CN110372924A - A kind of composite rubber water stop - Google Patents
A kind of composite rubber water stop Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- parts
- water stop
- composite rubber
- rubber
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
Landscapes
- 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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506372.4A CN110372924A (en) | 2019-06-12 | 2019-06-12 | A kind of composite rubber water stop |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910506372.4A CN110372924A (en) | 2019-06-12 | 2019-06-12 | A kind of composite rubber water stop |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110372924A true CN110372924A (en) | 2019-10-25 |
Family
ID=68250159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910506372.4A Pending CN110372924A (en) | 2019-06-12 | 2019-06-12 | A kind of composite rubber water stop |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110372924A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740404A (en) * | 1985-10-07 | 1988-04-26 | C. I. Kasei, Co. Ltd. | Waterstop |
| JP2001234080A (en) * | 2000-02-25 | 2001-08-28 | Fujikura Rubber Ltd | Water stop composition |
| CN105801933A (en) * | 2016-04-27 | 2016-07-27 | 袁春华 | Preparation method of expanded nano microsphere filled rubber waterproofing strap |
| 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 |
| CN108102161A (en) * | 2017-12-27 | 2018-06-01 | 天台汉腾橡胶有限公司 | A kind of nano modification waterstop and preparation method thereof |
| CN109629336A (en) * | 2018-10-29 | 2019-04-16 | 万玉梅 | A kind of preparation method of the flexible insulating paper of tension |
-
2019
- 2019-06-12 CN CN201910506372.4A patent/CN110372924A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4740404A (en) * | 1985-10-07 | 1988-04-26 | C. I. Kasei, Co. Ltd. | Waterstop |
| JP2001234080A (en) * | 2000-02-25 | 2001-08-28 | Fujikura Rubber Ltd | Water stop composition |
| CN105801933A (en) * | 2016-04-27 | 2016-07-27 | 袁春华 | Preparation method of expanded nano microsphere filled rubber waterproofing strap |
| 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 |
| CN108102161A (en) * | 2017-12-27 | 2018-06-01 | 天台汉腾橡胶有限公司 | A kind of nano modification waterstop and preparation method thereof |
| CN109629336A (en) * | 2018-10-29 | 2019-04-16 | 万玉梅 | A kind of preparation method of the flexible insulating paper of tension |
Non-Patent Citations (2)
| Title |
|---|
| 付长璟等: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 * |
| 张殿荣等: "《现代橡胶配方设计第二版》", 31 October 2001, 橡胶工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5934197B2 (en) | Epoxy composite | |
| CN110387222A (en) | A kind of porous gel sealing agent, preparation method and application | |
| CN106316192B (en) | Application of the temperature-sensitive hydrogel in improving agent on crack resistance of concrete freeze thawing performance | |
| CN103848935A (en) | Oil-absorptive resin and oil-absorptive expanding rubber comprising same | |
| KR101904151B1 (en) | Nitrile rubber composition, crosslinking nitrile rubber composition, and crosslinked rubber product | |
| CN102863667B (en) | Preparation method for water swelling nitrile butadiene rubber | |
| CN107417855B (en) | Organic-inorganic hybrid emulsion particle toughened hydrophobically associating hydrogel and preparation method thereof | |
| CN104017254B (en) | The preparation method of increasing reaction type butyronitrile water swelling rubber | |
| Wu et al. | Developing a polymer-based crack repairing material using interpenetrate polymer network (IPN) technology | |
| CN107558464A (en) | A kind of high-strength corrosion-resistant loses multidirectional GSZ | |
| CN110452598A (en) | Male-type heats graticule and preparation method thereof | |
| CN110183187A (en) | A kind of modified water-proofing anticracking cement mortar | |
| JP2021038407A (en) | Polymer latex composition and use thereof | |
| CN101161711A (en) | Water-absorption expanding rubber combination containing montmorillonite absorbent material and preparation method thereof | |
| CN110372924A (en) | A kind of composite rubber water stop | |
| CN108429218A (en) | The method that cable channel cover plate is prepared using retired insulator rubber and plug powder | |
| CN110294926A (en) | A kind of silicane-modified polyurethane material and its preparation method and application method | |
| CN104371638A (en) | One-component ketoxime removal type sealant and preparation method thereof | |
| CN1069669C (en) | Thermoplastic resin composition and its synthetic resin composite | |
| CN110903559A (en) | High-temperature-aging-resistant rubber water stop and preparation method thereof | |
| CN106088458A (en) | The good quality froth concrete precast floor of high water proofing property | |
| CN1155630C (en) | Copolymer latex for reinforcing oil well and its prepn | |
| CN113462036B (en) | Melting and chemical modification material for rubber-plastic waterstop and preparation method thereof | |
| CN114180929A (en) | Self-repairing material for concrete superfine cracks and preparation method thereof | |
| CN110066521A (en) | A kind of preparation method of tension waterstop |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |