CN117186555A - Water stop composite material and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of water stop materials, and discloses a water stop composite material which comprises the following components in parts by weight: 100-200 parts of ethylene propylene diene monomer, 0-20 parts of hydroxylated myrcene polymer or hydroxylated myrcene copolymer, 0-20 parts of butyl hydroxy rubber or butyl hydroxy rubber copolymer, 1-5 parts of silane coupling agent, 8-12 parts of quick extrusion carbon black N55090-120 parts, 8-12 parts of calcium oxide, 2-6 parts of anti-aging agent, 8-12 parts of hydroxylated carbon nano tube, 2-6 parts of zinc oxide, 1-5 parts of stearic acid, 1-6 parts of accelerator and 0.4-1.2 parts of sulfur. The invention has high tensile strength, high fatigue resistance, excellent low temperature resistance, large deformation resistance and good extrusion molding performance, and is suitable for the use requirements of water stops in the fields of expressway bridges, tunnels and the like.

Description

Water stop composite material and preparation method thereof

Technical Field

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

Background

When the highway bridge is constructed, the physical performance of the bridge can be improved, and the deformation problem caused by the load of the vehicle and the environmental change can be relieved by reasonably designing and installing the bridge expansion joint, so that the safe passing and the service life of the bridge as long as possible are ensured. However, the problems of pit, transverse crack, breakage and the like are easy to appear in the bridge expansion joint under the influence of long-term corrosion and dynamic loading vehicles in the natural open-air environment, and the normal service life of the bridge and smooth road traffic are affected.

The waterstop is used as an important part of a road bridge expansion joint, rainwater erosion can be caused when the design and the use performance are not up to standard, the infiltration rainwater in the waterstop can lead to a supporting beam and a transmission device to be corroded, the expansion joint is damaged to be used normally gradually, even the steel beam can be distorted, and the bridge support is invalid. If the rubber strip of the water stop belt is poor in cold brittleness, the elasticity is lost in winter, the strength is low, strong rain wash is used for generating water leakage, the fatigue resistance is poor, the operation mechanical damage is aged, the appearance size of a finished product is irregular, the water leakage is generated, and the like, the water stop belt can be damaged under the action of long-time and repeated stretching and shrinking in the use process of an expansion joint.

Functionalized liquid rubber is a novel polymer material developed in recent years, such as: the polymer material has special topological structure and active functional group, such as can cooperate with functional filler, and can replace traditional plasticizers such as oils, o-benzoic acid esters, aliphatic dibasic acids, epoxy esters, chlorine-containing compounds, phosphate esters and the like to be applied to rubber formulas, thereby reducing energy consumption in the processing process, improving mechanical property of formulas, improving low temperature resistance of formulas, improving dimensional stability and the like. Therefore, the invention provides a composite material which can be used in the fields of highway bridges, tunnels and the like for a long time and a preparation method thereof for improving the service effect and the service life of the water stop belt.

Disclosure of Invention

The invention aims to provide a water stop composite material suitable for the fields of highway bridges, tunnels and the like, which has high tensile strength, high fatigue resistance, excellent low temperature resistance, high deformation resistance and good extrusion molding performance, and is suitable for the use requirements of water stops in the fields of highway bridges, tunnels and the like.

In order to achieve the above object, the technical scheme of the present invention is as follows: the water stop composite material comprises the following components in parts by weight: 100-200 parts of ethylene propylene diene monomer rubber, 0-20 parts of hydroxylated myrcene polymer or hydroxylated myrcene copolymer, 0-20 parts of butyl hydroxy rubber or butyl hydroxy rubber copolymer, 1-5 parts of silane coupling agent, 8-120 parts of quick extrusion carbon black N55090, 8-12 parts of calcium oxide, 2-6 parts of anti-aging agent, 8-12 parts of hydroxylated carbon nano tube, 2-6 parts of zinc oxide, 1-5 parts of Stearic Acid (SA), 1-6 parts of accelerator and 0.4-1.2 parts of sulfur.

Further; the ethylene propylene diene monomer is EPDM 4869.

Further; the sulfur IS ordinary sulfur or Insoluble Sulfur (IS).

Further; the carbon nano tube is selected from one or more of multi-arm hydroxylation carbon nano tube powder with the length of 1-100 mu m.

Further; the molecular weight of the hydroxylation myrcene polymer or the hydroxylation myrcene copolymer is 5000-60000 g/mol; the molecular weight of the butyl hydroxy rubber or the butyl hydroxy rubber copolymer is 5000-60000 g/mol; all are liquid at normal temperature.

Further; the protective agent is one or more selected from protective wax or microcrystalline wax, an anti-aging agent 4020, an anti-aging agent 4010NA, nickel dithiocarbamate, nickel dibutyl dithiocarbamate, 2, 4-trimethyl-1, 2-dihydroquinoline and 1, 2-dihydro-6-ethoxy-2, 4-trimethylquinoline.

Further; the accelerator is one or more selected from dithio-carbamate accelerator, sulfenamide accelerator and thiuram accelerator; the dithiocarbamic acid salt is selected from one or more of zinc dimethyl dithiocarbamic acid (ZDMC), zinc diethyl dithiocarbamic acid (ZDC), zinc dibenzyl dithiocarbamic acid (ZBEC), zinc dibutyl dithiocarbamic acid (BZ) and zinc ethyl phenyl dithiocarbamic acid (PX); the sulfenamide accelerator is selected from one or more of N-cyclohexyl-2-benzothiazole sulfenamide (CZ), N-tertiary butyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N-dicyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylene thiocarbamoyl-N' -oxydiethylene sulfenamide; the thiuram accelerator is one or more selected from tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, diisobutylthiuram disulfide, tetrabenzylthiuram disulfide and tetrabutylthiuram disulfide.

Further; the silane coupling agent is selected from one or more of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide (silane coupling agent Si 69), gamma-aminopropyl triethoxysilane, gamma-thiopropyl trimethoxysilane and vinyl triethoxysilane.

The other technical scheme of the invention is as follows: the preparation method of the water stop composite material is carried out according to one of the following methods:

the method comprises the following steps: prefabricated mixture method:

weighing hydroxylated myrcene polymer or hydroxylated myrcene copolymer, butyl hydroxy rubber or butyl hydroxy rubber copolymer, silane coupling agent and hydroxylated carbon nanotube according to the formula, mixing, dispersing by a high-speed stirrer, heating to 110-120 ℃, rotating at 20-50 Hz, and discharging after high stirring for 1-3 hours to serve as master batch for later use;

weighing ethylene propylene diene monomer rubber, the master batch and all auxiliary agents except sulfur and accelerators according to a formula, plasticating by an internal mixer, uniformly mixing to obtain a rubber compound, and cooling and standing; dispersing sulfur and an accelerator in the mixed rubber by adopting an open mill, turning over the rubber, rolling, wrapping with a triangular bag to uniformly disperse the rubber, and thinning the rubber sheet for later use; shaping the rubber compound with sulfur and accelerator by a screw extruder and performing microwave vulcanization;

the second method is as follows: one-time addition molding method:

weighing ethylene propylene diene monomer, hydroxylated myrcene polymer or hydroxylated myrcene copolymer, butyl hydroxy rubber or butyl hydroxy rubber copolymer, silane coupling agent, hydroxylated carbon nano tube and all auxiliary agents except sulfur and accelerator according to a formula, mixing by an internal mixer to obtain a mixed rubber, and cooling and standing; dispersing sulfur and an accelerator in the mixed rubber by adopting an open mill, turning over the rubber, rolling, wrapping with a triangular bag to uniformly disperse the rubber, and thinning the rubber sheet for later use; and molding the rubber compound with the sulfur and the accelerator by adopting a screw extruder and performing microwave vulcanization.

The invention has the beneficial effects that:

1) According to the invention, ethylene propylene diene monomer raw materials are selected, the prepared water stop belt meets the requirements of practical bridge application, and the comprehensive waterproof and damping effects are good. The hydroxyl laurene polymer or the hydroxyl laurene copolymer, the butyl hydroxy rubber or the butyl hydroxy rubber copolymer are selected to replace common white oil, paraffin oil and other plasticizers to be used, and can cooperate with the carbon nano tube through chemical bonds and physical interactions, so that the grafting of high molecules on the surface of the carbon nano tube can be realized, the grafted high polymers have special topological structures, an adsorption bonding layer is formed when polymer chains are physically adsorbed on the surface of the carbon black nano particles, and the configuration of the adsorption bonding layer can be ring-type, chain rail-type, tail-type or the like. In particular, the flexible side chain of myrcene 'bottle brush structure' is beneficial to diffusion and permeation on the surface of filler, has great influence on contact angle, can remarkably improve the dispersibility of carbon black and inhibit strong interaction between fillers, and has no cross-linked side chain isopropylidene (ch=c (CH ₃ ) ₂ ) The units have a better affinity for the carbon black particles, a mechanism that differs from conventional strategies that enhance the interface between filler and rubber. The rubber compound has better combination effect with carbon black filler, can reduce energy consumption in the process of preparing the rubber compound by an internal mixer, improve mechanical property of a water stop belt, improve low temperature resistance of the water stop belt, and more importantly, improve green strength of the rubber compound, avoid defects of semi-finished products and improve dimensional stability during extrusion molding.

2) When the hydroxylated myrcene polymer or the hydroxylated myrcene copolymer, the butyl hydroxy rubber or the butyl hydroxy rubber copolymer are used for replacing a common plasticizer, the hydroxylated polymer and the hydroxylated carbon nano tube form a bridging bond through a silane coupling agent in a better way than the traditional non-hydroxylated product. In the rubber formula, the crosslinking bond and the hydroxylated carbon nanotube skeleton lead the hydroxylated polymer to play a better plasticizing effect than the polymer without functional groups and the traditional micromolecules, without precipitation phenomenon, and simultaneously have excellent mechanical property and anti-compression effect.

Drawings

FIG. 1 is a photograph of comparative example 1 extrudate;

fig. 2 is a photograph of the extrudate of example 1.

Detailed Description

Comparative example 1:

a water stop composite comprising the following components: 4869180g of EPDM, 550110g of quick-extrusion carbon black, 15g of white oil, 10g of calcium oxide, 1g of protective wax, 2g of anti-aging agent 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) Weighing 15g of white oil, 692g of silane coupling agent Si and 10g of 100 mu m hydroxylated carbon nanotube, mixing, dispersing by a high-speed stirrer, heating to 110 ℃, stirring at the rotating speed of 30 Hz, discharging for 120 minutes, and taking the mixture as modified hydroxylated carbon nanotube masterbatch;

2) Taking the modified hydroxylated carbon nanotube master batch, weighing 4869180g of EPDM, rapidly extruding N550110g of carbon black, 10g of calcium oxide, 1g of protective wax, 4010NA2g of anti-aging agent, 5g of ZnO and 1g of SA, sequentially putting into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to uniformly mix, discharging the rubber when the temperature is raised to 150 ℃, tabletting by an open mill to be about 2 mm thick, and standing the rubber mixture sheet for standby; and then sequentially wrapping the rubber compound sheet with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill, turning over the rubber compound three times, rolling three triangular bags to ensure that the rubber compound sheet IS uniformly dispersed, has smooth surface, and IS standby after the rubber compound sheet IS coated with 2 mm rubber. The water stop composite material is prepared by molding the rubber compound with the insoluble sulfur and the accelerator by a screw extruder (the burrs of the extruded product are serious as shown in figure 1) and performing microwave vulcanization.

The strong sheet, peel strength and low temperature brittle test pieces were prepared on a press vulcanizer and the physical mechanical properties, aging properties, peel strength and low temperature brittle test pieces were tested for properties, the material properties being shown in table 1.

Example 1:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid myrcene polymer, 10g of calcium oxide, 1g of protective wax, 2g of anti-aging agent 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) Preparing a hydroxylation liquid myrcene polymer, namely preparing the hydroxylation liquid myrcene polymer by using 100g of myrcene, 20g of 35% hydrogen peroxide as a catalyst and 100g of absolute ethyl alcohol as a solvent, wherein the polymerization temperature is 110 ℃, and performing polymerization reaction for 3 hours;

2) Weighing 15g of hydroxylated liquid myrcene polymer, 693g of silane coupling agent Si and 10g of 100 mu m hydroxylated carbon nanotube, mixing, dispersing by a high-speed stirrer, heating to 110 ℃, stirring at a rotating speed of 30 Hz, discharging for 120 minutes, and taking the mixture as modified hydroxylated carbon nanotube masterbatch for later use;

3) Weighing 180g of EPDM 4869, quick-extrusion carbon black N550110g, 10g of calcium oxide, 1g of protective wax, 4010NA2g of an anti-aging agent, 5g of ZnO and 1g of SA, sequentially putting into an internal mixer at the rotating speed of 55 r/min, mixing at the initial temperature of 80 ℃ uniformly, discharging rubber when the temperature is raised to 150 ℃, tabletting by an open mill to be about 2 mm thick, and standing the rubber compound sheet for later use; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. The rubber compound added with the insoluble sulfur and the accelerator is molded by a screw extruder (the surface of the extruded product is smooth as shown in figure 2) and is vulcanized by microwaves, so that the water stop composite material is prepared.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 2:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid myrcene/butadiene copolymer, 10g of calcium oxide, 1g of protective wax, 2g of 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) Preparing a hydroxylation liquid myrcene polymer, namely preparing the hydroxylation liquid myrcene polymer by using 70g of myrcene, 30g of butadiene, 20g of 35% hydrogen peroxide as a catalyst and 100g of absolute ethyl alcohol as a solvent, and performing polymerization reaction for 3 hours at a polymerization temperature of 110 ℃;

2) Weighing 15g of hydroxylation liquid myrcene/butadiene copolymer, 693g of silane coupling agent Si and 10g of 100 mu m hydroxylation carbon nano tube, mixing, dispersing by a high-speed stirrer, heating to 110 ℃, stirring at the rotating speed of 30 Hz, discharging for 120 minutes, and taking the mixture as modified hydroxylation carbon nano tube master batch for standby;

3) Weighing 180g of EPDM 4869, quick-extrusion carbon black N550110g, calcium oxide 10g, protective wax 1g, anti-aging agent 4010NA2g, znO 5g and SA 1g, sequentially putting into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to uniformly mix, discharging rubber when the temperature is raised to 150 ℃, tabletting by using an open mill to be about 2 mm thick, and standing the rubber compound sheet for standby; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 3:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid butadiene polymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDCC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) Preparing a hydroxylated liquid butadiene polymer, namely preparing the hydroxylated liquid butadiene polymer by using 100g of butadiene, 20g of 35% hydrogen peroxide as a catalyst and 100g of absolute ethyl alcohol as a solvent, wherein the polymerization temperature is 110 ℃, and the polymerization is carried out for 3 hours;

2) Weighing 15g of hydroxylated liquid butadiene polymer, 693g of silane coupling agent Si and 10g of 100 mu m hydroxylated carbon nanotube, mixing, dispersing by a high-speed stirrer, heating to 110 ℃, stirring at a rotating speed of 30 Hz, discharging for 120 minutes, and taking the mixture as modified hydroxylated carbon nanotube masterbatch for later use;

3) Weighing 180g of EPDM 4869, quick-extrusion carbon black N550110g, 10g of calcium oxide, 1g of protective wax, 4010NA2g, znO 5g and SA 1g, sequentially putting into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to uniformly mix, discharging the rubber when the temperature is raised to 150 ℃, tabletting by using an open mill to be about 2 mm thick, and standing the rubber compound sheet for later use; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 4:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid butadiene/isoprene copolymer, 10g of calcium oxide, 1g of protective wax, 2g of antioxidant 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) Preparing a hydroxylated liquid butadiene/isoprene copolymer, namely preparing the hydroxylated liquid butadiene/isoprene copolymer by using 70g of butadiene, 30g of isoprene, 20g of 35% hydrogen peroxide as a catalyst and 100g of absolute ethyl alcohol as a solvent, and performing polymerization reaction for 3 hours at a polymerization temperature of 110 ℃;

2) Weighing 15g of hydroxylated liquid butadiene/isoprene copolymer, 693g of silane coupling agent Si and 10g of 100 mu m hydroxylated carbon nanotube, mixing, dispersing by a high-speed stirrer, heating to 110 ℃, stirring at a rotating speed of 30 Hz, and discharging for 120 minutes to obtain modified hydroxylated carbon nanotube masterbatch;

3) Weighing 180g of EPDM 4869, quick-extrusion carbon black N550110g, 10g of calcium oxide, 1g of protective wax, 4010NA2g, znO 5g and SA 1g, sequentially putting into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to uniformly mix, discharging the rubber when the temperature is raised to 150 ℃, tabletting by using an open mill to be about 2 mm thick, and standing the rubber compound sheet for later use; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 5:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid myrcene polymer, 10g of calcium oxide, 1g of protective wax, 2g of 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) The procedure for the preparation of hydroxylated liquid myrcene polymer was as in example 1;

2) 180g of EPDM 4869, 550110g of quick-extrusion carbon black, 15g of hydroxylated liquid myrcene polymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO and 1g of SA are weighed, sequentially put into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to mix evenly, the mixture is discharged after the temperature is raised to 150 ℃, and the mixture is pressed into a sheet with the thickness of about 2 mm by an open mill, so as to obtain a mixed rubber sheet for standing for standby; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 6:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid myrcene/butadiene copolymer, 10g of calcium oxide, 1g of protective wax, 2g of 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) A hydroxylated liquid myrcene/butadiene copolymer was prepared in the same manner as in example 2;

2) 180g of EPDM 4869, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid myrcene/butadiene copolymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO and 1g of SA are sequentially put into an internal mixer at the rotating speed of 55 r/min, the initial temperature is 80 ℃ to be evenly mixed, the mixture is heated to 150 ℃ to discharge rubber, and the mixture is pressed into a sheet with the thickness of about 2 mm by an open mill, so as to obtain a rubber compound sheet for standing; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 7:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid butadiene polymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDCC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) The procedure of example 3 was followed to produce a hydroxylated liquid butadiene polymer;

2) 180g of EPDM 4869, 550110g of quick-extrusion carbon black, 15g of hydroxylated liquid butadiene polymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO and 1g of SA are sequentially put into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to mix evenly, the mixture is heated to 150 ℃ to discharge rubber, and the mixture is pressed into a sheet with the thickness of about 2 mm by an open mill, so that a rubber compound sheet is parked for standby; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

Example 8:

a water stop composite comprising the following components: 4869180g of EPDM, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid butadiene/isoprene copolymer, 10g of calcium oxide, 1g of protective wax, 2g of 4010NA, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO, 1g of SA, 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ.

The preparation method of the water stop composite material comprises the following steps:

1) The procedure of example 4 was followed to produce a hydroxylated liquid butadiene/isoprene copolymer;

2) 180g of EPDM 4869, 15g of quick-extrusion carbon black N550110g of hydroxylated liquid butadiene/isoprene copolymer, 10g of calcium oxide, 1g of protective wax, 4010NA2g, 10g of 100 mu m hydroxylated carbon nano tube, 693g of silane coupling agent Si, 5g of ZnO and 1g of SA are sequentially put into an internal mixer at the rotating speed of 55 r/min and the initial temperature of 80 ℃ to mix evenly, the mixture is heated to 150 ℃ to discharge rubber, and the mixture is pressed into a sheet with the thickness of about 2 mm by an open mill, so as to obtain a rubber compound sheet for standing; and then the mixed rubber IS sequentially coated with 0.5g of IS, 0.75g of TMTD, 2.0g of ZDMC, 2.0g of ZDC and 1.2g of CZ on an open mill for three times of rubber turning, three times of rolling, six times of triangular wrapping, uniform dispersion and smooth surface, and the lower 2 mm of rubber sheet for standby. And molding the rubber compound with the insoluble sulfur and the accelerator by adopting a screw extruder, and performing microwave vulcanization to obtain the water stop composite material.

Uniformly mixing all auxiliary agents, and standing the mixed rubber reaching the standard, vulcanizing according to the positive vulcanization time of the process, wherein the vulcanization pressure is as follows: 14.5MPa. Test samples for mechanical properties, peel strength and low-temperature brittleness were prepared, and the physical and mechanical properties, aging properties, peel strength and low-temperature brittleness were tested, and the material properties are shown in table 1.

TABLE 1 physical and mechanical Properties of Water stop composite Material

The above-described embodiments are merely preferred embodiments of the present invention, and the present invention is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.

Claims (8)

1. The water stop composite material is characterized by comprising the following components in parts by weight: 100-200 parts of ethylene propylene diene monomer, 0-20 parts of hydroxylated myrcene polymer or hydroxylated myrcene copolymer, 0-20 parts of butyl hydroxy rubber or butyl hydroxy rubber copolymer, 1-5 parts of silane coupling agent, 8-12 parts of quick extrusion carbon black N55090-120 parts, 8-12 parts of calcium oxide, 2-6 parts of anti-aging agent, 8-12 parts of hydroxylated carbon nano tube, 2-6 parts of zinc oxide, 1-5 parts of stearic acid, 1-6 parts of accelerator and 0.4-1.2 parts of sulfur.

2. The water stop composite of claim 1, wherein: the sulfur is common sulfur or insoluble sulfur.

3. The water stop composite of claim 1, wherein: the carbon nano tube is selected from one or more of multi-arm hydroxylation carbon nano tube powder with the length of 1-100 mu m.

4. The water stop composite of claim 1, wherein: the molecular weight of the hydroxylation myrcene polymer or the hydroxylation myrcene copolymer is 5000-60000 g/mol; the molecular weight of the butyl hydroxy rubber or the butyl hydroxy rubber copolymer is 5000-60000 g/mol; all are liquid at normal temperature.

5. The water stop composite of claim 1, wherein: the protective agent is one or more selected from protective wax or microcrystalline wax, an anti-aging agent 4020, an anti-aging agent 4010NA, nickel dithiocarbamate, nickel dibutyl dithiocarbamate, 2, 4-trimethyl-1, 2-dihydroquinoline and 1, 2-dihydro-6-ethoxy-2, 4-trimethylquinoline.

6. The water stop composite of claim 1, wherein: the accelerator is one or more selected from dithio-carbamate accelerator, sulfenamide accelerator and thiuram accelerator; the dithiocarbamic acid salt is selected from one or more of zinc dimethyl dithiocarbamic acid, zinc diethyl dithiocarbamic acid, zinc dibenzyl dithiocarbamic acid, zinc dibutyl dithiocarbamic acid and zinc ethyl phenyl dithiocarbamic acid; the sulfenamide accelerator is selected from one or more of N-cyclohexyl-2-benzothiazole sulfenamide, N-tertiary butyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N-dicyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylene thiocarbamoyl-N' -oxydiethylene sulfenamide; the thiuram accelerator is one or more selected from tetramethylthiuram disulfide, tetraethylthiuram disulfide, diisobutylthiuram disulfide, tetrabenzylthiuram disulfide and tetrabutylthiuram disulfide.

7. The water stop composite of claim 1, wherein: the silane coupling agent is selected from one or more of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, gamma-aminopropyl triethoxysilane, gamma-thiopropyl trimethoxysilane and vinyl triethoxysilane.

8. A method of preparing a water stop composite material according to claim 1, characterized by one of the following:

the method comprises the following steps: prefabricated mixture method:

weighing hydroxylated myrcene polymer or hydroxylated myrcene copolymer, butyl hydroxy rubber or butyl hydroxy rubber copolymer, silane coupling agent and hydroxylated carbon nanotube according to the formula, mixing, dispersing by a high-speed stirrer, heating to 110-120 ℃, rotating at 20-50 Hz, and discharging after high stirring for 1-3 hours to serve as master batch for later use;

weighing ethylene propylene diene monomer rubber, the master batch and all auxiliary agents except sulfur and accelerators according to a formula, plasticating by an internal mixer, uniformly mixing to obtain a rubber compound, and cooling and standing; dispersing sulfur and an accelerator in the mixed rubber by adopting an open mill, turning over the rubber, rolling, wrapping with a triangular bag to uniformly disperse the rubber, and thinning the rubber sheet for later use; shaping the rubber compound with sulfur and accelerator by a screw extruder and performing microwave vulcanization;

the second method is as follows: one-time addition molding method:

weighing ethylene propylene diene monomer, hydroxylated myrcene polymer or hydroxylated myrcene copolymer, butyl hydroxy rubber or butyl hydroxy rubber copolymer, silane coupling agent, hydroxylated carbon nano tube and all auxiliary agents except sulfur and accelerator according to a formula, mixing by an internal mixer to obtain a mixed rubber, and cooling and standing; dispersing sulfur and an accelerator in the mixed rubber by adopting an open mill, turning over the rubber, rolling, wrapping with a triangular bag to uniformly disperse the rubber, and thinning the rubber sheet for later use; and molding the rubber compound with the sulfur and the accelerator by adopting a screw extruder and performing microwave vulcanization.