Modified basic magnesium sulfate whisker, waterproof roll sheet, and preparation method and application thereof

Abstract

The invention relates to the field of building waterproofing, and discloses a modified basic magnesium sulfate whisker, a waterproof roll sheet, and a preparation method and application thereof. The preparation method of the modified basic magnesium sulfate whisker comprises: contacting the raw material basic magnesium sulfate whisker with a titanate coupling agent under stirring to obtain the modified basic magnesium sulfate whisker. Then, the modified basic magnesium sulfate whisker is used as a composition of a waterproof roll sheet with polypropylene, metallocene polyethylene, high-density polyethylene, and a polyolefin elastomer to prepare a waterproof roll sheet. The waterproof roll sheet provided by the invention has high puncture resistance and a simple production and processing process.

Description

Technical Field

[0001] The invention relates to the field of building waterproofing, and in particular to a method for preparing modified basic magnesium sulfate whiskers, a waterproof coiled material sheet composition, a waterproof coiled material sheet, and a preparation method and application thereof. Background Art

[0002] Waterproof membrane is mainly used in building walls, roofs, tunnels, roads, landfills, etc. It is a flexible building material product that can be rolled into a roll to resist the seepage of external rainwater and groundwater. As a leak-free connection between the project foundation and the building, it is a barrier to the waterproofing of the entire project and plays a vital role in the entire project. The main products are asphalt waterproof membrane and polymer waterproof membrane.

[0003] The structure of polymer waterproofing membrane is composed of high-density polyethylene sheet as the base material, pressure-sensitive adhesive coated in the interlayer, sand-coated on the surface, and the bottom high-density polyethylene sheet gives the polymer waterproofing membrane important physical properties. The puncture resistance of the waterproofing membrane is closely related to the characteristics of the sheet.

[0004] The polymer waterproofing membrane has the advantages of being able to bond tightly with the concrete structure cast on its surface, preventing water leakage, and being easy and quick to construct. The polymer waterproofing membrane needs to be able to withstand the construction load directly acting on it by the main building and the impact of the concrete cast on the building floor, forming a high-strength waterproof layer, strong resistance to water pressure, and puncture and tear resistance, and is suitable for construction applications in underground projects.

[0005] CN109294067A discloses a glass fiber reinforced polypropylene plastic and a preparation method thereof, comprising the following raw materials in parts by weight: 100-130 parts of polypropylene, 10-20 parts of metallocene polyethylene, 10-20 parts of low-density polyethylene, 0.5-0.7 parts of POE elastomer toughener, 0.3-0.5 parts of zinc stearate, 5-10 parts of glass fiber, 2-4 parts of SiC whiskers, 0.5-1 parts of phosphite antioxidants, 0.5-1 parts of organosilicon spherical micropowders, 0.1-0.3 parts of nano titanium dioxide, 0.2-0.5 parts of tourmaline powder, 0.1-0.3 parts of N-(trichloromethylthio)phthalimide, 1-3 parts of thyme essential oil, and 0.1-0.3 parts of cinnamon essential oil. Although the polypropylene plastic provided by the prior art has antibacterial properties and can improve the strength of polypropylene plastic to a certain extent, it has the defects of complex raw material types, inconvenient processing and uneven dispersion.

[0006] CN114193881A discloses a polymer pre-laid waterproof coiled material and a preparation method thereof, comprising a heat-oxidation-resistant waterproof layer, a flexible layer, and a fabric reinforcement layer arranged between the heat-oxidation-resistant waterproof layer and the flexible layer; the heat-oxidation-resistant waterproof layer, the flexible layer, and the fabric reinforcement layer are solidified into one by extrusion molding; the heat-oxidation-resistant waterproof layer is the outer layer of the waterproof coiled material, and the heat-oxidation-resistant waterproof layer comprises the following components: ultra-high molecular weight polyethylene resin, HDPE resin, whiskers, compatibilizer, lubricating aid, and macromolecular antioxidant masterbatch. Although the pre-laid waterproof coiled material provided by the prior art can resist long-term heat-oxidation aging to a certain extent, the production and processing process of the prior art is complicated.

[0007] Therefore, developing a sheet with high puncture resistance is particularly important for improving the performance of waterproof membranes. Summary of the invention

[0008] The purpose of the present invention is to overcome the above problems existing in the prior art and to provide a waterproof roll sheet material with high puncture resistance and simple production and processing process.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for preparing modified basic magnesium sulfate whiskers, the method comprising: contacting a raw material basic magnesium sulfate whisker with a titanate coupling agent under stirring to obtain the modified basic magnesium sulfate whiskers;

[0010] The average length of the raw material basic magnesium sulfate whiskers is 20-80 μm, and the average diameter is less than 1 μm;

[0011] The titanate coupling agent is selected from at least one of a monoalkoxy coupling agent, a monoalkoxy pyrophosphate coupling agent, and a chelate coupling agent;

[0012] The weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.02-0.20.

[0013] The second aspect of the present invention provides modified basic magnesium sulfate whiskers prepared by the method described in the first aspect.

[0014] The third aspect of the present invention provides a composition for preparing a waterproof roll sheet, wherein the composition contains the following components which are stored separately or in a mixture of two or more:

[0015] Polypropylene, metallocene polyethylene, high-density polyethylene, polyolefin elastomer, modified basic magnesium sulfate whisker;

[0016] Relative to 100 parts by weight of the polypropylene, the content of the metallocene polyethylene is 65-115 parts by weight, the content of the high-density polyethylene is 20-50 parts by weight, the content of the polyolefin elastomer is 20-50 parts by weight, and the content of the modified basic magnesium sulfate whisker is 24-42 parts by weight;

[0017] The polyolefin elastomer is selected from at least one of ethylene-octene copolymer, ethylene-hexene copolymer and ethylene-butene copolymer;

[0018] The modified basic magnesium sulfate whisker is the modified basic magnesium sulfate whisker described in the second aspect.

[0019] The fourth aspect of the present invention provides a method for preparing a waterproof roll sheet, which is carried out using the components in the composition described in the third aspect, comprising:

[0020] (1) first mixing polypropylene, metallocene polyethylene, high-density polyethylene, and polyolefin elastomer to obtain a mixture I;

[0021] (2) performing a second mixing of the mixture I and the modified basic magnesium sulfate whisker to obtain a mixture II;

[0022] (3) Extruding the mixture II to obtain the waterproof roll sheet.

[0023] The fifth aspect of the present invention provides a waterproof roll sheet prepared by the method described in the fourth aspect.

[0024] The sixth aspect of the present invention provides the use of the waterproof roll sheet material described in the fifth aspect in building waterproof materials.

[0025] The technical solution provided by the present invention has at least the following advantages compared with the prior art:

[0026] (1) The method for preparing modified magnesium sulfate whiskers provided by the present invention is simple to operate, low in cost, and highly practical;

[0027] (2) The modified magnesium sulfate whiskers prepared by the method provided by the present invention have excellent interfacial properties and better compatibility with the other components in the composition provided by the present invention;

[0028] (3) The present invention uses modified basic magnesium sulfate whiskers as fillers, and combined with the other features of the technical solution provided by the present invention, the prepared waterproof roll sheet has higher puncture resistance and strong adaptability to harsh environments. DETAILED DESCRIPTION

[0029] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0030] It should be noted that, in various aspects of the present invention, for the same components or terms in various aspects, the present invention is only described once in one aspect without repeated description, which should not be understood by those skilled in the art as a limitation of the present invention.

[0031] As mentioned above, the first aspect of the present invention provides a method for preparing modified basic magnesium sulfate whiskers, the method comprising: contacting a raw material basic magnesium sulfate whisker with a titanate coupling agent under stirring to obtain the modified basic magnesium sulfate whiskers;

[0032] The average length of the raw material basic magnesium sulfate whiskers is 20-80 μm, and the average diameter is less than 1 μm;

[0033] The titanate coupling agent is selected from at least one of a monoalkoxy coupling agent, a monoalkoxy pyrophosphate coupling agent, and a chelate coupling agent;

[0034] The weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.02-0.20.

[0035] Preferably, the titanate coupling agent is a monoalkoxy coupling agent.

[0036] More preferably, the titanate coupling agent is monoalkoxy isopropyl triisostearyl titanate.

[0037] Particularly preferably, the titanate coupling agent is purchased from Yizheng Tianyang Chemical Co., Ltd. with a brand name of A9.

[0038] Preferably, the raw material basic magnesium sulfate whiskers have an average length of 40-60 μm and an average diameter of less than 1 μm.

[0039] Preferably, the weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.05-0.15.

[0040] Preferably, the contacting conditions at least meet the following conditions: rotation speed of 120-180 rpm, temperature of 15-35° C., and time of 8-10 min.

[0041] As mentioned above, the second aspect of the present invention provides modified basic magnesium sulfate whiskers prepared by the method described in the first aspect.

[0042] As mentioned above, the third aspect of the present invention provides a composition for preparing a waterproof roll sheet, wherein the composition contains the following components which are stored separately or in a mixture of two or more:

[0043] Polypropylene, metallocene polyethylene, high-density polyethylene, polyolefin elastomer, modified basic magnesium sulfate whisker;

[0044] Relative to 100 parts by weight of the polypropylene, the content of the metallocene polyethylene is 65-115 parts by weight, the content of the high-density polyethylene is 20-50 parts by weight, the content of the polyolefin elastomer is 20-50 parts by weight, and the content of the modified basic magnesium sulfate whisker is 24-42 parts by weight;

[0045] The polyolefin elastomer is selected from at least one of ethylene-octene copolymer, ethylene-hexene copolymer and ethylene-butene copolymer;

[0046] The modified basic magnesium sulfate whisker is the modified basic magnesium sulfate whisker described in the second aspect.

[0047] In the present invention, the modified basic magnesium sulfate whisker has better interface performance and better compatibility with the other components in the composition provided by the present invention. The inventors of the present invention have found that the waterproof roll sheet prepared by using the modified basic magnesium sulfate whisker as a filler and combining the other features of the technical solution provided by the present invention has higher puncture resistance.

[0048] Preferably, the polyolefin elastomer is ethylene-octene copolymer. The inventors of the present invention have found that in this preferred case, the waterproof roll sheet prepared by the solution of the present invention has higher puncture resistance.

[0049] Preferably, the density of the polypropylene is 0.890-0.910 g / cm 3 , the melt mass flow rate at 230°C and a load of 2.16 kg is 2.4-3.6 g / 10 min.

[0050] Preferably, the tensile yield stress of the polypropylene is ≥29 MPa, and the isotactic index is ≥95%.

[0051] In the present invention, the method for determining the tensile yield stress of the polypropylene refers to GB / T1040.2-2006, and the method for determining the isotactic index of the polypropylene refers to GB / T2412-2008.

[0052] Particularly preferably, the polypropylene is purchased from PetroChina Daqing Petrochemical Company with a grade of T30S.

[0053] Preferably, the density of the metallocene polyethylene is 0.934-0.938 g / cm 3 , the melt mass flow rate at 190°C and a load of 2.16 kg is 2.7-3.3 g / 10 min.

[0054] Preferably, the metallocene polyethylene has a tensile elongation at break of ≥500% and a tensile yield stress of ≥14 MPa.

[0055] In the present invention, the determination method of the tensile elongation at break and the tensile yield stress of the metallocene polyethylene refers to GB / T1040.2-2006.

[0056] Particularly preferably, the metallocene polyethylene is purchased from Sinopec with a grade of E332H.

[0057] The metallocene polyethylene described in the present invention refers to a polyethylene product prepared by using a metallocene catalyst, which makes the lateral branching arrangement of the polyethylene more regular and orderly on the basis of the original structure, and can improve the toughness of the material.

[0058] The inventors of the present invention have found that by using a metallocene polyethylene product having specific physical and mechanical properties in combination with the other features of the technical solution provided by the present invention, the waterproof roll sheet prepared has higher puncture resistance.

[0059] Preferably, the density of the high-density polyethylene is 0.940-0.950 g / cm 3 , the melt mass flow rate at 190°C and a load of 2.16 kg is 0.15-0.25 g / 10 min.

[0060] Preferably, the high-density polyethylene has a tensile elongation at break of ≥480% and a tensile yield stress of ≥24 MPa.

[0061] In the present invention, the tensile elongation at break and the tensile yield stress of the high-density polyethylene are measured according to ASTM D882.

[0062] Particularly preferably, the high-density polyethylene is purchased from Saudi Chevron Phillips with the brand name HHM TR-144.

[0063] Preferably, the density of the polyolefin elastomer is 0.860-0.880 g / cm 3 , the melt mass flow rate at 190°C and a load of 2.16 kg is 0.38-0.62 g / min.

[0064] Preferably, the tensile yield stress of the polyolefin elastomer is ≥9.5 MPa.

[0065] In the present invention, the tensile yield stress of the polyolefin elastomer is measured according to ASTM D638.

[0066] Particularly preferably, the polyolefin elastomer is purchased from Dow Chemical Company, USA, with brand number 8150.

[0067] As mentioned above, the fourth aspect of the present invention provides a method for preparing a waterproof roll sheet, which is carried out using the components in the composition described in the third aspect, comprising:

[0068] (1) first mixing polypropylene, metallocene polyethylene, high-density polyethylene, and polyolefin elastomer to obtain a mixture I;

[0069] (2) performing a second mixing of the mixture I and the modified basic magnesium sulfate whisker to obtain a mixture II;

[0070] (3) Extruding the mixture II to obtain the waterproof roll sheet.

[0071] Preferably, in step (1), the first mixing conditions at least meet the following conditions: a rotation speed of 120-180 rpm, a temperature of 15-35° C., and a time of 8-15 min.

[0072] Preferably, in step (2), the second mixing conditions at least meet the following conditions: a rotation speed of 120-180 rpm, a temperature of 15-35° C., and a time of 8-10 min.

[0073] Preferably, in step (3), the extrusion molding temperature is 200-250°C.

[0074] It should be noted that the present invention has no particular limitation on the equipment or method used for the stirring and extrusion molding. Those skilled in the art can use conventional technical means in the art to operate. The present invention exemplarily provides a specific implementation method in the following text. For example, a high-speed stirrer is used for stirring and a twin-screw extruder is used for extrusion molding. Those skilled in the art should not understand this as a limitation of the present invention.

[0075] As mentioned above, the fifth aspect of the present invention provides a waterproof roll sheet prepared by the method described in the fourth aspect.

[0076] As mentioned above, the sixth aspect of the present invention provides the use of the waterproof roll sheet material described in the fifth aspect in building waterproof materials.

[0077] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials used are all common commercially available products.

[0078] Some of the raw materials and their sources used in the following examples are shown in Table 1:

[0079] Table 1

[0080]

[0081]

[0082] In the following examples, unless otherwise specified, each "part" or each "part by weight" means 100 g.

[0083] High-speed mixer: model HBQD-50, manufacturer: Guangdong Hongbao Machinery Technology Co., Ltd.;

[0084] Twin-screw extruder: model is CTE75plus, manufacturer is Coperion Machinery Co., Ltd.

[0085] Preparation Example 1

[0086] Under stirring, the raw material basic magnesium sulfate whisker is contacted with a titanate coupling agent to obtain the modified basic magnesium sulfate whisker, which is named as X1.

[0087] The raw material basic magnesium sulfate whisker is basic magnesium sulfate whisker I, and the amount is 10 parts by weight, the titanate coupling agent is titanate coupling agent I, and the weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.10;

[0088] The contact conditions are: rotation speed of 100 rpm, temperature of 25° C., and time of 9 minutes.

[0089] Preparation Example 2

[0090] This preparation example adopts a process similar to that of Preparation Example 1, except that the weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.20, and the modified basic magnesium sulfate whisker is prepared and named X2.

[0091] Preparation Example 3

[0092] This preparation example adopts a process similar to that of Preparation Example 1, except that the weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.40, and the modified basic magnesium sulfate whisker is prepared and named X3.

[0093] Preparation Example 4

[0094] This preparation example adopts a process similar to that of Preparation Example 1, except that the basic magnesium sulfate whisker I is replaced with an equal weight portion of basic magnesium sulfate whisker II to prepare the modified basic magnesium sulfate whisker, which is named X4.

[0095] Preparation Example 5

[0096] This preparation example adopts a process similar to that of Preparation Example 1, except that the basic magnesium sulfate whisker I is replaced with an equal weight portion of basic magnesium sulfate whisker III to prepare the modified basic magnesium sulfate whisker, which is named X5.

[0097] Preparation Example 6

[0098] This preparation example adopts a process similar to that of Preparation Example 1, except that the raw material basic magnesium sulfate whisker is replaced with talcum powder in equal parts by weight to prepare modified talcum powder, which is named X6.

[0099] Preparation Example 7

[0100] This preparation example adopts a process similar to that of Preparation Example 1, except that titanate coupling agent I is replaced by titanate coupling agent II to prepare the modified basic magnesium sulfate whisker, which is named X7.

[0101] Preparation Example 8

[0102] This preparation example adopts a process similar to that of Preparation Example 1, except that the titanate coupling agent I is replaced with zinc stearate to prepare the modified basic magnesium sulfate whisker, which is named X8.

[0103] Example 1

[0104] (1) first mixing polypropylene, metallocene polyethylene, high-density polyethylene, and polyolefin elastomer to obtain a mixture I;

[0105] (2) performing a second mixing of the mixture I and the modified basic magnesium sulfate whisker to obtain a mixture II;

[0106] (3) Extruding the mixture II to obtain the waterproof roll sheet, named P1.

[0107] The dosage of each component and the production process parameters are listed in Table 2.

[0108] Example 2 and Example 3 are carried out using a process similar to Example 1, except that different waterproof roll sheets are used in terms of formulation and production process parameters. The waterproof roll sheets are named P2 and P3, respectively. See Table 2 for details.

[0109] Example 4

[0110] This example is carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used is replaced by an equal weight portion of X2 instead of X1, and a waterproof roll sheet is prepared, named P4.

[0111] Example 5

[0112] This example is carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used is replaced by an equal weight portion of X4 instead of X1, and a waterproof roll sheet is prepared, named P5.

[0113] Example 6

[0114] This example is carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used is replaced by an equal weight portion of X7 instead of X1, and a waterproof roll sheet is prepared, named P6.

[0115] Example 7

[0116] This example is carried out using a process similar to that of Example 1, except that the polyolefin elastomer I is replaced with an equal weight portion of polyolefin elastomer II to prepare a waterproof roll sheet, named P7.

[0117] Comparative Example 1

[0118] This comparative example was carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used was replaced by an equal weight portion of X3 instead of X1, and a waterproof roll sheet was prepared, named DP1.

[0119] Comparative Example 2

[0120] This comparative example was carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used was replaced by an equal weight portion of X5 instead of X1 to prepare a waterproof roll sheet, named DP2.

[0121] Comparative Example 3

[0122] This comparative example was carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker X1 was replaced with an equal weight portion of modified talcum powder X6 to prepare a waterproof roll sheet, named DP3.

[0123] Comparative Example 4

[0124] This comparative example was carried out using a process similar to that of Example 1, except that the modified basic magnesium sulfate whisker used was replaced by an equal weight portion of X8 instead of X1 to prepare a waterproof roll sheet, named DP4.

[0125] Table 2

[0126]

[0127] Test Case

[0128] The puncture resistance of the waterproof roll sheet prepared in each example was measured according to GB / T23457-2017 standard, and the results are shown in Table 3.

[0129] Table 3

[0130]

[0131] It can be seen from the above results that the waterproof roll sheet material obtained by the method provided by the present invention has higher puncture resistance, and the processing process of the waterproof roll sheet material is simple, the operation is convenient, and it has higher market value and economic value.

[0132] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A composition for preparing a waterproof roll sheet, characterized in that: The composition contains the following components which are stored independently or in combination: Polypropylene, metallocene polyethylene, high-density polyethylene, polyolefin elastomer, modified basic magnesium sulfate whisker; Relative to 100 parts by weight of the polypropylene, the content of the metallocene polyethylene is 65-115 parts by weight, the content of the high-density polyethylene is 20-50 parts by weight, the content of the polyolefin elastomer is 20-50 parts by weight, and the content of the modified basic magnesium sulfate whisker is 24-42 parts by weight; The polyolefin elastomer is selected from at least one of ethylene-octene copolymer, ethylene-hexene copolymer and ethylene-butene copolymer; The modified basic magnesium sulfate whisker is a product prepared by the following method: Under stirring, the raw material basic magnesium sulfate whisker is contacted with a titanate coupling agent to obtain the modified basic magnesium sulfate whisker; The average length of the raw material basic magnesium sulfate whiskers is 20-80 μm, and the average diameter is less than 1 μm; The titanate coupling agent is a monoalkoxy type coupling agent; The weight ratio of the raw material basic magnesium sulfate whisker to the titanate coupling agent is 1:0.05-0.

15.

2. The composition according to claim 1, wherein The polypropylene has a density of 0.890-0.910 g / cm³ and a melt mass flow rate of 2.4-3.6 g / 10 min at 230° C. and a load of 2.16 kg; and / or The metallocene polyethylene has a density of 0.934-0.938 g / cm³ and a melt mass flow rate of 2.7-3.3 g / 10 min at 190° C. and a load of 2.16 kg; and / or The high-density polyethylene has a density of 0.940-0.950 g / cm³ and a melt mass flow rate of 0.15-0.25 g / 10 min at 190° C. and a load of 2.16 kg; and / or The polyolefin elastomer has a density of 0.860-0.880 g / cm³, and a melt mass flow rate of 0.38-0.62 g / min at 190° C. and a load of 2.16 kg.

3. The composition according to claim 1 or 2, characterized in that The contacting conditions at least meet the following requirements: rotation speed of 120-180 rpm, temperature of 15-35° C., and time of 8-10 min.

4. A method for preparing a waterproof roll sheet, characterized in that: The method is carried out using the components in the composition according to any one of claims 1 to 3, comprising: (1) performing a first mixing of polypropylene, metallocene polyethylene, high-density polyethylene, and polyolefin elastomer to obtain a mixture I; (2) performing a second mixing of the mixture I and the modified basic magnesium sulfate whisker to obtain a mixture II; (3) Extruding the mixture II to obtain the waterproof roll sheet.

5. The method according to claim 4, wherein: In step (1), the first mixing conditions at least meet the following conditions: a rotation speed of 120-180 rpm, a temperature of 15-35° C., and a time of 8-15 min; and / or, In step (2), the second mixing conditions at least meet the following conditions: a rotation speed of 120-180 rpm, a temperature of 15-35° C., and a time of 8-10 min; and / or, In step (3), the extrusion molding temperature is 200-250°C.

6. The waterproof roll sheet prepared by the method according to claim 4 or 5.

7. Use of the waterproof roll sheet material according to claim 6 in building waterproof materials.

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