Modified fluorosilicone rubber and its preparation method, rubber composition for waterproofing membranes, waterproofing membranes and their preparation methods and applications

Abstract

The present invention relates to the field of polymer waterproofing membranes, and discloses a modified fluorosilicone rubber and its preparation method, a rubber compound composition for waterproofing membranes, a waterproofing membrane and its preparation method and application; the method includes: S1, performing a first mixing on graphite, a filler and a silane coupling agent to obtain a mixture I; S2, performing a second mixing on the fluorosilicone rubber and the mixture I to obtain a mixture II; S3, performing an extrusion granulation treatment on the mixture II to obtain the modified fluorosilicone rubber; relative to 100 parts by weight of the fluorosilicone rubber, the dosage of the filler is 10-20 parts by weight, the dosage of the graphite is 1-10 parts by weight, and the dosage of the silane coupling agent is 1-3 parts by weight. The waterproofing membrane prepared by using the modified fluorosilicone rubber provided by the present invention can simultaneously have excellent weather resistance and thermal stability.

Description

Technical Field

[0001] The present invention relates to the field of polymer waterproof coiled materials, and particularly relates to a modified fluorosilicone rubber, a preparation method thereof, a rubber compound composition for waterproof coiled materials, a waterproof coiled material, a preparation method thereof and an application thereof. Background Art

[0002] The main raw material of the exposed waterproof coiled material is polyolefin elastomer. Since this material contains a double bond structure inside, it will react with oxygen when used outdoors for a long time, and the physical properties of the waterproof coiled material will decline significantly. Currently, the existing technology is to add anti-aging additives to improve the overall weather resistance of the waterproof coiled material, but the anti-aging additives have the disadvantages of precipitation and high price.

[0003] CN110982160A discloses a preparation method of a weather-resistant optoelectronic PE sheath material. The method includes: (1) putting LLDPE, homopolypropylene, antioxidant, DCP, and co-crosslinking agent into a high-speed mixer, mixing evenly and then putting them into a twin-screw extruder for extrusion granulation to obtain material A; (2) putting fluorosilicone rubber, fatty alcohol polyoxyethylene polyoxypropylene ether, HDPE, carbon black, and antioxidant into a kneader for kneading treatment and then discharging, putting them into a twin-screw extruder for extrusion granulation to obtain a fluorosilicone rubber masterbatch, called material B; (3) putting material A, material B, LLDPE, homopolypropylene, nano calcium carbonate, and POE into a high-speed mixer, mixing evenly and then putting them into a twin-screw extruder for extrusion granulation to obtain an optoelectronic PE sheath material. This method will cause the nano calcium carbonate to agglomerate in the fluorosilicone rubber, resulting in a decrease in the tensile strength retention rate performance after artificial weathering.

[0004] CN110982160A discloses a conductive rubber composition, including the following components in parts by mass: 50 parts to 100 parts of silicone rubber, 20 parts to 80 parts of fluororubber, 100 parts to 400 parts of conductive filler, 0.5 part to 4 parts of vulcanizing agent, and 3 parts to 15 parts of silane coupling agent; the crosslinking reaction of this scheme needs to be completed at high temperature. Directly participating the silane coupling agent in the crosslinking reaction will cause the decomposition of the silane coupling agent, and finally cause the conductive filler to agglomerate in the fluororubber and silicone rubber, affecting the tensile strength retention rate performance and dimensional change rate after aging. Summary of the Invention

[0005] The purpose of the present invention is to solve the problems of poor weather resistance and thermal stability existing in the existing waterproof coiled materials.

[0006] To achieve the above purpose, the first aspect of the present invention provides a method for preparing a modified fluorosilicone rubber, and the method includes:

[0007] S1. First, mix graphite, filler, and silane coupling agent to obtain Mixture I. The conditions for the first mixing include: temperature of 65 - 75°C and time of 1.5 - 3 h.

[0008] S2. Then, mix fluorosilicone rubber and Mixture I to obtain Mixture II. The conditions for the second mixing include: temperature of 165 - 190°C and time of 5 - 20 min.

[0009] S3. Next, perform extrusion granulation on Mixture II to obtain the modified fluorosilicone rubber.

[0010] Relative to 100 parts by weight of the fluorosilicone rubber, the dosage of the filler is 10 - 20 parts by weight, the dosage of the graphite is 1 - 10 parts by weight, and the dosage of the silane coupling agent is 1 - 3 parts by weight.

[0011] The second aspect of the present invention provides a modified fluorosilicone rubber prepared by the method described in the first aspect.

[0012] The third aspect of the present invention provides a rubber compound composition for waterproof coiled materials, which contains the following components stored separately or mixed in two or more:

[0013] Polyolefin elastomer, linear low - density polyethylene, polypropylene, modified fluorosilicone rubber, cross - linker, cross - linking accelerator;

[0014] Relative to 100 parts by weight of the polyolefin elastomer, the content of the linear low - density polyethylene is 35 - 65 parts by weight, the content of the polypropylene is 2 - 18 parts by weight, the content of the modified fluorosilicone rubber is 1 - 15 parts by weight, the content of the cross - linker is 1 - 5 parts by weight, and the content of the cross - linking accelerator is 0.5 - 5 parts by weight;

[0015] The modified fluorosilicone rubber is the modified fluorosilicone rubber described in the second aspect.

[0016] The fourth aspect of the present invention provides a method for preparing a waterproof coiled material, which is carried out using the composition described in the third aspect and includes:

[0017] (1) Contact - mix the composition containing polyolefin elastomer, linear low - density polyethylene, polypropylene, modified fluorosilicone rubber, cross - linker, and cross - linking accelerator to obtain an intermediate material;

[0018] (2) Extrusion - mold and wind up the intermediate material in sequence to obtain the waterproof coiled material.

[0019] The fifth aspect of the present invention provides a waterproof coiled material prepared by the method described in the fourth aspect.

[0020] The sixth aspect of the present invention provides an application of the waterproof coiled material described in the fifth aspect in the field of building waterproofing.

[0021] The waterproof coiled material prepared by using the modified fluorosilicone rubber provided by the present invention can simultaneously have excellent weather resistance and thermal stability; compared with the prior art, the production process is simpler and it is easier to achieve mass production. Detailed implementation manners

[0022] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] As described above, the first aspect of the present invention provides a method for preparing a modified fluorosilicone rubber, and the method includes:

[0024] S1. Perform a first mixing on graphite, a filler, and a silane coupling agent to obtain a mixture I; the conditions for the first mixing include: the temperature is 65 - 75 °C, and the time is 1.5 - 3 h;

[0025] S2. Perform a second mixing on the fluorosilicone rubber and the mixture I to obtain a mixture II; the conditions for the second mixing include: the temperature is 165 - 190 °C, and the time is 5 - 20 min;

[0026] S3. Perform an extrusion granulation treatment on the mixture II to obtain the modified fluorosilicone rubber;

[0027] Relative to 100 parts by weight of the fluorosilicone rubber, the dosage of the filler is 10 - 20 parts by weight, the dosage of the graphite is 1 - 10 parts by weight, and the dosage of the silane coupling agent is 1 - 3 parts by weight.

[0028] Preferably, in step S1, the first mixing is carried out in the presence of a solvent.

[0029] Preferably, relative to 100 parts by weight of graphite, the dosage of the solvent is 140 - 160 parts by weight; more preferably, the solvent is ethanol.

[0030] More preferably, in step S1, the operation method of the first mixing includes: dropping the silane coupling agent to perform the first mixing with the material containing the solvent, the filler, and the graphite; preferably, the dropping speed is 0.1 - 0.3 ml / s.

[0031] Preferably, before performing the second mixing, the mixture I is dried to obtain a mixture I with a solvent content of not more than 0.01 wt%.

[0032] Preferably, the second mixing is carried out under stirring conditions, and the stirring conditions include: a stirring speed of 40 - 60 rpm.

[0033] Preferably, the Shore A hardness of the fluorosilicone rubber is 40 - 60, the tensile strength is 9 - 10 MPa, and the elongation at break is 300% - 400%. The inventors found that under this preferred specific embodiment, the weather resistance and thermal stability of the waterproof coiled material obtained by the present invention are better.

[0034] Preferably, the average particle diameter of the filler is 7 - 13 μm.

[0035] More preferably, the filler is calcium powder.

[0036] In order to endow the waterproof coiled material with better weather resistance and thermal stability, preferably, the silane coupling agent uses a silane coupling agent with an amino functional group, such as at least one selected from KH-550 silane coupling agent, KH-470 silane coupling agent, KH-792 silane coupling agent, KH602 silane coupling agent, KH580 silane coupling agent, Si-902 silane coupling agent, ND-42 silane coupling agent.

[0037] As described above, the second aspect of the present invention provides a modified fluorosilicone rubber prepared by the method described in the first aspect.

[0038] As described above, the third aspect of the present invention provides a rubber compound composition for a waterproof coiled material, and this composition contains the following components stored independently or mixed with two or more of them:

[0039] Polyolefin elastomer, linear low-density polyethylene, polypropylene, modified fluorosilicone rubber, crosslinking agent, crosslinking accelerator;

[0040] Relative to 100 parts by weight of the polyolefin elastomer, the content of the linear low-density polyethylene is 35 - 65 parts by weight, the content of the polypropylene is 2 - 18 parts by weight, the content of the modified fluorosilicone rubber is 1 - 15 parts by weight, the content of the crosslinking agent is 1 - 5 parts by weight, and the content of the crosslinking accelerator is 0.5 - 5 parts by weight;

[0041] The modified fluorosilicone rubber is the modified fluorosilicone rubber described in the second aspect above.

[0042] Preferably, relative to 100 parts by weight of the polyolefin elastomer, the content of the linear low-density polyethylene is 40-60 parts by weight, the content of the polypropylene is 5-15 parts by weight, the content of the modified fluorosilicone rubber is 3-10 parts by weight, the content of the crosslinking agent is 1-3 parts by weight, and the content of the crosslinking accelerator is 0.5-3 parts by weight. The inventors have found that under this preferred specific embodiment, the weather resistance and thermal stability of the waterproof coiled material obtained by the present invention are better.

[0043] More preferably, the melt index of the polyolefin elastomer is 1.0-4.0 g / 10 min.

[0044] Preferably, the degree of polymerization of the polypropylene is 4000-10000, the density is 0.88-0.92 g / cm3, and the melt index is 2.0-4.0 g / 10 min.

[0045] Preferably, the density of the linear low-density polyethylene is 0.90-0.94 g / cm3, and the melt index is 1.0-4.0 g / 10 min.

[0046] Preferably, the crosslinking agent is selected from at least one of sulfur, organic peroxides, melamine formaldehyde resin, urea formaldehyde resin, and phenolic resin.

[0047] Preferably, the crosslinking accelerator is selected from at least one of diethylamine, zinc oxide, and divinylbenzene.

[0048] As described above, the fourth aspect of the present invention provides a method for preparing a waterproof coiled material, which is carried out using the composition described in the foregoing third aspect, and includes:

[0049] (1) Contact-mixing a composition containing a polyolefin elastomer, linear low-density polyethylene, polypropylene, modified fluorosilicone rubber, crosslinking agent, and crosslinking accelerator to obtain an intermediate material;

[0050] (2) Extrusion-molding and winding the intermediate material in sequence to obtain the waterproof coiled material.

[0051] Preferably, the contact mixing is carried out under stirring conditions, and the conditions for the contact mixing include: temperature 60-100 °C, rotation speed 30-60 rpm, and time 0.5-1.5 h.

[0052] Preferably, in step (2), the extrusion molding is carried out by three-roll calendering, and the conditions for the extrusion molding include: the temperature of the three rolls is 30-50 °C, and the gap between the three rolls is 0.9-1.5 mm.

[0053] In the present invention, the winding is carried out by conventional methods in the art, which will not be elaborated herein. Those skilled in the art should not construe this as a limitation to the present invention.

[0054] As described above, the fifth aspect of the present invention provides a waterproof coiled material prepared by the method described in the foregoing fourth aspect.

[0055] As described above, the sixth aspect of the present invention provides the application of the waterproof coiled material described in the foregoing fifth aspect in the field of building waterproofing.

[0056] The present invention will be described in detail below through examples.

[0057] In the following examples, unless otherwise specified, the reagents and raw materials involved are commercially available products. The reagents are all analytical pure products, and ethanol is anhydrous ethanol.

[0058] In the following examples, unless otherwise specified, each part by weight represents 0.1 kg.

[0059] Raw materials

[0060] Graphite: Purchased from Daikin Industries, Ltd., Japan;

[0061] Filler I: Calcium powder: The average particle diameter is 10 μm, purchased from Guangzhou Jialiang Co., Ltd.;

[0062] Filler II: Calcium powder: The average particle diameter is 6.5 μm, purchased from Zhenjiang Sentong Calcium Carbonate Factory;

[0063] Fluorosilicone rubber I: Extrusion-type fluorosilicone rubber M1050, Shore A hardness is 51, tensile strength is 9.2 MPa, elongation at break is 337%, purchased from Wellbo New Materials Technology Co., Ltd.;

[0064] Fluorosilicone rubber II: Extrusion-type fluorosilicone rubber M1070, Shore A hardness is 74, tensile strength is 9.4 MPa, elongation at break is 273%, purchased from Wellbo New Materials Technology Co., Ltd.;

[0065] Silane coupling agent I: KH-550, purchased from Hangzhou Jessica Chemical Co., Ltd.;

[0066] Silane coupling agent II: KH-560, purchased from Hangzhou Jessica Chemical Co., Ltd.;

[0067] Polyolefin elastomer I: The melt index is 1.8 g / 10 min, purchased from Dow Chemical Company, USA;

[0068] Linear low-density polyethylene: The density is 0.92 g / cm3, and the melt index is 1.6 g / 10 min, purchased from Guangzhou Branch of Sinopec;

[0069] Polypropylene: The degree of polymerization is 4000 - 10000, the density is 0.89 g / cm3, and the melt index is 3 g / 10 min. It is purchased from Fujian Zhongjing Petrochemical Company;

[0070] Crosslinking agent: Dicumyl peroxide (DCP), purchased from Anhui Xiangyun Rubber and Plastic Co., Ltd.;

[0071] Crosslinking accelerator: Zinc oxide, purchased from Dalian Jinshi Zinc Oxide Co., Ltd.

[0072] Preparation Example 1

[0073] This preparation example is used to illustrate the modified fluorosilicone rubber described in the present invention according to the formula and process parameters in Table 1 and is prepared by the method described below.

[0074] The method for preparing the modified fluorosilicone rubber includes the following steps:

[0075] S1. In the presence of absolute ethanol, the silane coupling agent is added dropwise (the dropping rate is 0.1 ml / s) to be first mixed with the filler and graphite to obtain mixture I; the mixture I is dried at 80°C for 40 min; the conditions for the first mixing are: the temperature is 70°C and the time is 2 h; relative to 100 parts by weight of graphite, the amount of absolute ethanol used is 150 parts by weight;

[0076] S2. The fluorosilicone rubber and the mixture I are second mixed to obtain mixture II; the conditions for the second mixing are: the temperature is 180°C, the time is 10 min, and the stirring speed is 50 rpm;

[0077] S3. The mixture II is subjected to extrusion granulation to obtain the modified fluorosilicone rubber.

[0078] Without special instructions, the remaining preparation examples are carried out using a process similar to that of Preparation Example 1. The difference is that the formulas and process parameters used in each preparation example are different. For details, see Table 1 (note: the parameters not listed in Table 1 are the same as the corresponding parameters in Preparation Example 1).

[0079] Table 1

[0080]

[0081]

[0082] Example 1

[0083] This example is used to illustrate the waterproof coiled material described in the present invention according to the formula in Table 2 and is prepared by the method described below.

[0084] The method for preparing the waterproof coiled material includes the following steps:

[0085] (1) Contact and mix a composition containing polyolefin elastomer, linear low-density polyethylene, polypropylene, modified fluorosilicone rubber, crosslinking agent, and crosslinking accelerator to obtain an intermediate material; the conditions for the contact mixing are: temperature is 80°C, rotation speed is 45 rpm, and time is 1 h;

[0086] (2) Extrusion mold and wind up the intermediate material in sequence to obtain the waterproof coiled material; the conditions for the extrusion molding include: the temperature of the three rollers is 45°C, and the gap between the three rollers is 1.5 mm.

[0087] Without special instructions, the remaining examples are carried out using a process similar to that of Example 1. The difference is that the formulations used in each example are different. For details, see Table 2 (note: the parameters not listed in Table 2 are the same as the corresponding parameters in Example 1).

[0088] Table 2

[0089]

[0090]

[0091] Example 4

[0092] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of modified fluorosilicone rubber Z3 is used to replace modified fluorosilicone rubber Z1 in Example 1.

[0093] The rest are the same as those in Example 1.

[0094] The waterproof coiled material S4 is prepared.

[0095] Example 5

[0096] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of modified fluorosilicone rubber Z4 is used to replace modified fluorosilicone rubber Z1 in Example 1.

[0097] The rest are the same as those in Example 1.

[0098] The waterproof coiled material S5 is prepared.

[0099] Example 6

[0100] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of modified fluorosilicone rubber Z5 is used to replace modified fluorosilicone rubber Z1 in Example 1.

[0101] The rest are the same as those in Example 1.

[0102] The waterproof coiled material S6 is prepared.

[0103] Example 7

[0104] This example is carried out using a process similar to that of Example 1. The difference is that in this example, relative to 100 parts by weight of the polyolefin elastomer I, the content of the linear low-density polyethylene is 65 parts by weight, the content of the polypropylene is 18 parts by weight, the content of the modified fluorosilicone rubber is 15 parts by weight, the content of the crosslinking agent is 5 parts by weight, and the content of the crosslinking accelerator is 5 parts by weight.

[0105] The rest are the same as those in Example 1.

[0106] The waterproof coiled material S7 is prepared.

[0107] Comparative Example 1

[0108] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of the modified fluorosilicone rubber DZ1 is used to replace the modified fluorosilicone rubber Z1 in Example 1.

[0109] The rest are the same as those in Example 1.

[0110] The waterproof coiled material DS1 is prepared.

[0111] Comparative Example 2

[0112] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of the modified fluorosilicone rubber DZ2 is used to replace the modified fluorosilicone rubber Z1 in Example 1.

[0113] The rest are the same as those in Example 1.

[0114] The waterproof coiled material DS2 is prepared.

[0115] Comparative Example 3

[0116] This example is carried out using a process similar to that of Example 1. The difference is that in this example, an equal mass of the fluorosilicone rubber I is used to replace the modified fluorosilicone rubber Z1 in Example 1.

[0117] The rest are the same as those in Example 1.

[0118] The waterproof coiled material DS3 is prepared.

[0119] Test Example

[0120] Tensile strength test standard (method): Conducted according to Method B in GB / T 328.9-2007.

[0121] Artificial weathering tensile strength test standard (method): Conducted according to the standard (Part 6.17) of GB 27789-2011.

[0122] Tensile strength retention rate test standard (method): Q = (Q2 / Q1) * 100%;

[0123] Where: Q — Tensile strength retention rate (%);

[0124] Q2 — Tensile strength after artificial weathering;

[0125] Q1 — Tensile strength without treatment;

[0126] Dimensional change rate test standard (method): Conduct according to the standard of GB / T 328.13.

[0127] S = (S1 - S0) / S0;

[0128] Where:

[0129] S — Dimensional change rate, expressed in %;

[0130] S1 — Dimension after treatment, in millimeters (mm);

[0131] S0 — Dimension before treatment, in millimeters (mm);

[0132] Use the above test methods to conduct performance tests on the waterproof coiled materials obtained in each example. The test results are shown in Table 3.

[0133] Table 3

[0134]

[0135] It can be seen from the results in Table 3 that the waterproof coiled materials prepared by using the modified fluorosilicone rubber provided by the present invention have better tensile strength retention rate and dimensional change rate.

[0136] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A method for preparing modified fluorosilicone rubber, characterized in that, The method includes: S1. First mix graphite, filler, and silane coupling agent to obtain mixture I; the conditions for the first mixing include: temperature of 65 - 75°C and time of 1.5 - 3 h; the average particle diameter of the filler is 7 - 13 μm; S2. Second mix fluorosilicone rubber and mixture I to obtain mixture II; the conditions for the second mixing include: temperature of 165 - 190°C and time of 5 - 20 min; S3. Perform extrusion granulation on mixture II to obtain the modified fluorosilicone rubber; Relative to 100 parts by weight of the fluorosilicone rubber, the dosage of the filler is 10 - 20 parts by weight, the dosage of the graphite is 1 - 10 parts by weight, and the dosage of the silane coupling agent is 1 - 3 parts by weight.

2. The method according to claim 1, wherein The Shore A hardness of the fluorosilicone rubber is 40 - 60, the tensile strength is 9 - 10 MPa, and the elongation at break is 300% - 400%; And / or, the silane coupling agent uses a silane coupling agent with an amino functional group.

3. The method according to claim 1 or 2, characterized in that, The filler is calcium powder.

4. The modified fluorosilicone rubber prepared by the method according to claim 1 or 2.

5. A rubber compound composition for waterproofing membranes, characterized in that, This composition contains the following components stored independently or in a mixture of two or more: Polyolefin elastomer, linear low density polyethylene, polypropylene, modified fluorosilicone rubber, crosslinking agent, crosslinking accelerator; Relative to 100 parts by weight of the polyolefin elastomer, the content of the linear low density polyethylene is 35 - 65 parts by weight, the content of the polypropylene is 2 - 18 parts by weight, the content of the modified fluorosilicone rubber is 1 - 15 parts by weight, the content of the crosslinking agent is 1 - 5 parts by weight, and the content of the crosslinking accelerator is 0.5 - 5 parts by weight. The modified fluorosilicone rubber is the modified fluorosilicone rubber described in claim 4.

6. The composition according to claim 5, wherein Relative to 100 parts by weight of the polyolefin elastomer, the content of the linear low density polyethylene is 40 - 60 parts by weight, the content of the polypropylene is 5 - 15 parts by weight, the content of the modified fluorosilicone rubber is 3 - 10 parts by weight, the content of the crosslinking agent is 1 - 3 parts by weight, and the content of the crosslinking accelerator is 0.5 - 3 parts by weight.

7. The composition according to claim 5 or 6, characterized in that, The melt index of the polyolefin elastomer is 1.0 - 4.0 g / 10 min; And / or, the degree of polymerization of the polypropylene is 4000 - 10000, the density is 0.88 - 0.92 g / cm3, and the melt index is 2.0 - 4.0 g / 10 min; And / or, the density of the linear low density polyethylene is 0.90 - 0.94 g / cm3, and the melt index is 1.0 - 4.0 g / 10 min.

8. A method for preparing a waterproof coiled material, characterized in that, This method is carried out using the composition according to any one of claims 5 - 7 and includes: (1) Contact mix the composition containing polyolefin elastomer, linear low density polyethylene, polypropylene, modified fluorosilicone rubber, crosslinking agent, and crosslinking accelerator to obtain an intermediate material; (2) Successively perform extrusion molding and winding on the intermediate material to obtain the waterproof coiled material.

9. The method according to claim 8, wherein The contact mixing is carried out under stirring conditions, and the conditions of the contact mixing include: the temperature is 60-100°C, the rotation speed is 30-60 rpm, and the time is 0.5-1.5 h.

10. A waterproof coiled material prepared by the method according to claim 8 or 9.

11. The application of the waterproof coiled material according to claim 10 in the field of building waterproofing.

Images