CN116515179B - Rubber and plastic water stop for tunnel and preparation method and application thereof - Google Patents
Rubber and plastic water stop for tunnel and preparation method and application thereof Download PDFInfo
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- CN116515179B CN116515179B CN202310778185.8A CN202310778185A CN116515179B CN 116515179 B CN116515179 B CN 116515179B CN 202310778185 A CN202310778185 A CN 202310778185A CN 116515179 B CN116515179 B CN 116515179B
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Abstract
The invention provides a rubber and plastic water stop belt for a tunnel, and belongs to the technical field of rubber materials. According to the invention, the glycidyl methacrylate is added to modify the natural rubber, so that the fusion capability between the natural rubber and the linear low-density polyethylene and between the natural rubber and the polyvinyl chloride interface can be improved, a modulus gradient is formed between the natural rubber and the polyvinyl chloride and between the natural rubber and the linear low-density polyethylene, the natural rubber has better tensile strength and elongation at break, the mechanical property and the large deformation capability are improved, and the requirements of the rubber water stop on the earthquake damage resistance and the large deformation generated during the earthquake are met. According to the invention, the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is added, the epoxy functionality of the epoxy resin is high, a crosslinked three-dimensional structure is easy to form, and the friction between molecular chains can be increased, so that the damping performance is improved; meanwhile, the molecular chain contains more benzene ring macromolecular structures, so that the friction resistance during molecular chain movement is further increased, and the damping performance is improved.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a rubber and plastic water stop belt for a tunnel, and a preparation method and application thereof.
Background
Between the European and Pacific seismic bands at the ground of China.
The tunnel is used as an important traffic building facility, can improve the traffic technical state, and plays an important role in shortening the running distance, protecting the natural environment, improving the transportation capacity, reducing accidents and the like. According to the tunnel engineering earthquake damage statistics, when the tunnel structure is in the movable fracture zone area, serious earthquake damage such as lining collapse, steel bar fracture, whole ring fracture and the like often occur. Conventional wisdom considers the effect of an earthquake on a tunnel to be primarily from transverse shear waves in the seismic waves, delivering the largest portion of the seismic energy. Seismic waves are superimposed on the static strain of the tunnel lining and surrounding rock formations by cycling alternating compressive and tensile strains within the tunnel wall. The original strain state in the lining is generally compressive strain, and after compressive strain generated by seismic shock is applied to the lining, the lining may be compressed to generate spalling. If the applied tensile strain is greater than the original compressive strain, the final tensile strain will cause the lining to crack.
The water stop belt utilizes the characteristics of high elasticity, compression deformation and the like of rubber, generates elastic deformation at the joint of concrete, plays the roles of effectively firmly sealing, preventing water leakage, water seepage and shock absorption and buffering of the building structure. But the common rubber water stop has limited deformation capability and lower damping performance, and can not meet the deformation and damping requirements of the concrete joints of the tunnel of the earthquake fracture zone.
Disclosure of Invention
In view of the above, the invention aims to provide a rubber and plastic water stop for a tunnel, and a preparation method and application thereof. The tunnel rubber and plastic water stop belt provided by the invention has excellent mechanical property, strong deformability and high damping performance, and can meet the deformation and damping requirements of the concrete joint of the tunnel with the earthquake fracture zone.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a tunnel rubber and plastic water stop belt, which comprises the following raw materials in parts by mass:
70-90 parts of natural rubber;
5-15 parts of glycidyl methacrylate;
10-30 parts of linear low density polyethylene;
5-10 parts of polyvinyl chloride;
0.3-1 parts of dicumyl peroxide;
20-50 parts of filler;
0.5-2.5 parts of vulcanizing agent;
4-9 parts of an active agent;
1-3 parts of an accelerator;
1-3 parts of an anti-aging agent;
the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is characterized by further comprising a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, wherein the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises the following raw materials in parts by mass based on the parts by mass of the natural rubber:
10-20 parts of styrene-butadiene rubber;
1-4 parts of maleic anhydride;
0.5-1 part of an initiator;
3-8 parts of epoxy resin.
Preferably, the natural rubber is solid natural rubber, and the density of the natural rubber is 0.90-0.99 g/cm 3 The strength grade is 1 grade;
the viscosity of the glycidyl methacrylate at 25 ℃ is 1.5-4.5 mpa-s.
Preferably, the linear low density polyethylene has a density of 0.91-0.94 g/cm 3 The melt index is 0.8-1.5 g/10min;
the polyvinyl chloride has a number average molecular weight of 5-11 ten thousand and a softening temperature of 70-100 ℃.
Preferably, the styrene-butadiene rubber is emulsion polymerized styrene-butadiene rubber, and the molecular weight of the styrene-butadiene rubber is 10-30 ten thousand;
the epoxy resin is bisphenol A epoxy resin, and the epoxy value of the epoxy resin is 0.18-0.40 eq/100g.
Preferably, the filler comprises, in parts by mass:
15-35 parts of carbon black;
5-15 parts of wollastonite powder;
the density of wollastonite powder is 2.8-3.2 g/cm 3 The granularity is 700-1500 meshes; the wollastonite powder surface is modified by a coupling agent.
Preferably, the vulcanizing agent comprises the following components in parts by weight:
0.5-1.5 parts of sulfur;
0.5-2 parts of dibenzoic acid peroxide.
Preferably, the initiator is dibenzoyl peroxide;
the active agent is stearic acid and/or zinc oxide;
the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide;
the anti-aging agent is N-isopropyl-N' -phenyl p-phenylenediamine.
The invention provides a preparation method of the tunnel rubber and plastic water stop belt, which comprises the following steps:
mixing styrene-butadiene rubber, maleic anhydride, an initiator and epoxy resin to obtain a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent;
mixing natural rubber, glycidyl methacrylate and dicumyl peroxide to obtain modified natural rubber;
pre-mixing the modified natural rubber, linear low-density polyethylene, polyvinyl chloride, an active agent, an anti-aging agent, a filler and a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and discharging rubber to obtain a pre-mixed rubber material;
secondary mixing is carried out on the pre-mixed rubber material, a vulcanizing agent and an accelerator to obtain a secondary mixed rubber material;
and (3) carrying out thin-pass extrusion vulcanization molding on the secondary mixed rubber material to obtain the tunnel rubber and plastic water stop belt.
Preferably, the extrusion speed of extrusion vulcanization molding is 1-3 m/min, and the vulcanization temperature is 150-240 ℃.
The invention provides application of the tunnel rubber and plastic water stop belt in a concrete joint of a tunnel with an earthquake fracture zone.
The invention provides a tunnel rubber and plastic water stop belt, which comprises the following raw materials in parts by mass: 70-90 parts of natural rubber; 5-15 parts of glycidyl methacrylate; 10-30 parts of linear low density polyethylene; 5-10 parts of polyvinyl chloride; 0.3-1 parts of dicumyl peroxide; 20-50 parts of filler; 0.5-2.5 parts of vulcanizing agent; 4-9 parts of an active agent; 1-3 parts of an accelerator; 1-3 parts of an anti-aging agent; the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is characterized by further comprising a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, wherein the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises the following raw materials in parts by mass based on the parts by mass of the natural rubber: 10-20 parts of styrene-butadiene rubber; 1-4 parts of maleic anhydride; 0.5-1 part of an initiator; 3-8 parts of epoxy resin. Compared with the prior art, the tunnel rubber and plastic water stop belt provided by the invention has the following advantages:
(1) The linear low-density polyethylene has the performances of high strength, good toughness, good environmental stress cracking resistance, high impact strength, high tearing strength and the like, but has poor compatibility with natural rubber, and can not fully exert the performance advantages. According to the invention, the glycidyl methacrylate is added, so that on one hand, the natural rubber is modified by using the glycidyl methacrylate, the fusion capability between the natural rubber and a linear low-density polyethylene and polyvinyl chloride interface is improved, the natural rubber and the linear low-density polyethylene are fully fused and blended, and the mechanical property of the natural rubber is improved; on the other hand, the performance advantage that the elastic modulus of the polyvinyl chloride is between that of the natural rubber and that of the linear low-density polyethylene is fully exerted, so that the modulus gradient is formed between the natural rubber and the linear low-density polyethylene, the thickness of the interface layer between the two phases of the rubber and the linear low-density polyethylene is increased, the adhesion capability of the two phases of the blend is enhanced, the binding force is stronger, and the mechanical property is more excellent. After copolymerization, the natural rubber has better tensile strength and elongation at break, improves mechanical property and large deformation capacity, and meets the requirements of the rubber water stop belt on resistance to earthquake damage and large deformation during earthquake.
(2) The invention uses styrene-butadiene rubber grafted epoxy resin macromolecular damping agent to replace traditional externally added damping auxiliary agents such as graphite, petroleum resin and the like, thereby improving the damping performance of rubber from the molecular structure. The epoxy resin has high epoxy functionality, is easy to form a cross-linked three-dimensional structure, increases friction between molecular chains and improves damping performance; meanwhile, the molecular chain contains more benzene ring macromolecular structures, so that the friction resistance during molecular chain movement is further increased, and the damping performance is improved. On one hand, styrene-butadiene rubber is grafted to epoxy resin through maleic anhydride, so that the dispersibility of the epoxy resin macromolecular damping agent in the rubber is improved; on the other hand, the strong reactive epoxy group on the glycidyl methacrylate modified natural rubber molecule can be crosslinked with the carboxyl in the maleic anhydride molecule grafted on the styrene-butadiene rubber, so that the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is linked to the natural rubber macromolecules, and the friction damping performance among rubber molecules is improved.
Furthermore, wollastonite powder is used as a filler component, and wollastonite has a needle-shaped structure, so that the tensile strength and flexural strength of the material can be further improved, and the damping performance can be improved.
The example results show that the tensile strength of the tunnel rubber and plastic water stop belt provided by the invention is 18.4-23.8 MPa, the elongation at break is 758-991 MPa, the equivalent damping ratio is 17.3-18.8%, and the constant compression set is 18.9-20.9%.
The invention provides the preparation method of the tunnel rubber and plastic water stop belt, which is simple to operate, low in cost and easy to realize industrialized mass production.
Detailed Description
The invention provides a tunnel rubber and plastic water stop belt, which comprises the following raw materials in parts by mass:
70-90 parts of natural rubber;
5-15 parts of glycidyl methacrylate;
10-30 parts of linear low density polyethylene;
5-10 parts of polyvinyl chloride;
0.3-1 parts of dicumyl peroxide;
20-50 parts of filler;
0.5-2.5 parts of vulcanizing agent;
4-9 parts of an active agent;
1-3 parts of an accelerator;
1-3 parts of an anti-aging agent;
the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is characterized by further comprising a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, wherein the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises the following raw materials in parts by mass based on the parts by mass of the natural rubber:
10-20 parts of styrene-butadiene rubber;
1-4 parts of maleic anhydride;
0.5-1 part of an initiator;
3-8 parts of epoxy resin.
The sources of the raw materials used in the present invention are all commercially available unless otherwise specified.
The tunnel rubber-plastic water stop belt provided by the invention comprises 70-90 parts of natural rubber, preferably 75-85 parts of natural rubber and more preferably 80 parts of natural rubber. In the invention, the natural rubber is preferably solid natural rubber, and the density of the natural rubber is preferably 0.90-0.99 g/cm 3 More preferably 0.93 to 0.95g/cm 3， The strength rating is preferably 1. In the invention, the natural rubber has excellent mechanical property, rebound resilience, insulativity and waterproofness.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 5-15 parts of glycidyl methacrylate, preferably 8-12 parts, and more preferably 10 parts. In the invention, the viscosity of the glycidyl methacrylate at 25 ℃ is preferably 1.5-4.5 mpa.s, more preferably 3-4 mpa.s. The glycidyl methacrylate contains double bonds in the molecule, can be polymerized with double bonds in the natural rubber by free radicals, and meanwhile, the epoxy groups with strong reactivity are easy to carry out ring-opening addition with carboxylic acid or amine, so that the compatibility of the grafted natural rubber with polymers (polyethylene and polyvinyl chloride) and styrene-butadiene rubber grafted epoxy resin macromolecular damping agents is improved.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 10-30 parts of linear low-density polyethylene, preferably 15-25 parts, and more preferably 20 parts. In the invention, the density of the linear low density polyethylene is preferably 0.91-0.94 g/cm 3 More preferably 0.92 to 0.93g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melt index is preferably 0.8-1.5 g/10min, more preferably 1-1.2 g/10min, measured at 190 ℃ under a load of 2.16 kg. In the invention, the linear low-density polyethylene is copolymerized with a small amount of alpha-olefin on the main chain of the linear ethylene, is a molecular structure with a very short and small comonomer branched chain, has the advantages of high strength, good toughness, heat resistance, cold resistance and the like, and also has good environmental stress cracking resistance, impact resistance, tear resistance and other properties, and the natural rubber has better mechanical property and large deformation capability after copolymerization.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 5-10 parts of polyvinyl chloride, preferably 6-8 parts. In the invention, the polyvinyl chloride preferably has a number average molecular weight of 5 to 11 ten thousand, more preferably 7 to 10 ten thousand, and a softening temperature of 70 to 100 ℃, more preferably 80 to 90 ℃. In the invention, the polyvinyl chloride performance is between natural rubber and linear low density polyethylene, and the invention has the advantages of high elasticity of rubber, high modulus of polyethylene material and the like, so that a modulus gradient is formed between the rubber and the polyvinyl chloride and the linear low density polyethylene, the thickness of a two-phase interface layer of the rubber and the linear low density polyethylene is increased, the adhesion capability of two phases of the blend is enhanced, the binding force is stronger, and the mechanical property is more excellent.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 0.3-1 part of dicumyl peroxide, and preferably 0.5-0.8 part of dicumyl peroxide. In the present invention, the dicumyl peroxide functions as a crosslinking agent.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 20-50 parts of filler, preferably 30-40 parts. In the present invention, the filler preferably comprises, in parts by mass: 15-35 parts of carbon black, preferably 20-30 parts; 5-15 parts of wollastonite powder, preferably 8-12 parts, and more preferably 10 parts. In the present invention, the carbon black is used for reinforcing a rubber structure, and the wollastonite powder is used for increasing damping performance.
In the invention, the particle size of the carbon black is preferably 30-70 nm, more preferably 40-60 nm; in the invention, the density of wollastonite powder is preferably 2.8-3.2 g/cm 3 More preferably 3g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The granularity is preferably 700-1500 meshes, more preferably 1000-1200 meshes; the wollastonite powder surface is preferably modified by a coupling agent, and the coupling agent is preferably a silane coupling agent and/or a titanate coupling agent; the method for modifying the coupling agent is not particularly limited, and modification methods well known to those skilled in the art can be used.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 0.5-2.5 parts of vulcanizing agent, preferably 1-2 parts, and more preferably 1.5 parts. In the invention, the vulcanizing agent comprises the following components in parts by weight: 0.5-1.5 parts of sulfur, preferably 1 part; 0.5 to 2 parts of dibenzoic acid peroxide, more preferably 1 to 1.5 parts.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 4-9 parts of an active agent, preferably 5-8 parts, and more preferably 4-7 parts. In the present invention, the active agent is preferably stearic acid and/or zinc oxide.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 1-3 parts of accelerator, preferably 2 parts. In the present invention, the accelerator is preferably N-cyclohexyl-2-benzothiazole sulfenamide.
Based on the mass parts of the natural rubber, the tunnel rubber plastic water stop belt provided by the invention comprises 1-3 parts of an anti-aging agent, preferably 2 parts. In the present invention, the antioxidant is preferably N-isopropyl-N' -phenyl-p-phenylenediamine.
The tunnel rubber-plastic water stop belt provided by the invention further comprises a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and the raw materials of the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprise 10-20 parts of styrene-butadiene rubber, preferably 12-18 parts of styrene-butadiene rubber, and more preferably 15 parts of styrene-butadiene rubber based on the mass parts of the natural rubber. In the invention, the styrene-butadiene rubber is preferably emulsion styrene-butadiene rubber, and the molecular weight of the styrene-butadiene rubber is preferably 10 ten thousand to 30 ten thousand, more preferably 20 ten thousand. In the invention, the physical structure performance, the processing performance and the service performance of products of the styrene-butadiene rubber are close to those of natural rubber, but the performances of water resistance, damping, wear resistance, heat resistance, aging resistance and the like are better than those of the natural rubber.
Based on the mass parts of the natural rubber, the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises 1-4 parts of maleic anhydride, and more preferably 2-3 parts.
Based on the mass parts of the natural rubber, the raw materials of the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprise 0.5-1 part of initiator, and preferably 0.6-0.8 part of initiator. In the present invention, the initiator is preferably dibenzoyl peroxide (BPO).
Based on the mass parts of the natural rubber, the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises 3-8 parts of epoxy resin, preferably 4-6 parts. In the present invention, the epoxy resin is preferably bisphenol A epoxy resin, and the epoxy value of the epoxy resin is preferably 0.18 to 0.40 eq/100g, more preferably 0.2 to 0.3eq/100g. In the invention, bisphenol A epoxy resin has high epoxy functionality, provides more crosslinking points, is easy to form a crosslinked three-dimensional structure, increases friction between molecular chains and improves damping performance; meanwhile, the molecular chain contains more benzene ring macromolecular structures, so that the friction resistance during molecular chain movement is further increased, and the damping performance is improved.
The invention provides a preparation method of the tunnel rubber and plastic water stop belt, which comprises the following steps:
mixing styrene-butadiene rubber, maleic anhydride, an initiator and epoxy resin to obtain a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent;
mixing natural rubber, glycidyl methacrylate and dicumyl peroxide to obtain modified natural rubber;
pre-mixing the modified natural rubber, linear low-density polyethylene, polyvinyl chloride, an active agent, an anti-aging agent, a filler and a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and discharging rubber to obtain a pre-mixed rubber material;
secondary mixing is carried out on the pre-mixed rubber material, a vulcanizing agent and an accelerator to obtain a secondary mixed rubber material;
and (3) carrying out thin-pass extrusion vulcanization molding on the secondary mixed rubber material to obtain the tunnel rubber and plastic water stop belt.
According to the invention, styrene-butadiene rubber, maleic anhydride, an initiator and epoxy resin are mixed to obtain the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent. The mixing is preferably carried out in an internal mixer. In the present invention, the kneading is specifically preferably:
firstly, styrene-butadiene rubber, maleic anhydride and an initiator are subjected to first mixing, and then epoxy resin is added for second mixing. In the invention, the rate of the first mixing is preferably 60-100 r/min, more preferably 80-90 r/min, and the time is preferably 0.3-1 h, more preferably 0.5-0.8 h. In the present invention, the rate of the second kneading is preferably 60 to 100r/min, more preferably 80 to 90r/min, and the time is preferably 1 to 2 hours, more preferably 1.5 hours. In the invention, the temperature of the first mixing is preferably 70-140 ℃, more preferably 80-120 ℃; the temperature of the second kneading is preferably 80 to 150 ℃, more preferably 100 to 130 ℃.
According to the invention, the natural rubber, glycidyl methacrylate and dicumyl peroxide are mixed to obtain the modified natural rubber. The mixing is preferably carried out in an internal mixer. In the invention, the temperature of the mixing is preferably 100-140 ℃, more preferably 110-120 ℃, and the time is preferably 240-600 s, more preferably 300-500 s; the mixing speed is preferably 40-80 r/min, more preferably 50-70 r/min.
After the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent and the modified natural rubber are obtained, the modified natural rubber, the linear low density polyethylene, the polyvinyl chloride, the active agent, the anti-aging agent, the filler and the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent are pre-mixed, and the pre-mixed rubber material is obtained after rubber discharge. The invention preferably carries out the premixing in an internal mixer. In the present invention, the premixing is particularly preferably:
firstly, carrying out first mixing on modified natural rubber, linear low-density polyethylene and polyvinyl chloride, and then adding an active agent, an anti-aging agent, a filler and a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent to carry out second mixing. In the invention, the speed of the first mixing is preferably 20-50 r/min, more preferably 30-40 r/min, and the time is preferably 30-120 s, more preferably 60-90 s. In the present invention, the rate of the second kneading is preferably the same as that of the first kneading, and the time of the second kneading is preferably 120 to 240s, more preferably 150 to 180s. In the invention, the temperature of the first mixing is preferably 70-140 ℃, more preferably 80-120 ℃; the temperature of the second kneading is preferably 80 to 150 ℃, more preferably 100 to 130 ℃.
In the present invention, the removal of the gum material means that the gum material is taken out of the internal mixer.
After the premixed rubber material is obtained, the pre-mixed rubber material, a vulcanizing agent and an accelerator are subjected to secondary mixing, so that secondary mixed rubber material is obtained. The secondary mixing is preferably carried out in an internal mixer. In the present invention, the temperature of the secondary kneading is preferably 60 to 80 ℃, more preferably 70 ℃, and the time is preferably 30 to 90 seconds, more preferably 50 to 80 seconds. In the invention, the rate of the secondary mixing is preferably 40-80 r/min, more preferably 50-70 r/min.
After the secondary mixed rubber material is obtained, the invention performs thin-pass extrusion vulcanization molding on the secondary mixed rubber material to obtain the tunnel rubber and plastic water stop belt. The invention preferably performs the thin pass in an open mill. In the present invention, the number of thin passes is preferably 3 to 6, more preferably 4 to 5.
In the present invention, the extrusion vulcanization molding preferably includes extrusion molding and vulcanization setting. In the present invention, the extrusion molding rate is preferably 1 to 3m/min, more preferably 2m/min. In the invention, the temperature of the vulcanization shaping is preferably 150-240 ℃, more preferably 180-220 ℃, and the time of the vulcanization shaping is preferably 10-40 min, more preferably 20-30 min.
The invention provides application of the tunnel rubber and plastic water stop belt in a concrete joint of a tunnel with an earthquake fracture zone.
The tunnel rubber and plastic water stop belt, the preparation method and the application thereof provided by the invention are described in detail below by combining with the examples, but the tunnel rubber and plastic water stop belt and the preparation method and the application thereof are not to be construed as limiting the protection scope of the invention.
Example 1
The preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 70 parts by weight of natural rubber, 5 parts by weight of glycidyl methacrylate and 0.3 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set to 100 ℃ and the mixing is carried out for 240 seconds.
(2) 10 parts by weight of styrene-butadiene rubber, 1 part by weight of maleic anhydride and 0.5 part by weight of initiator dibenzoyl peroxide are added into an internal mixer, the rotating speed is set to be 60r/min, the mixing is carried out for 0.3h, 3 parts by weight of epoxy resin is added, and the mixing is continued for 1h, so that the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is prepared.
(3) Adding modified natural rubber, 30 parts by weight of linear low-density polyethylene, 10 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 20r/min, and mixing for 120s; then adding 4 parts by weight of active agent, 1 part by weight of anti-aging agent, 35 parts by weight of carbon black, 15 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 120 seconds to discharge rubber.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled at 60 ℃, adding 0.5 part by weight of sulfur, 2 parts by weight of dicumyl peroxide and 1 part by weight of accelerator until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 30 seconds; and (3) carrying out thin-pass 3 times on the secondary mixed rubber material on an open mill to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 150 ℃, and the extrusion speed is 1m/min.
Example 2
The preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 90 parts by weight of natural rubber, 15 parts by weight of glycidyl methacrylate and 1 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set to 140 ℃ and the mixing is carried out for 600 seconds.
(2) Adding 20 parts by weight of styrene-butadiene rubber, 4 parts by weight of maleic anhydride and 1 part by weight of initiator dibenzoyl peroxide into an internal mixer, setting the rotating speed to 100r/min, mixing for 1h, adding 8 parts by weight of epoxy resin, and continuing mixing for 2h to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding modified natural rubber, 10 parts by weight of linear low-density polyethylene, 5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 50r/min, and mixing for 30s; then adding 9 parts by weight of active agent, 3 parts by weight of anti-aging agent, 15 parts by weight of carbon black, 5 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 240 seconds to discharge rubber.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled to be 80 ℃, adding 1.5 parts by weight of sulfur, 0.5 part by weight of dicumyl peroxide and 3 parts by weight of accelerator until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 90 seconds; and (3) thinning the secondary mixed rubber material on an open mill for 6 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 240 ℃, and the extrusion speed is 3m/min.
Example 3
The preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 75 parts by weight of natural rubber, 7.5 parts by weight of glycidyl methacrylate and 0.4 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set at 120 ℃ and the mixing is carried out for 300 seconds.
(2) Adding 12 parts by weight of styrene-butadiene rubber, 1.5 parts by weight of maleic anhydride and 0.6 part by weight of initiator dibenzoyl peroxide into an internal mixer, setting the rotating speed to be 70r/min, mixing for 0.5h, adding 4 parts by weight of epoxy resin, and continuously mixing for 1.2h to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding modified natural rubber, 25 parts by weight of linear low-density polyethylene, 8.5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 25r/min, and mixing for 100s; then adding 4 parts by weight of zinc oxide, 1.5 parts by weight of stearic acid, 1.5 parts by weight of N-isopropyl-N' -phenyl p-phenylenediamine, 30 parts by weight of carbon black, 12 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 140s for rubber discharging.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled to be 65 ℃, adding 0.7 part by weight of sulfur, 1.5 parts by weight of dicumyl peroxide and 1.5 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide until all the vulcanizing agent and the accelerator are eaten into the sizing material, and carrying out secondary mixing for 40s; and (3) thinning the secondary mixed rubber material on an open mill for 4 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 180 ℃, and the extrusion speed is 1.5m/min.
Example 4
The preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 80 parts by weight of natural rubber, 9 parts by weight of glycidyl methacrylate and 0.6 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set at 125 ℃ and the mixing is carried out for 400s.
(2) Adding 14 parts by weight of styrene-butadiene rubber, 2.5 parts by weight of maleic anhydride and 0.7 part by weight of initiator dibenzoyl peroxide into an internal mixer, setting the rotating speed to be 80r/min, mixing for 0.7h, adding 6 parts by weight of epoxy resin, and continuously mixing for 1.5h to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding modified natural rubber, 20 parts by weight of linear low-density polyethylene, 7.5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 35r/min, and mixing for 80s; then adding 4.5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of N-isopropyl-N' -phenyl p-phenylenediamine, 25 parts by weight of carbon black, 9 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 180 seconds for rubber discharging.
(4) Putting the sizing material into an internal mixer, when the temperature is controlled to be 70 ℃, adding 1 part by weight of sulfur, 1.2 parts by weight of dicumyl peroxide and 2 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 60 seconds; and (3) thinning the secondary mixed rubber material on an open mill for 5 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 200 ℃, and the extrusion speed is 2m/min.
Example 5
The preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 85 parts by weight of natural rubber, 12.5 parts by weight of glycidyl methacrylate and 0.8 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set at 125 ℃ and the mixing is carried out for 400s.
(2) 16 parts by weight of styrene-butadiene rubber, 3.5 parts by weight of maleic anhydride and 0.9 part by weight of initiator dibenzoyl peroxide are added into an internal mixer, the rotating speed is set to 90r/min, the mixing is carried out for 0.9h, 7 parts by weight of epoxy resin is added, and the mixing is continued for 1.8h, so as to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding modified natural rubber, 15 parts by weight of linear low-density polyethylene, 6.5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 45r/min, and mixing for 60s; then adding 5.5 parts by weight of zinc oxide, 2.5 parts by weight of stearic acid, 2.5 parts by weight of N-isopropyl-N' -phenyl p-phenylenediamine, 20 parts by weight of carbon black, 7 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 220 seconds for rubber discharging.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled at 75 ℃, putting 1.2 parts by weight of sulfur, 0.8 part by weight of dicumyl peroxide and 2.5 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide into the internal mixer until all the vulcanizing agent and the accelerator are eaten into the sizing material, and carrying out secondary mixing for 70s; and (3) thinning the secondary mixed rubber material on an open mill for 6 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 220 ℃, and the extrusion speed is 2.5m/min.
Comparative example 1
In contrast to example 1, the preparation method of the tunnel rubber and plastic water stop is as follows:
(1) 70 parts by weight of natural rubber were charged into an internal mixer, the temperature was set at 100℃and the mixture was kneaded for 240s.
(2) 10 parts by weight of styrene-butadiene rubber, 1 part by weight of maleic anhydride and 0.5 part by weight of initiator dibenzoyl peroxide are added into an internal mixer, the rotating speed is set to be 60r/min, the mixing is carried out for 0.3h, 3 parts by weight of epoxy resin is added, and the mixing is continued for 1h, so that the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is prepared.
(3) Adding modified natural rubber, 30 parts by weight of linear low-density polyethylene, 10 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 20r/min, and mixing for 120s; then adding 4 parts by weight of active agent, 1 part by weight of anti-aging agent, 35 parts by weight of carbon black, 15 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 120 seconds to discharge rubber.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled at 60 ℃, adding 0.5 part by weight of sulfur, 2 parts by weight of dicumyl peroxide and 1 part by weight of accelerator until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 30 seconds; and (3) carrying out thin-pass 3 times on the secondary mixed rubber material on an open mill to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 150 ℃, and the extrusion speed is 1m/min.
Comparative example 2
In contrast to example 2, the preparation method of the tunnel rubber and plastic water stop is as follows:
(1) 90 parts by weight of natural rubber, 15 parts by weight of glycidyl methacrylate and 1 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set to 140 ℃ and the mixing is carried out for 600 seconds.
(2) Adding modified natural rubber, 10 parts by weight of linear low-density polyethylene, 5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 50r/min, and mixing for 30s; then adding 9 parts by weight of active agent, 3 parts by weight of anti-aging agent, 15 parts by weight of carbon black and 5 parts by weight of wollastonite powder, and continuously mixing for 240s to discharge rubber.
(3) Putting the sizing material into an internal mixer, and when the temperature is controlled to be 80 ℃, adding 1.5 parts by weight of sulfur, 0.5 part by weight of dicumyl peroxide and 3 parts by weight of accelerator until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 90 seconds; and (3) thinning the secondary mixed rubber material on an open mill for 6 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(4) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 240 ℃, and the extrusion speed is 3m/min.
Comparative example 3
In contrast to example 3, the method for preparing the tunnel rubber and plastic water stop is as follows:
(1) 75 parts by weight of natural rubber, 7.5 parts by weight of glycidyl methacrylate and 0.4 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set at 120 ℃ and the mixing is carried out for 300 seconds.
(2) Adding 12 parts by weight of styrene-butadiene rubber, 1.5 parts by weight of maleic anhydride and 0.6 part by weight of initiator dibenzoyl peroxide into an internal mixer, setting the rotating speed to be 70r/min, mixing for 0.5h, adding 4 parts by weight of epoxy resin, and continuously mixing for 1.2h to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding the modified natural rubber into an internal mixer, setting the rotating speed to 25r/min, and mixing for 100s; then adding 4 parts by weight of zinc oxide, 1.5 parts by weight of stearic acid, 1.5 parts by weight of N-isopropyl-N' -phenyl p-phenylenediamine, 30 parts by weight of carbon black, 12 parts by weight of wollastonite powder and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 140s for rubber discharging.
(4) Putting the sizing material into an internal mixer, and when the temperature is controlled to be 65 ℃, adding 0.7 part by weight of sulfur, 1.5 parts by weight of dicumyl peroxide and 1.5 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide until all the vulcanizing agent and the accelerator are eaten into the sizing material, and carrying out secondary mixing for 40s; and (3) thinning the secondary mixed rubber material on an open mill for 4 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 180 ℃, and the extrusion speed is 1.5m/min.
Comparative example 4
In contrast to example 4, the preparation method of the tunnel rubber and plastic water stop is as follows:
the preparation method of the tunnel rubber and plastic water stop belt comprises the following steps:
(1) 80 parts by weight of natural rubber, 9 parts by weight of glycidyl methacrylate and 0.6 part by weight of dicumyl peroxide as a crosslinking agent are added into an internal mixer, and the temperature is set at 125 ℃ and the mixing is carried out for 400s.
(2) Adding 14 parts by weight of styrene-butadiene rubber, 2.5 parts by weight of maleic anhydride and 0.7 part by weight of initiator dibenzoyl peroxide into an internal mixer, setting the rotating speed to be 80r/min, mixing for 0.7h, adding 6 parts by weight of epoxy resin, and continuously mixing for 1.5h to prepare the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent.
(3) Adding modified natural rubber, 20 parts by weight of linear low-density polyethylene, 7.5 parts by weight of polyvinyl chloride and the mixture into an internal mixer, setting the rotating speed to 35r/min, and mixing for 80s; then adding 4.5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of N-isopropyl-N' -phenyl p-phenylenediamine, 25 parts by weight of carbon black, 9 parts by weight of white carbon black and styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and continuously mixing for 180 seconds for rubber discharging.
(4) Putting the sizing material into an internal mixer, when the temperature is controlled to be 70 ℃, adding 1 part by weight of sulfur, 1.2 parts by weight of dicumyl peroxide and 2 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide until the vulcanizing agent and the accelerator are completely eaten into the sizing material, and carrying out secondary mixing for 60 seconds; and (3) thinning the secondary mixed rubber material on an open mill for 5 times to prepare final rubber, thereby obtaining the rubber matrix of the tunnel rubber-plastic water stop belt.
(5) And extruding the rubber matrix of the tunnel rubber-plastic water stop belt, forming by microwave vulcanization, wherein the vulcanization temperature is 200 ℃, and the extrusion speed is 2m/min.
Performance testing
The tunnel rubber and plastic water stop tapes obtained in the above examples and comparative examples were tested for tensile strength, elongation at break, equivalent damping ratio, and constant compression set, and the results are shown in table 1.
Wherein, the tensile strength and the elongation at break are tested according to the rule of the measurement of the tensile stress and strain properties of vulcanized rubber or thermoplastic rubber (GB/T528);
equivalent damping ratio was measured according to the general rule of section 1 (GB/T9870.1-2006) two-piece shear test for the determination of the dynamic Properties of vulcanized rubber or thermoplastic rubber
Constant compression set is tested according to the specification GB/T7759.1 determination of compression set of vulcanizates or thermoplastic rubbers.
Table 1 raw materials and Properties of the rubber and plastic Water stops for the examples and comparative examples
As can be seen from Table 1, the tunnel rubber and plastic water stop provided by the invention has better strength, elongation and damping performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A rubber and plastic water stop belt for a tunnel comprises the following raw materials in parts by mass:
70-90 parts of natural rubber;
5-15 parts of glycidyl methacrylate;
10-30 parts of linear low density polyethylene;
5-10 parts of polyvinyl chloride;
0.3-1 parts of dicumyl peroxide;
20-50 parts of filler;
0.5-2.5 parts of vulcanizing agent;
4-9 parts of an active agent;
1-3 parts of an accelerator;
1-3 parts of an anti-aging agent;
the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent is characterized by further comprising a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, wherein the styrene-butadiene rubber grafted epoxy resin macromolecular damping agent comprises the following raw materials in parts by mass based on the parts by mass of the natural rubber:
10-20 parts of styrene-butadiene rubber;
1-4 parts of maleic anhydride;
0.5-1 part of an initiator;
3-8 parts of epoxy resin;
the natural rubber is solid natural rubber, and the density of the natural rubber is 0.90-0.99 g/cm 3 The strength grade is 1 grade;
the viscosity of the glycidyl methacrylate at 25 ℃ is 1.5-4.5 mpa-s;
the filler comprises the following components in parts by mass:
15-35 parts of carbon black;
5-15 parts of wollastonite powder;
the wollastonite powder has a density of 2.8~3.2g/cm 3 The granularity is 700-1500 meshes; the wollastonite powder surface is modified by a coupling agent;
the vulcanizing agent comprises the following components in parts by weight:
0.5-1.5 parts of sulfur;
0.5-2 parts of dibenzoic acid peroxide.
2. The tunnel rubber and plastic water stop according to claim 1, wherein the linear low density polyethylene has a density of 0.91-0.94 g/cm 3 The melt index is 0.8-1.5 g/10min; the melt index was measured at 190℃under a load of 2.16 kg;
the polyvinyl chloride has a number average molecular weight of 5-11 ten thousand and a softening temperature of 70-100 ℃.
3. The tunnel rubber-plastic water stop according to claim 1, wherein the styrene-butadiene rubber is emulsion styrene-butadiene rubber, and the molecular weight of the styrene-butadiene rubber is 10-30 ten thousand;
the epoxy resin is bisphenol A epoxy resin, and the epoxy value of the epoxy resin is 0.18-0.40 eq/100g.
4. The tunnel rubber and plastic water stop according to claim 1, wherein the initiator is dibenzoyl peroxide;
the active agent is stearic acid and/or zinc oxide;
the accelerator is N-cyclohexyl-2-benzothiazole sulfenamide;
the anti-aging agent is N-isopropyl-N' -phenyl p-phenylenediamine.
5. The method for preparing the tunnel rubber and plastic water stop belt according to any one of claims 1-4, comprising the following steps:
mixing styrene-butadiene rubber, maleic anhydride, an initiator and epoxy resin to obtain a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent;
mixing natural rubber, glycidyl methacrylate and dicumyl peroxide to obtain modified natural rubber;
pre-mixing the modified natural rubber, linear low-density polyethylene, polyvinyl chloride, an active agent, an anti-aging agent, a filler and a styrene-butadiene rubber grafted epoxy resin macromolecular damping agent, and discharging rubber to obtain a pre-mixed rubber material;
secondary mixing is carried out on the pre-mixed rubber material, a vulcanizing agent and an accelerator to obtain a secondary mixed rubber material;
and (3) carrying out thin-pass extrusion vulcanization molding on the secondary mixed rubber material to obtain the tunnel rubber and plastic water stop belt.
6. The method according to claim 5, wherein the extrusion speed of the extrusion vulcanization molding is 1 to 3m/min, and the vulcanization temperature is 150 to 240 ℃.
7. The use of the tunnel rubber and plastic water stop according to any one of claims 1 to 4 or the tunnel rubber and plastic water stop prepared by the preparation method according to claim 5 or 6 in a tunnel concrete joint of an earthquake fracture zone.
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| JPH0834089A (en) * | 1994-07-25 | 1996-02-06 | Lintec Corp | Damping sheet |
| JPH08176352A (en) * | 1994-12-22 | 1996-07-09 | Ntn Corp | Damping elastic body composition |
| CN1337979A (en) * | 1998-12-04 | 2002-02-27 | Syh技术控股有限公司 | Thermoplastic rubber composition |
| JP2009235336A (en) * | 2008-03-28 | 2009-10-15 | Tokai Rubber Ind Ltd | Highly damping rubber composition and vibration control damper obtained by using the same |
| WO2014050734A1 (en) * | 2012-09-25 | 2014-04-03 | 東レ株式会社 | Natural rubber-containing thermoplastic resin composition and molded article thereof |
| CN105037832A (en) * | 2015-09-16 | 2015-11-11 | 合肥海畅电气技术有限公司 | Arc extinguishing shell material of motor protection controller |
| CN114213805A (en) * | 2021-12-07 | 2022-03-22 | 中国科学院金属研究所 | A kind of high toughness, high damping graphene/styrene-butadiene rubber/epoxy resin composite material and preparation method thereof |
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2023
- 2023-06-29 CN CN202310778185.8A patent/CN116515179B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834089A (en) * | 1994-07-25 | 1996-02-06 | Lintec Corp | Damping sheet |
| JPH08176352A (en) * | 1994-12-22 | 1996-07-09 | Ntn Corp | Damping elastic body composition |
| CN1337979A (en) * | 1998-12-04 | 2002-02-27 | Syh技术控股有限公司 | Thermoplastic rubber composition |
| JP2009235336A (en) * | 2008-03-28 | 2009-10-15 | Tokai Rubber Ind Ltd | Highly damping rubber composition and vibration control damper obtained by using the same |
| WO2014050734A1 (en) * | 2012-09-25 | 2014-04-03 | 東レ株式会社 | Natural rubber-containing thermoplastic resin composition and molded article thereof |
| CN105037832A (en) * | 2015-09-16 | 2015-11-11 | 合肥海畅电气技术有限公司 | Arc extinguishing shell material of motor protection controller |
| CN114213805A (en) * | 2021-12-07 | 2022-03-22 | 中国科学院金属研究所 | A kind of high toughness, high damping graphene/styrene-butadiene rubber/epoxy resin composite material and preparation method thereof |
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