CN104277258B - A kind of preparation method of the water swelling rubber of good weatherability - Google Patents
A kind of preparation method of the water swelling rubber of good weatherability Download PDFInfo
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- CN104277258B CN104277258B CN201410507768.8A CN201410507768A CN104277258B CN 104277258 B CN104277258 B CN 104277258B CN 201410507768 A CN201410507768 A CN 201410507768A CN 104277258 B CN104277258 B CN 104277258B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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- 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
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- 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
Abstract
The preparation method that the present invention relates to the water swelling rubber of a kind of good weatherability, belongs to technical field of polymer materials.Comprise the steps: the 1st step, by weight to take nitrile rubber 30～50 parts, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 3～5 parts, chlorinated polypropylene 4～6 parts, open refining uniformly with mill；3rd step, add polyvinylpyrrolidone 2～4 parts, white carbon black 2～4 parts and white carbon 1～3 part, open refining uniformly；4th step, adds vulcanization accelerator 1～2 part, opens refining uniformly, and bottom sheet stands, standby；5th step, after vulcanizing press sulfur, die sinking, after standing,.The water absorbing properties of the water sucting rubber that the present invention prepares is good, and weather resistance is excellent, uses after repeatedly in acidic aqueous solution, and water absorbing properties can keep.
Description
Technical field
The preparation method that the present invention relates to the water swelling rubber of a kind of good weatherability, belongs to technical field of polymer materials.
Background technology
Water swelling rubber (WaterSwellingRubber is called for short WSR) is a kind of new functional macromolecule material developed by Japan the phase at the end of the seventies in last century.Within 1976, Japanese Xu electricity Chemical Co., Ltd has applied for the patent of invention of water swelling rubber first.WSR introduces hydrophilic group or hydrophilic component in traditional elastic matrix (such as rubber and thermoplastic elastomer (TPE)) and makes, several times or even the hundreds times of sole mass or volume it is expandable to after the water suction of this product, adapt to malformation, and produce the bigger bulbs of pressure, while the elasticity keeping matrix and intensity, also there is the ability of water conservation sealing.Water swelling rubber is as a kind of new type functional material.
Owing to this material is the coalition of non-polar rubber and polar hydrophilic component, thus it and apolar surfaces are (such as Colophonium, plastics, rubber) and polar surfaces (such as cement bonded sand oar, reinforced concrete) all there is the closely sealed characteristic of good infiltration, simultaneously material again can imbibition repeatedly, water retention property is stable, unique elasticity and imbibition dual-use function, can durable seal for a long time, thus it is widely used in tunnel, subway, culvert, building, basement, swimming pool, underground engineering, the waterproof leakproof seal of the job facilities such as offshore oil production, also it is automobile simultaneously, container, precision instrument, medicine, the waterproof of food, the desirable seal material of damp-prrof packing etc..
Elastic matrix is mainly made up of high polymerization degree carbon, hydrogen chain link, itself is lyophobic dust.After introducing hydrophilic group or hydrophilic component in the base, when contacting with water again, hydrone can enter in matrix, extremely strong affinity is formed with the hydrophilic radical in rubber, and the hydroaropic substance in rubber is dissolved or swelling, forming permeable pressure head inside and outside rubber, this pressure reduction promotes that water is to rubber internal penetration.Hydroaropic substance constantly absorbs moisture, causes rubber to deform upon.When rubber self anti deformational force and permeable pressure head are equal, reaching balance, namely reach hydrostatic maximum swelling rate, imbibition effect keeps relative stability.
The preparation of water sucting rubber is broadly divided into two big classes: physical blending process, chemical graft process.
Physical blending process is rubber polymer, hydroaropic substance, filler and auxiliary agent etc. according to a certain ratio on double roll mill after mixing, then with the molding sulfuration such as vulcanizing press or extruder.Physical blending process can as desired to regulate technical recipe, preparation technology is simple, raw material sources are extensive, production cost is relatively low, and rapidly, shortcoming is owing to highly polar hydrophilic substance (water-absorbing resin) cohesiveness own is bigger in initial water suction, in rubber, ubiquity disperses bad and poor compatibility, after immersion, water-absorbing resin easily departs from from rubber matrix, and Reusability expansion rate can decline, and its hot strength can reduce with the increase of expansion rate.Chemical graft process is often referred to hydrophilic monomer or oligomer non-polar high polymer chain grafting, or the method that WSR is prepared in block copolymerization, and it is mainly for the preparation of hydrophilic polyurethane and rubber graft copolymer two class WSR.Polyurethanes WSR adopts the hydrophilic oligomer of active end group or polymer (such as Polyethylene Glycol, polyether Glycols) to react with multicomponent isocyanate and make, its specific network structure gives polyurethane with high resiliency, and Hydrophilicrto polyether block makes it have higher water absorbing capacity.Rubber graft copolymer class WSR is the hydrophilic group that induces one in rubber macromolecular chain, so as to realizing caoutchouc elasticity and absorptive combination.The WSR advantage that chemical grafting obtains is to have the advantages that micro compatibility is good, intensity is high, the repetitive process stable physical property that product imbibition in the application and dehydration are restored, shortcoming is that graft reaction is difficult, technique is loaded down with trivial details, relatively costly, and imbibition multiplying power is low, body of rubber poor flexibility.In view of economy considers, most industry produces WSR and adopts physical blending process.
Summary of the invention
Being solved the technical problem that of the present invention is to solve the water swelling rubber prepared of physical blending process to absorb water after long-term use and can decline, it is provided that the preparation method of the water swelling rubber of a kind of good weatherability.
Technical scheme:
A kind of preparation method of the water swelling rubber of good weatherability,
1st step, by weight, takes nitrile rubber 30～50 parts, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C(carbon) ion, obtain modified butadiene acrylonitrile rubber；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 3～5 parts, chlorinated polypropylene 4～6 parts, open refining uniformly with mill；
3rd step, add polyvinylpyrrolidone 2～4 parts, white carbon black 2～4 parts and white carbon 1～3 part, open refining uniformly；
4th step, adds vulcanization accelerator 1～2 part, opens refining uniformly, and bottom sheet stands, standby；
5th step, vulcanizing press vulcanize after, die sinking, after standing,.
Preferably, in the 1st step, C ion consumption is 1～3 part；Ion energy is 20～30keV；Beam current density scope is 0.5～0.8mA/cm2；The ion source adopted is purity is the graphite of more than 98%.
Preferably, in the 2nd step, the roll spacing of mill is 2mm, time 3～5min.
Preferably, in the 3rd step, the roll spacing of mill is 2mm, time 8～12min.
Preferably, in the 4th step, the roll spacing of mill is 0.4mm, time 3～5min.
Preferably, in the 5th step, curing temperature is 150～170 DEG C, time 20～40min, pressure 8～12MPa.
Preferably, in the 4th step, vulcanization accelerator refers to captax or altax.
Preferably, in the 1st step, it is additionally added 3～5 parts of silicone rubber.
Preferably, in the 2nd step, it is additionally added vinyl acetate 2～4 parts, hydroxy silicon oil 1～4 part.
Preferably, the chlorinty preferable range 28～32% of chlorinated polypropylene.
Beneficial effect
The water absorbing properties of the water sucting rubber that the present invention prepares is good, and weather resistance is excellent, uses after repeatedly in acidic aqueous solution, and water absorbing properties can keep.
Detailed description of the invention
Embodiment 1
1st step, take nitrile rubber 30Kg, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；C ion consumption is 1Kg；Ion energy is 20keV；Beam current density scope is 0.5mA/cm2；The ion source adopted is purity is the graphite of 99%；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 3Kg, chlorinated polypropylene (chlorinity 28%) 4Kg, open refining uniformly with mill, and the roll spacing of mill is 2mm, time 3min；
3rd step, adding polyvinylpyrrolidone 2Kg, white carbon black 2Kg and white carbon 1Kg, open refining uniformly, the roll spacing of mill is 2mm, time 8min；
4th step, adds accelerator M 1Kg, opens refining uniformly, and the roll spacing of mill is 0.4mm, time 3min, bottom sheet, stands, standby；
5th step, at vulcanizing press sulfur, curing temperature is 150 DEG C, time 20min, pressure 8MPa, die sinking, after standing,.
Embodiment 2
1st step, take nitrile rubber 50Kg, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；C ion consumption is 3Kg；Ion energy is 30keV；Beam current density scope is 0.8mA/cm2；The ion source adopted is purity is the graphite of 99%；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 5Kg, chlorinated polypropylene (chlorinity 28%) 6Kg, open refining uniformly with mill, and the roll spacing of mill is 2mm, time 5min；
3rd step, adding polyvinylpyrrolidone 4Kg, white carbon black 4Kg and white carbon 3Kg, open refining uniformly, the roll spacing of mill is 2mm, time 12min；
4th step, adds accelerator M 2Kg, opens refining uniformly, and the roll spacing of mill is 0.4mm, time 5min, bottom sheet, stands, standby；
5th step, at vulcanizing press sulfur, curing temperature is 170 DEG C, time 40min, pressure 12MPa, die sinking, after standing,.
Embodiment 3
1st step, take nitrile rubber 40Kg, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；C ion consumption is 2Kg；Ion energy is 25keV；Beam current density scope is 0.6mA/cm2；The ion source adopted is purity is the graphite of 99%；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 4Kg, chlorinated polypropylene (chlorinity 28%) 5Kg, open refining uniformly with mill, and the roll spacing of mill is 2mm, time 4min；
3rd step, adding polyvinylpyrrolidone 3Kg, white carbon black 3Kg and white carbon 2Kg, open refining uniformly, the roll spacing of mill is 2mm, time 10min；
4th step, adds accelerator M 2Kg, opens refining uniformly, and the roll spacing of mill is 0.4mm, time 4min, bottom sheet, stands, standby；
5th step, at vulcanizing press sulfur, curing temperature is 160 DEG C, time 30min, pressure 10MPa, die sinking, after standing,.
Embodiment 4
It is distinctive in that with embodiment 3, the 1st step is additionally added silicone rubber.
1st step, take nitrile rubber 40Kg, silicone rubber 3～5Kg, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；C ion consumption is 2Kg；Ion energy is 25keV；Beam current density scope is 0.6mA/cm2；The ion source adopted is purity is the graphite of 99%；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 4Kg, chlorinated polypropylene (chlorinity 28%) 5Kg, open refining uniformly with mill, and the roll spacing of mill is 2mm, time 4min；
3rd step, adding polyvinylpyrrolidone 3Kg, white carbon black 3Kg and white carbon 2Kg, open refining uniformly, the roll spacing of mill is 2mm, time 10min；
4th step, adds accelerator M 2Kg, opens refining uniformly, and the roll spacing of mill is 0.4mm, time 4min, bottom sheet, stands, standby；
5th step, at vulcanizing press sulfur, curing temperature is 160 DEG C, time 30min, pressure 10MPa, die sinking, after standing,.
Embodiment 5
It is distinctive in that with embodiment 4: the 2nd step is additionally added vinyl acetate, hydroxy silicon oil.
1st step, take nitrile rubber 40Kg, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtain modified butadiene acrylonitrile rubber；C ion consumption is 2Kg；Ion energy is 25keV；Beam current density scope is 0.6mA/cm2；The ion source adopted is purity is the graphite of 99%；
2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained are mixed homogeneously with sodium polyacrylate 4Kg, chlorinated polypropylene (chlorinity 28%) 5Kg, vinyl acetate 3Kg, hydroxy silicon oil 3Kg, open refining uniformly with mill, and the roll spacing of mill is 2mm, time 4min；
3rd step, adding polyvinylpyrrolidone 3Kg, white carbon black 3Kg and white carbon 2Kg, open refining uniformly, the roll spacing of mill is 2mm, time 10min；
4th step, adds accelerator M 2Kg, opens refining uniformly, and the roll spacing of mill is 0.4mm, time 4min, bottom sheet, stands, standby；
5th step, at vulcanizing press sulfur, curing temperature is 160 DEG C, time 30min, pressure 10MPa, die sinking, after standing,.
Embodiment 6
Be distinctive in that with embodiment 5: the chlorinty of chlorinated polypropylene is respectively adopted 25%, 30%, 32%, 35%(is as the 1st group, the 2nd group, the 3rd group, the 4th group).
Performance test
The sample prepared is cut out, is dipped in tap water, under room temperature, take out weighing at set intervals, want rapid filter paper to suck the moisture of specimen surface when every day weighs, after reaching capacity until water suction, be dried to constant weight in 50 DEG C.Water absorption rate and rate of weight loss computing formula are as follows:
Weight × 100% before rubber weight water absorption rate (%)=(weight before weight-rubber water absorbent after rubber water absorbent)/rubber water absorbent；
Weight × 100% before rubber weight loss rate (%)=(weight after the weight before rubber water absorbent-rubber water absorbent drying)/rubber water absorbent；
After above-mentioned tap water soak test, sample is taken out, then soak after 72 hours in 1% hydrochloric acid solution, then dry 8 hours at 120 DEG C, then carry out tap water soak test, according to being measured in the same method water absorption rate.
The hardness of the vulcanized test specimens of water sucting rubber measures according to GB/T531, and hot strength and elongation at break are tested according to GB/T528.
The sample tests that above example prepares is as follows, adopts conventional blending type water sucting rubber as comparison.
As can be seen from the table, water sucting rubber provided by the invention, relative to common water absorption product, has better water absorption, and this, mainly due to after being modifiied by C injection, improves its hydrophilic, it is possible to compatible with water-absorbing resin better.It addition, by adding silicone rubber, it is also possible to improve its mechanical strength simultaneously；Introducing by vinyl acetate, hydroxy silicon oil, it is possible to improve its water absorbing properties, from the four of embodiment 6 groups of contrast tests it can be seen that can solve to improve the technical problem of water suction tympanites rate performance by adjusting the chlorinity of chlorinated polypropylene.
Claims (9)
1. the preparation method of the water swelling rubber of a good weatherability, it is characterised in that comprise the steps: the 1st step, by weight, takes nitrile rubber 30～50 parts, after pulverizing, with ion implantation apparatus, nitrile rubber is injected C ion, obtains modified butadiene acrylonitrile rubber；2nd step, the modified butadiene acrylonitrile rubber the 1st step obtained is mixed homogeneously with sodium polyacrylate 3～5 parts, chlorinated polypropylene 4～6 parts, opens refining uniformly with mill；3rd step, adds polyvinylpyrrolidone 2～4 parts, white carbon black 2～4 parts and white carbon 1～3 part, opens refining uniformly；4th step, adds vulcanization accelerator 1～2 part, opens refining uniformly, and bottom sheet stands, standby；5th step, after vulcanizing press sulfur, die sinking, after standing,；Wherein, in the 1st step, C ion consumption is 1～3 part, and ion energy is 20～30keV, and beam current density scope is 0.5～0.8mA/cm2, the ion source of employing is purity is the graphite of more than 98%.
2. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 2nd step, the roll spacing of mill is 2mm, time 3～5min.
3. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 3rd step, the roll spacing of mill is 2mm, time 8～12min.
4. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 4th step, the roll spacing of mill is 0.4mm, time 3～5min.
5. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 5th step, curing temperature is 150～170 DEG C, time 20～40min, pressure 8～12MPa.
6. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: vulcanization accelerator refers to captax or altax.
7. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 1st step, it is additionally added 3～5 parts of silicone rubber.
8. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: in the 2nd step, it is additionally added vinyl acetate 2～4 parts, hydroxy silicon oil 1～4 part.
9. the preparation method of the water swelling rubber of good weatherability according to claim 1, it is characterised in that: the chlorinty preferable range 28～32% of chlorinated polypropylene.
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| CN104530503B (en) * | 2015-01-28 | 2016-04-20 | 河南职业技术学院 | The preparation method of the tire that a kind of earth-catching property is good |
| CN104558868B (en) * | 2015-02-21 | 2017-01-25 | 江苏兴华胶带股份有限公司 | Preparation method of corrosion-resistant flame-retardant cable rubber material |
| CN105061834A (en) * | 2015-08-05 | 2015-11-18 | 苏州赛斯德工程设备有限公司 | Preparation method of water-swelling rubber |
| CN105968594A (en) * | 2016-06-23 | 2016-09-28 | 安徽荣达阀门有限公司 | Weather-resistant water-swelling waterproof rubber sealing material and preparation method thereof |
| CN106614200A (en) * | 2016-12-14 | 2017-05-10 | 浙江海洋大学 | Support rod type purse seine aquaculture engineering shore connecting technique |
| CN107859501B (en) * | 2017-12-28 | 2020-12-04 | 河北鸿凯石油科技有限公司 | Self-expansion clamping and sealing device |
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| CN102875700B (en) * | 2012-10-12 | 2014-04-09 | 武汉工程大学 | Method for modifying rubber base of water swelling nitrile rubber |
| CN104017254B (en) * | 2014-06-20 | 2016-03-02 | 武汉工程大学 | The preparation method of increasing reaction type butyronitrile water swelling rubber |
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Effective date of registration: 20171110 Address after: 211111 Jiangsu Province, Nanjing Zijin (Jiangning) technology start-ups in particular communities (Jiangning District Mo Zhou Road No. 12) Patentee after: Nanjing Valley Intellectual Property Service Co., Ltd. Address before: 215000 Jiangsu city of Suzhou province high tech Zone No. 121 Hua Feng Lu Patentee before: Suzhou Changsheng Electromechanical Co., Ltd. |