature is 180 ℃, and the screw rotating speed is 250 rpm; s120, weighing and uniformly mixing the raw material components of the middle layer according to the formula in the table 1, and then respectively putting the raw material components into a double-screw extruder for extrusion, cooling and granulation to obtain upper-layer granules, lower-layer granules and middle-layer granules; wherein the length-diameter ratio of the screw of the double-screw extruder is 40:1, the temperature of each zone of the double-screw extruder is 50 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃ in sequence from the zone 1 to the zone 10, the head temperature is 180 ℃, and the screw rotating speed is 250 rpm; s200, casting the prepared granules of the upper surface layer, the prepared granules of the lower surface layer and the prepared granules of the middle layer into the granules of the upper surface layer, the prepared granules of the middle layer and the prepared granules of the middle layer by a three-layer casting machine at the casting temperature of 180-220 ℃ to obtain the granules of the upper surface layer, the prepared granules of the middle layer and the prepared granules of the middle layer, wherein the thickness ratio of the upper surface layer to the middle layer to the lower surface layer is 1: 8: 1, the total thickness of the composite waterproof board is 2 mm; and S300, crosslinking the composite waterproof sheet material prepared in the S200 through ultraviolet radiation to obtain the composite waterproof roll material. It should be noted that: the upper and lower skin layers in comparative examples 1 and 4 were prepared using intermediate layer pellets cast, with the upper, intermediate and lower skin layers having a thickness ratio of 1: 8: 1, thickness of 2 mm.

In addition to the practical choices presented in the above specific embodiments, preferably, the thickness ratio of the upper surface layer, the middle layer and the lower surface layer is (0.5-1.5): (6.5-8.5): (0.5-1.5); the thickness ratio of the upper skin layer, the middle layer and the lower skin layer described in examples 1-4 was 1: 8: 1 is selected for optimum thickness.

The composite waterproofing membranes prepared in the examples and comparative examples were tested under the same test conditions, and the test results are shown in the following table 2:

TABLE 2

In table 2, "unzipping" means that the weld position is not peeled apart.

As can be seen from the data results of examples 1-4 in Table 2: the composite waterproof coiled material provided by the invention has excellent performances of high temperature resistance, low temperature resistance, easy welding and the like, and solves the problem that the heat resistance and the low temperature resistance of the existing waterproof board are insufficient.

As can be seen from the formulations and test data of examples 1-3, as the amount of HDPE added increases, the heat welding performance decreases (the peel strength of the joint decreases at the same heat welding temperature), and a higher heat welding temperature is required, the heat distortion temperature slightly increases;

from the comparison results in comparative example 2 and example 1, it can be seen that: compared with example 1, in comparative example 2, no PE bonding resin is added to the upper and lower surface layers, so that the seam peel strength is remarkably reduced; the peel strength of the composite waterproof roll prepared by the embodiment of the scheme of the invention is well improved.

From the results of comparison of example 1, example 4, comparative example 3, it can be seen that: compared with the examples 1 and 4, the cross-linking agent amount beyond the limit of the invention is added in the comparative example 3, although the heat distortion temperature is improved to a certain extent, the low temperature resistance, the tensile bending strength and the tearing strength are all reduced remarkably; from the comparison results between example 4 and example 1, it is clear that in example 4, the tensile flexural strength, heat distortion temperature, and other properties are slightly improved compared to example 1 by increasing the amount of the crosslinking agent in addition to example 1. It can be known that proper crosslinking can obviously improve the heat distortion temperature and various physical properties, but excessive crosslinking can further improve the heat distortion temperature, but most of the materials form a three-dimensional network structure, the molecular weight is increased, the movement among molecules is limited, the materials are changed from tough to brittle, and other physical properties are reduced.

As can be seen from comparative example 1, the peel strength obtained by the test of comparative example 1, in which only the irradiation crosslinked polyethylene material of the middle layer is used as the waterproof roll, is very poor, mainly because the melting property of the material is deteriorated with the generation of crosslinking, the material is crosslinked to a certain degree, and even only can be swelled, the thermal welding property of the crosslinked middle layer material is reduced, and the peel force is reduced; therefore, the composite waterproof roll provided by the invention is matched with the upper surface layer and the lower surface layer by taking the irradiation crosslinked polyethylene material as the middle layer, so that the performance of the composite waterproof roll is comprehensively improved, and the composite waterproof roll has excellent performances such as high temperature resistance, low temperature resistance, welding resistance and the like. Compared with the comparative example 1, the thermal deformation temperature is obviously reduced, the high temperature resistance is poor, and the tensile bending strength and the tearing strength are also reduced to some extent;

finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.