CN110372924A - A kind of composite rubber water stop - Google Patents

A kind of composite rubber water stop Download PDF

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Publication number
CN110372924A
CN110372924A CN201910506372.4A CN201910506372A CN110372924A CN 110372924 A CN110372924 A CN 110372924A CN 201910506372 A CN201910506372 A CN 201910506372A CN 110372924 A CN110372924 A CN 110372924A
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parts
water stop
composite rubber
rubber
agent
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李承忠
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/06Making microcapsules or microballoons by phase separation
    • B01J13/14Polymerisation; cross-linking
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42Nitriles
    • C08F220/44Acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2206Oxides; Hydroxides of metals of calcium, strontium or barium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18Spheres
    • C08L2205/20Hollow spheres

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of composite rubber water stops, belong to technical field of polymer materials.According to parts by weight, it successively weighs: 50~60 parts of nitrile rubbers, 30~40 parts of natural rubbers, 20~30 parts of chlorinated polyethylene rubbers, 5~10 parts of plasticizer, 2~5 parts of heat stabilizers, 8~12 parts of vulcanizing agents, 10~18 parts of calcium oxide, 8~15 parts of toluene di-isocyanate(TDI)s, 10~15 parts of microballoons and 15~18 parts of micro-capsules, nitrile rubber is mixed with natural rubber, and chlorinated polyethylene rubber is added, plasticizer, heat stabilizer, vulcanizing agent, calcium oxide, toluene di-isocyanate(TDI), microballoon and micro-capsule, after being stirred, obtain rubber mixture, by rubber mixture mixing, after vulcanization, compression moulding, up to composite rubber water stop.The composite rubber water stop of technical solution of the present invention preparation has the characteristics that excellent waterproof performance and mechanical property, has broad prospects in the development of high polymer material technology industry.

Description

A kind of composite rubber water stop
Technical field
The invention discloses a kind of composite rubber water stops, belong to technical field of polymer materials.
Background technique
Rubber fastening band and water stop rubber system add various auxiliary agents using natural rubber and various synthetic rubber as primary raw material And filler material, it plasticated, be kneaded, compression moulding, description is more, there is bridge type, mountain type, p-type, U-shaped, Z-type, B-mode, T Type, H-type, E type, Q type etc..
In rubber fastening band work progress, due to the stone of many of concrete wedge angle and the reinforcing bar of sharp sword, so Pour pound locating water-stopping band when, it should be noted that the impact force smash is poured, in order to avoid puncture rubber fastening band since strength is excessive.Such as hair Existing fracture phenomena should repair in time, otherwise deform in seam and when by hydraulic pressure, rubber fastening band can resist the ability of external force Just it will be greatly reduced.It in positioning rubber waterstop, has to make it to keep open and flat in interface locations, can not allow waterstop Rolling is twisted together as discovery has torsion not show as that should be aligned in time.When casting fixed waterstop, water band-offset should be prevented It moves, in order to avoid unilateral shorten, influences water-stagnating effect.It must also be fullyd shake in casting and compacting of concrete, in order to avoid waterstop and concrete Water-stagnating effect is influenced in conjunction with bad.Sealing belt lacing must be bonded well, and if construction site condition has, heat cure can be used The method of connection.
Rubber fastening band mixes a variety of auxiliary agents and filler material using natural rubber or various synthetic rubber as primary raw material, warp The processes such as plasticizing, mixing, calendering and vulcanization are made.It can be classified as buried rubber fastening band and back sticking type rubber again according to service condition Glue waterstop.The sealing material has good elasticity, wearability, resistance to ag(e)ing and tear resistance, adaptive deformation ability is strong, Waterproof performance is good, and temperature use scope is -45 DEG C~+60 DEG C.When temperature is more than 70 DEG C and rubber fastening band by strong oxygen When change is acted on or corroded by organic solvents such as oils, rubber fastening band must not be used.Generally often poured with after in outer wall of basement It is used when belt construction.
Buried water strip is the waterproof material that concrete seam is important in tunnel, is mounted among tunnel double-lining, can be with It deforms with the displacement of tunnel deformation joint without losing water stopping function, using its sealing and soft feature, water is intercepted Except two linings.
Current waterstop is all smaller in lateral stiffness, it is easy to be bent.The quality of sealing belt construction is also tunnel water proofing Pith, at present waterstop construction when, be to erect the side of waterstop, the other side is hanging, and with reinforcing bar clamp general Waterstop " end " is flat, although ensure that sagging, deformation does not occur in construction for waterstop, increases the construction time, delays Construction speed virtually increases construction cost, and waterstop is directly contacted with reinforcing bar, this is resulted between waterstop and reinforcing bar Concrete is difficult closely knit, and concrete between waterstop and reinforcing bar also easily causes crackle, stomata etc., shadow during upper number Construction quality is rung, leakage hidden trouble is increased.Remove reinforcing bar clamp, waterstop can be due to self gravity, it is easy to occur Sagging, deformation, and during poured concrete, waterstop as impact, flowing and the process of vibrating of concrete and It shifts, the anchored end that not can guarantee waterstop thus can be anchored completely around in concrete, cause waterstop complete Performance its water-proof function.Due to non-binding power between waterstop rubber and concrete, after waterstop shifts, make seam crossing Concrete is thinning, causes " chip off-falling " phenomenon, seriously affects traffic safety.
Waterstop, for the presentation quality for guaranteeing waterstop, prevents starved, upper and lower level between mold when producing vulcanization The sum of semi-finished product film is greater than mold cavity thickness, and rubber is fluid state in Pressurized-heated, and extra rubber is needed from mould Have delivery end outflow, while will drive stiffening plate, change origin-location, causes reinforcement plate spacing excessive, substandard product.
And traditional waterstop adds water-absorbing resin, and sealing effect is played in the expansion after being absorbed water by water-absorbing resin, increases Stress inside waterstop, the mechanical property of reduced waterstop, and so that the water-stagnating effect of waterstop is affected, because This, the shortcomings that how improving traditional rubber fastening band, develops the rubber fastening band with good comprehensive performance and is in the hope of exploring Problem to be solved.
Summary of the invention
The present invention solves the technical problem of: water-absorbing resin is added for traditional waterstop, and is inhaled by water-absorbing resin Sealing effect is played in expansion after water, increases the stress inside waterstop, the mechanical property of reduced waterstop, and make to stop The water-stagnating effect of water band is affected, and provides a kind of composite rubber water stop.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of composite rubber water stop is made of the raw material of following parts by weight: 50~60 parts of nitrile rubbers, 30~40 parts of days Right rubber, 20~30 parts of chlorinated polyethylene rubbers, 5~10 parts of plasticizer, 2~5 parts of heat stabilizers, 8~12 parts of vulcanizing agents, 10~ 18 parts of calcium oxide, 8~15 parts of toluene di-isocyanate(TDI)s, 10~15 parts of microballoons and 15~18 parts of micro-capsules;
The microballoon the preparation method comprises the following steps:
(1) according to parts by weight, it successively weighs: 200~300 parts of deionized waters, 70~100 parts of sodium chloride, 2.0~2.5 parts of hydrogen Deionized water is mixed with sodium chloride, and hydroxide is added by magnesia, 5~10 parts of Magnesium dichloride hexahydrates, 1~2 part of dispersing agent Magnesium, Magnesium dichloride hexahydrate and dispersing agent after being stirred, obtain aqueous mixture;
(2) according to parts by weight, it successively weighs: 10~15 parts of acrylonitrile, 1~3 part of vinylidene chloride, 10~12 parts of methacrylic acids Methyl esters, 1~3 part of butyl acrylate, 15~20 parts of low-boiling foaming agents, 2~4 parts of initiators and 4~5 parts of crosslinking agents, by propylene Nitrile is mixed with methyl methacrylate, and vinylidene chloride is added, butyl acrylate, low-boiling foaming agent, initiator and crosslinking agent, After being stirred, oil mixture is obtained;
(3) oil mixture object mixed with water 1:1 in mass ratio is mixed, emulsification obtains mix emulsion fluid;
(4) after being stirred to react mix emulsion fluid under nitrogen atmosphere, mixture of microspheres is obtained, adjusts the pH to 2 of mixture of microspheres ~3, it filters, washs, it is dry, obtain microballoon;
The micro-capsule the preparation method comprises the following steps:
(5) according to parts by weight, it successively weighs: 10~20 parts of styrene, 10~12 parts of divinylbenzenes, 2~5 parts of benzoyl peroxides Formyl, 12~15 parts of epoxy resin, 8~12 parts of epoxy propane butyl ethers, 5~7 parts of surfactants and 40~50 parts of deionizations Surfactant is mixed with deionized water, and styrene is added by water, divinylbenzene, divinylbenzene, epoxy resin and ring Ethylene Oxide butyl ether after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, obtains micro-capsule.
The plasticizer phthalic acid two (2- ethyl hexyl) ester, dioctyl phthalate or BBP(Butyl Benzyl Phthalate In any one.
The heat stabilizer is anti-aging agent RD, any one in antioxidant 4020 or paraffin.
The vulcanizing agent is any one in sulphur or benzoyl peroxide.
The dispersing agent is dispersing agent NNO, any one in Dispersant MF or dispersing agent 5040.
The low-boiling foaming agent is to mix isooctane with normal octane 1:1 in mass ratio, and isooctane quality 0.2 is added ~0.4 times of isopentane, is stirred, and obtains low-boiling foaming agent.
The initiator is potassium peroxydisulfate, any one in sodium peroxydisulfate or azodiisobutyronitrile.
The crosslinking agent is any one in three acrylic acid propane front three alcohol esters or ethylene glycol dimethacrylate.
The surfactant is any one in gum arabic or neopelex.
The isocyanate-modified oxidation stone of nitrile rubber quality 8~10% can also be added in the composite rubber water stop Black alkene;The preparation process of the isocyanate-modified graphene oxide are as follows: according to parts by weight, successively take 10~20 parts of oxidation stones Black alkene, 30~40 parts of toluene di-isocyanate(TDI)s, 30~40 parts of acetone, after mixing, 3~5h of heating reflux reaction is washed using filter It washs and is dried in vacuo, obtain isocyanate-modified graphene oxide.
The beneficial effects of the present invention are:
(1) calcium oxide, microballoon and micro-capsule are added when preparing composite rubber water stop by the present invention, are cooperated and are assisted by three To solve technical problem, during three plays a role, firstly, the microballoon being added has thermal expansivity, after product meets water, It can be reacted into the hydrone in product with calcium oxide, amount of heat be discharged while forming calcium hydroxide, so that microballoon be made to send out Volume expansion is given birth to, mutual extrusion after microsphere expansion makes interiors of products moisture diffusion by blocking, effectively moisture avoided further to seep It penetrates into inside, to reduce the hole of interiors of products, improves the waterproofness of product, secondly as the expansion of microballoon, thus It is squeezed interiors of products space, squeeze the pressure of generation and then ruptures the micro-capsule being added, epoxy resin core material is sudden and violent It is exposed in product, since the hydrone that interiors of products enters can be reacted with the toluene di-isocyanate(TDI) being added in product, generate amine Substance and carbon dioxide, the amine substance of generation can promote the solidification of epoxy resin under heat effect, to improve product Crosslinking degree, and then further increase the breaking strength of product and waterproof performance, and the carbon dioxide generated can be with oxidation The calcium hydroxide that calcium is formed reacts, and enhanced winnofil crystal is formed inside product system, thus effectively It avoids the calcium hydroxide of small volume from being gradually lost under water function, to introduce new moisture diffusion channel, effectively avoids The decline of product waterproof property in use, to make the breaking strength of product further increase, simultaneously because carbonic acid Filling of the calcium to interiors of products hole, can be such that the waterproofness of product further increases;
(2) technical solution of the present invention is by being further introduced into isocyanate-modified graphene oxide, graphene oxide with first It is conjugated area's hydroxyl in phenylene diisocyanate reaction process, in molecular structure and edge carboxyl institute band reactive hydrogen atom can be with Toluene di-isocyanate(TDI) reacts, and forms chemical bonding, to introduce toluene two at graphene oxide edge and conjugation area The molecular structure of isocyanate structural, introducing can effectively widen graphene oxide interlamellar spacing, and graphene oxide is made in the base may be used With with monolithic layer structure disperses, and the originally hydrophilic hydroxyl and carboxyl transformation of interlayer be for hydrophobic structure, so as to solid in product After chemical conversion type, in surface and the internal water blocking layer structure for forming continuous sheet, and the introducing of laminated structure can effectively extend moisture Diffusion path, avoid moisture further penetrates into inside.
Specific embodiment
According to parts by weight, 10~20 parts of graphene oxides are successively taken, 30~40 parts of toluene di-isocyanate(TDI)s, 30~40 parts Acetone, after mixing, 3~5h of heating reflux reaction, using filter, washing and vacuum drying obtain isocyanate-modified graphite oxide Alkene;According to parts by weight, it successively weighs: 200~300 parts of deionized waters, 70~100 parts of sodium chloride, 2.0~2.5 parts of hydroxides Magnesium, 5~10 parts of Magnesium dichloride hexahydrates, 1~2 part of dispersing agent mix deionized water with sodium chloride, and to deionized water and chlorination Magnesium hydroxide, Magnesium dichloride hexahydrate and dispersing agent are added in the mixture of sodium, in temperature be 30~50 DEG C, revolving speed be 300~ Under conditions of 400r/min, after being stirred 30~40min, aqueous mixture is obtained;According to parts by weight, it successively weighs: 10~ 15 parts of acrylonitrile, 1~3 part of vinylidene chloride, 10~12 parts of methyl methacrylates, 1~3 part of butyl acrylate, 15~20 parts low Boiling point blowing agent, 2~4 parts of initiators and 4~5 parts of crosslinking agents, acrylonitrile is mixed with methyl methacrylate, and to acrylonitrile With vinylidene chloride, butyl acrylate, low-boiling foaming agent, initiator and crosslinking are added in the mixture of methyl methacrylate Agent is 30~50 DEG C in temperature, under conditions of revolving speed is 350~380r/min, after being stirred 20~40min, it is mixed to obtain oily phase Close object;Oil mixture object mixed with water 1:1 in mass ratio is mixed, under conditions of revolving speed is 6000~8000r/min After emulsifying 5~12min, mix emulsion fluid is obtained, the rate into mix emulsion fluid with 18~25mL/min is passed through nitrogen, and in temperature Degree is 60~65 DEG C, under conditions of revolving speed is 300~400r/min, after being stirred to react 6~8h, obtains mixture of microspheres, uses quality The hydrochloric acid that score is 10~15% adjusts the pH to 2~3 of mixture of microspheres, and filtering obtains filter cake, filter cake is washed with deionized 8 After~10 times, and microballoon is obtained after dry 1~2h under conditions of being 70~80 DEG C in temperature;According to parts by weight, it successively weighs: 10~20 parts of styrene, 10~12 parts of divinylbenzenes, 2~5 parts of benzoyl peroxides, 12~15 parts of epoxy resin, 8~12 parts Epoxy propane butyl ether, 5~7 parts of surfactants and 40~50 parts of deionized waters, surfactant is mixed with deionized water In three-necked flask, styrene, divinylbenzene, divinylbenzene, epoxy resin and propylene oxide are added into three-necked flask Butyl ether, and nitrogen is passed through into three-necked flask with the rate of 20~30mL/min, in temperature be 70~80 DEG C, revolving speed 240 Under conditions of~350r/min, after being stirred to react 7~8h, filtering obtains micro-capsule blank, micro-capsule blank is washed with deionized 8 After~10 times, dry 1~3h under conditions of being 70~80 DEG C in temperature obtains micro-capsule;According to parts by weight, it successively weighs: 50~ 60 parts of nitrile rubbers, 30~40 parts of natural rubbers, 20~30 parts of chlorinated polyethylene rubbers, 5~10 parts of plasticizer, 2~5 parts of heat are steady Determine agent, 8~12 parts of vulcanizing agents, 10~18 parts of calcium oxide, 8~15 parts of toluene di-isocyanate(TDI)s, 10~15 parts of microballoons, 15~18 parts The isocyanate-modified graphene oxide of micro-capsule and nitrile rubber quality 8~10% mixes nitrile rubber with natural rubber In blender, and chlorinated polyethylene rubber is added into blender, plasticizer, heat stabilizer, vulcanizing agent, calcium oxide, toluene Diisocyanate, microballoon, micro-capsule and isocyanate-modified graphene oxide, in temperature be 30~60 DEG C, revolving speed be 300~ Under conditions of 400r/min, after being stirred 30~40min, obtain rubber mixture, by rubber mixture in temperature be 80~100 Under conditions of DEG C, after 15~30min of mixing, mixing material is obtained, by mixing material under conditions of temperature is 120~160 DEG C, vulcanization 5 After~10min, compression moulding is to get composite rubber water stop.The plasticizer phthalic acid two (2- ethyl hexyl) ester, adjacent benzene Any one in diformazan dioctyl phthalate or BBP(Butyl Benzyl Phthalate.The heat stabilizer be anti-aging agent RD, antioxidant 4020 or Any one in paraffin.The vulcanizing agent is any one in sulphur or benzoyl peroxide.The dispersing agent is dispersing agent Any one in NNO, Dispersant MF or dispersing agent 5040.The low-boiling foaming agent be by isooctane and normal octane in mass ratio 1:1 mixing, and 0.2~0.4 times of isooctane quality of isopentane is added, it is stirred, obtains low-boiling foaming agent.The initiator For potassium peroxydisulfate, any one in sodium peroxydisulfate or azodiisobutyronitrile.The crosslinking agent is three acrylic acid propane front three alcohol esters Or any one in ethylene glycol dimethacrylate.The surfactant is gum arabic or neopelex In any one.
Example 1
According to parts by weight, 20 parts of graphene oxides, 40 parts of toluene di-isocyanate(TDI)s are successively taken, 40 parts of acetone after mixing, heat Back flow reaction 5h, using filter, washing and vacuum drying obtain isocyanate-modified graphene oxide;According to parts by weight, successively Weigh: 300 parts of deionized waters, 100 parts of sodium chloride, 2.5 parts of magnesium hydroxides, 10 parts of Magnesium dichloride hexahydrates, 2 parts of dispersing agents will be gone Ionized water is mixed with sodium chloride, and magnesium hydroxide is added into the mixture of deionized water and sodium chloride, Magnesium dichloride hexahydrate and Dispersing agent is 50 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred 40min, obtains aqueous mixture;By weight Number meter is measured, is successively weighed: 15 parts of acrylonitrile, 3 parts of vinylidene chlorides, 12 parts of methyl methacrylates, 3 parts of butyl acrylates, 20 Part low-boiling foaming agent, 4 parts of initiators and 5 parts of crosslinking agents, acrylonitrile is mixed with methyl methacrylate, and to acrylonitrile and Vinylidene chloride, butyl acrylate, low-boiling foaming agent, initiator and crosslinking agent are added in the mixture of methyl methacrylate, It is 50 DEG C in temperature, under conditions of revolving speed is 380r/min, after being stirred 40min, obtains oil mixture;By oil mixture Object mixed with water 1:1 in mass ratio mixing obtains mixing and emulsifying after emulsifying 12min under conditions of revolving speed is 8000r/min Liquid, the rate into mix emulsion fluid with 25mL/min are passed through nitrogen, and are 65 DEG C in temperature, and revolving speed is the condition of 400r/min Under, after being stirred to react 8h, mixture of microspheres is obtained, the pH to 3 of mixture of microspheres is adjusted with the hydrochloric acid that mass fraction is 15%, is filtered, Filter cake, after filter cake is washed with deionized 10 times, and obtain microballoon after dry 2h under conditions of being 80 DEG C in temperature;By weight Number meter is measured, is successively weighed: 20 parts of styrene, 12 parts of divinylbenzenes, 5 parts of benzoyl peroxides, 15 parts of epoxy resin, 12 parts Surfactant and deionized water are mixed in three mouthfuls of burnings by epoxy propane butyl ether, 7 parts of surfactants and 50 parts of deionized waters In bottle, styrene, divinylbenzene, divinylbenzene, epoxy resin and epoxy propane butyl ether are added into three-necked flask, and It is passed through nitrogen into three-necked flask with the rate of 30mL/min, is 80 DEG C in temperature, under conditions of revolving speed is 350r/min, stirs After reacting 8h, filtering obtains micro-capsule blank, after micro-capsule blank is washed with deionized 10 times, under conditions of temperature is 80 DEG C Dry 3h, obtains micro-capsule;According to parts by weight, it successively weighs: 60 parts of nitrile rubbers, 40 parts of natural rubbers, 30 parts of haloflexes Rubber, 10 parts of plasticizer, 5 parts of heat stabilizers, 12 parts of vulcanizing agents, 18 parts of calcium oxide, 15 parts of toluene di-isocyanate(TDI)s, 15 parts micro- Ball, the isocyanate-modified graphene oxide of 18 parts of micro-capsules and nitrile rubber quality 10%, by nitrile rubber and natural rubber It is mixed in blender, and chlorinated polyethylene rubber is added into blender, plasticizer, heat stabilizer, vulcanizing agent, calcium oxide, Toluene di-isocyanate(TDI), microballoon, micro-capsule and isocyanate-modified graphene oxide, in temperature be 60 DEG C, revolving speed 400r/min Under conditions of, after being stirred 40min, rubber mixture is obtained, by rubber mixture under conditions of temperature is 100 DEG C, mixing After 30min, mixing material is obtained, by mixing material under conditions of temperature is 160 DEG C, after vulcanizing 10min, compression moulding is to get compound Rubber fastening band.The plasticizer phthalic acid two (2- ethyl hexyl) ester.The heat stabilizer is anti-aging agent RD.The vulcanization Agent is sulphur.The dispersing agent is dispersing agent NNO.The low-boiling foaming agent is by isooctane and normal octane 1:1 in mass ratio Mixing, and 0.4 times of isooctane quality of isopentane is added, it is stirred, obtains low-boiling foaming agent.The initiator is persulfuric acid Potassium.The crosslinking agent is three acrylic acid propane front three alcohol esters.The surfactant is gum arabic.
Example 2
According to parts by weight, it successively weighs: 300 parts of deionized waters, 100 parts of sodium chloride, 2.5 parts of magnesium hydroxides, 10 part of six hydration Magnesium chloride, 2 parts of dispersing agents mix deionized water with sodium chloride, and hydrogen is added into the mixture of deionized water and sodium chloride Magnesia, Magnesium dichloride hexahydrate and dispersing agent are 50 DEG C in temperature, under conditions of revolving speed is 400r/min, are stirred 40min Afterwards, aqueous mixture is obtained;According to parts by weight, it successively weighs: 15 parts of acrylonitrile, 3 parts of vinylidene chlorides, 12 parts of methyl methacrylates Ester, 3 parts of butyl acrylates, 20 parts of low-boiling foaming agents, 4 parts of initiators and 5 parts of crosslinking agents, by acrylonitrile and methyl methacrylate Ester mixing, and vinylidene chloride is added into the mixture of acrylonitrile and methyl methacrylate, butyl acrylate, low boiling point foaming Agent, initiator and crosslinking agent are 50 DEG C in temperature, under conditions of revolving speed is 380r/min, after being stirred 40min, obtain oily phase Mixture;Oil mixture object mixed with water 1:1 in mass ratio is mixed, is emulsified under conditions of revolving speed is 8000r/min After 12min, mix emulsion fluid is obtained, the rate into mix emulsion fluid with 25mL/min is passed through nitrogen, and is 65 DEG C in temperature, turns Under conditions of speed is 400r/min, after being stirred to react 8h, mixture of microspheres is obtained, adjusts microballoon with the hydrochloric acid that mass fraction is 15% The pH to 3 of mixture, filtering, obtains filter cake, after filter cake is washed with deionized 10 times, and does under conditions of being 80 DEG C in temperature After dry 2h, microballoon is obtained;According to parts by weight, it successively weighs: 20 parts of styrene, 12 parts of divinylbenzenes, 5 parts of benzoyl peroxide first Acyl, 15 parts of epoxy resin, 12 parts of epoxy propane butyl ethers, 7 parts of surfactants and 50 parts of deionized waters, by surfactant with Deionized water is mixed in three-necked flask, and styrene, divinylbenzene, divinylbenzene, asphalt mixtures modified by epoxy resin are added into three-necked flask Rouge and epoxy propane butyl ether, and nitrogen is passed through into three-necked flask with the rate of 30mL/min, it is 80 DEG C in temperature, revolving speed is Under conditions of 350r/min, after being stirred to react 8h, filtering obtains micro-capsule blank, after micro-capsule blank is washed with deionized 10 times, Dry 3h under conditions of being 80 DEG C in temperature, obtains micro-capsule;According to parts by weight, successively weigh: 60 parts of nitrile rubbers, 40 parts natural Rubber, 30 parts of chlorinated polyethylene rubbers, 10 parts of plasticizer, 5 parts of heat stabilizers, 12 parts of vulcanizing agents, 15 parts of toluene di-isocyanate(TDI)s, Nitrile rubber and natural rubber are mixed in blender by 15 parts of microballoons and 18 parts of micro-capsules, and chlorination is added into blender and gathers Ethylene rubber, plasticizer, heat stabilizer, vulcanizing agent, toluene di-isocyanate(TDI), microballoon and micro-capsule are 60 DEG C in temperature, and revolving speed is Under conditions of 400r/min, after being stirred 40min, rubber mixture is obtained, the condition for being 100 DEG C in temperature by rubber mixture Under, after mixing 30min, mixing material is obtained, by mixing material under conditions of temperature is 160 DEG C, after vulcanizing 10min, compression moulding, i.e., Obtain composite rubber water stop.The plasticizer phthalic acid two (2- ethyl hexyl) ester.The heat stabilizer is anti-aging agent RD.Institute Stating vulcanizing agent is sulphur.The dispersing agent is dispersing agent NNO.The low-boiling foaming agent is that isooctane and normal octane are pressed quality It is mixed than 1:1, and 0.4 times of isooctane quality of isopentane is added, be stirred, obtain low-boiling foaming agent.The initiator is Potassium peroxydisulfate.The crosslinking agent is three acrylic acid propane front three alcohol esters.The surfactant is gum arabic.
Example 3
According to parts by weight, it successively weighs: 20 parts of styrene, 12 parts of divinylbenzenes, 5 parts of benzoyl peroxides, 15 parts of epoxies Resin, 12 parts of epoxy propane butyl ethers, 7 parts of surfactants and 50 parts of deionized waters, surfactant and deionized water are mixed Together in styrene, divinylbenzene, divinylbenzene, epoxy resin and epoxy third in three-necked flask, are added into three-necked flask Alkane butyl ether, and nitrogen is passed through into three-necked flask with the rate of 30mL/min, it is 80 DEG C in temperature, revolving speed is 350r/min's Under the conditions of, after being stirred to react 8h, filtering, obtain micro-capsule blank, after micro-capsule blank is washed with deionized 10 times, in temperature be 80 Dry 3h, obtains micro-capsule under conditions of DEG C;According to parts by weight, it successively weighs: 60 parts of nitrile rubbers, 40 parts of natural rubbers, 30 parts Chlorinated polyethylene rubber, 10 parts of plasticizer, 5 parts of heat stabilizers, 12 parts of vulcanizing agents, 18 parts of calcium oxide, 15 parts of toluene diisocynates Nitrile rubber and natural rubber are mixed in blender by ester and 18 parts of micro-capsules, and haloflex rubber is added into blender Glue, plasticizer, heat stabilizer, vulcanizing agent, calcium oxide, toluene di-isocyanate(TDI) and micro-capsule are 60 DEG C in temperature, and revolving speed is Under conditions of 400r/min, after being stirred 40min, rubber mixture is obtained, the condition for being 100 DEG C in temperature by rubber mixture Under, after mixing 30min, mixing material is obtained, by mixing material under conditions of temperature is 160 DEG C, after vulcanizing 10min, compression moulding, i.e., Obtain composite rubber water stop.The plasticizer phthalic acid two (2- ethyl hexyl) ester.The heat stabilizer is anti-aging agent RD.Institute Stating vulcanizing agent is sulphur.The surfactant is gum arabic.
Example 4
According to parts by weight, it successively weighs: 300 parts of deionized waters, 100 parts of sodium chloride, 2.5 parts of magnesium hydroxides, 10 part of six hydration Magnesium chloride, 2 parts of dispersing agents mix deionized water with sodium chloride, and hydrogen is added into the mixture of deionized water and sodium chloride Magnesia, Magnesium dichloride hexahydrate and dispersing agent are 50 DEG C in temperature, under conditions of revolving speed is 400r/min, are stirred 40min Afterwards, aqueous mixture is obtained;According to parts by weight, it successively weighs: 15 parts of acrylonitrile, 3 parts of vinylidene chlorides, 12 parts of methyl methacrylates Ester, 3 parts of butyl acrylates, 20 parts of low-boiling foaming agents, 4 parts of initiators and 5 parts of crosslinking agents, by acrylonitrile and methyl methacrylate Ester mixing, and vinylidene chloride is added into the mixture of acrylonitrile and methyl methacrylate, butyl acrylate, low boiling point foaming Agent, initiator and crosslinking agent are 50 DEG C in temperature, under conditions of revolving speed is 380r/min, after being stirred 40min, obtain oily phase Mixture;Oil mixture object mixed with water 1:1 in mass ratio is mixed, is emulsified under conditions of revolving speed is 8000r/min After 12min, mix emulsion fluid is obtained, the rate into mix emulsion fluid with 25mL/min is passed through nitrogen, and is 65 DEG C in temperature, turns Under conditions of speed is 400r/min, after being stirred to react 8h, mixture of microspheres is obtained, adjusts microballoon with the hydrochloric acid that mass fraction is 15% The pH to 3 of mixture, filtering, obtains filter cake, after filter cake is washed with deionized 10 times, and does under conditions of being 80 DEG C in temperature After dry 2h, microballoon is obtained;Parts by weight meter, successively weighs: 60 parts of nitrile rubbers, 40 parts of natural rubbers, 30 parts of haloflex rubbers Glue, 10 parts of plasticizer, 5 parts of heat stabilizers, 12 parts of vulcanizing agents, 18 parts of calcium oxide, 15 parts of toluene di-isocyanate(TDI)s, 15 parts of microballoons, Nitrile rubber and natural rubber are mixed in blender, and chlorinated polyethylene rubber is added into blender, plasticizer, heat is surely Determine agent, vulcanizing agent, calcium oxide, toluene di-isocyanate(TDI), microballoon is 60 DEG C in temperature, under conditions of revolving speed is 400r/min, stirs After mixing mixing 40min, rubber mixture is obtained, by rubber mixture under conditions of temperature is 100 DEG C, after mixing 30min, is obtained close Refining material, by mixing material under conditions of temperature is 160 DEG C, after vulcanizing 10min, compression moulding is to get composite rubber water stop.Institute State plasticizer phthalic acid two (2- ethyl hexyl) ester.The heat stabilizer is anti-aging agent RD.The vulcanizing agent is sulphur.It is described Dispersing agent is dispersing agent NNO.The low-boiling foaming agent is to mix isooctane with normal octane 1:1 in mass ratio, and be added different The isopentane that 0.4 times of octane quality, is stirred, and obtains low-boiling foaming agent.The initiator is potassium peroxydisulfate.The crosslinking agent For three acrylic acid propane front three alcohol esters.
Comparative example: the composite rubber water stop of Wuxi material production Co., Ltd production.
Example 1 to the resulting composite rubber water stop of example 4 and comparative example product are subjected to performance detection, specific detection side Method is as follows:
Anti-permeability performance is tested according to JG/T193 and ASTMD5084, and calculation permeability coefficient;It is measured using omnipotent mechanics instrument The mechanical property of test specimen.Test condition: tensile elongation 100mm, tensile speed 10mm/min.Every group of test specimen, which stretches 10 times, to be taken Average value finally obtains breaking strength.Test specimen is placed in water after impregnating 36h and utilizes the power of omnipotent mechanics instrument measurement test specimen again Learn performance.Test condition: tensile elongation 100mm, tensile speed 10mm/min test its breaking strength.
Specific testing result is as shown in table 1:
1 composite rubber water stop performance test results of table
By 1 testing result of table it is found that the composite rubber water stop of technical solution of the present invention preparation have excellent waterproof performance and The characteristics of mechanical property, has broad prospects in the development of high polymer material technology industry.

Claims (10)

1. a kind of composite rubber water stop, which is characterized in that be made of the raw material of following parts by weight: 50~60 parts of butyronitrile rubbers Glue, 30~40 parts of natural rubbers, 20~30 parts of chlorinated polyethylene rubbers, 5~10 parts of plasticizer, 2~5 parts of heat stabilizers, 8~12 Part vulcanizing agent, 10~18 parts of calcium oxide, 8~15 parts of toluene di-isocyanate(TDI)s, 10~15 parts of microballoons and 15~18 parts of micro-capsules;
The microballoon the preparation method comprises the following steps:
(1) according to parts by weight, it successively weighs: 200~300 parts of deionized waters, 70~100 parts of sodium chloride, 2.0~2.5 parts of hydrogen Deionized water is mixed with sodium chloride, and hydroxide is added by magnesia, 5~10 parts of Magnesium dichloride hexahydrates, 1~2 part of dispersing agent Magnesium, Magnesium dichloride hexahydrate and dispersing agent after being stirred, obtain aqueous mixture;
(2) according to parts by weight, it successively weighs: 10~15 parts of acrylonitrile, 1~3 part of vinylidene chloride, 10~12 parts of methacrylic acids Methyl esters, 1~3 part of butyl acrylate, 15~20 parts of low-boiling foaming agents, 2~4 parts of initiators and 4~5 parts of crosslinking agents, by propylene Nitrile is mixed with methyl methacrylate, and vinylidene chloride is added, butyl acrylate, low-boiling foaming agent, initiator and crosslinking agent, After being stirred, oil mixture is obtained;
(3) oil mixture object mixed with water 1:1 in mass ratio is mixed, emulsification obtains mix emulsion fluid;
(4) after being stirred to react mix emulsion fluid under nitrogen atmosphere, mixture of microspheres is obtained, adjusts the pH to 2 of mixture of microspheres ~3, it filters, washs, it is dry, obtain microballoon;
The micro-capsule the preparation method comprises the following steps:
(5) according to parts by weight, it successively weighs: 10~20 parts of styrene, 10~12 parts of divinylbenzenes, 2~5 parts of benzoyl peroxides Formyl, 12~15 parts of epoxy resin, 8~12 parts of epoxy propane butyl ethers, 5~7 parts of surfactants and 40~50 parts of deionizations Surfactant is mixed with deionized water, and styrene is added by water, divinylbenzene, divinylbenzene, epoxy resin and ring Ethylene Oxide butyl ether after being stirred to react, is filtered, is washed under nitrogen atmosphere, dry, obtains micro-capsule.
2. a kind of composite rubber water stop according to claim 1, it is characterised in that: the plasticizer phthalic acid two (2- ethyl hexyl) ester, any one in dioctyl phthalate or BBP(Butyl Benzyl Phthalate.
3. a kind of composite rubber water stop according to claim 1, it is characterised in that: the heat stabilizer is anti-aging agent Any one in RD, antioxidant 4020 or paraffin.
4. a kind of composite rubber water stop according to claim 1, it is characterised in that: the vulcanizing agent is sulphur or peroxide Change any one in benzoyl.
5. a kind of composite rubber water stop according to claim 1, it is characterised in that: the dispersing agent is dispersing agent NNO, Any one in Dispersant MF or dispersing agent 5040.
6. a kind of composite rubber water stop according to claim 1, it is characterised in that: the low-boiling foaming agent is will be different Octane is mixed with normal octane 1:1 in mass ratio, and 0.2~0.4 times of isooctane quality of isopentane is added, and is stirred, is obtained low Boiling point blowing agent.
7. a kind of composite rubber water stop according to claim 1, it is characterised in that: the initiator is potassium peroxydisulfate, Any one in sodium peroxydisulfate or azodiisobutyronitrile.
8. a kind of composite rubber water stop according to claim 1, it is characterised in that: the crosslinking agent is three acrylic acid third Any one in alkane front three alcohol ester or ethylene glycol dimethacrylate.
9. a kind of composite rubber water stop according to claim 1, it is characterised in that: the surfactant is Arab Any one in natural gum or neopelex.
10. a kind of composite rubber water stop according to claim 1, it is characterised in that: in the composite rubber water stop The isocyanate-modified graphene oxide of nitrile rubber quality 8~10% can also be added;The isocyanate-modified graphite oxide The preparation process of alkene are as follows: according to parts by weight, successively take 10~20 parts of graphene oxides, 30~40 parts of toluene di-isocyanate(TDI)s, 30~40 parts of acetone, after mixing, 3~5h of heating reflux reaction, using filter, washing and vacuum drying are obtained isocyanate-modified Graphene oxide.
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JP2001234080A (en) * 2000-02-25 2001-08-28 Fujikura Rubber Ltd Water stop composition
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CN108084483A (en) * 2017-12-05 2018-05-29 山东瑞丰高分子材料股份有限公司 Dedicated heat-swellable polymer microballoon of Corvic foaming and preparation method thereof
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