CN104017254B - The preparation method of increasing reaction type butyronitrile water swelling rubber - Google Patents
The preparation method of increasing reaction type butyronitrile water swelling rubber Download PDFInfo
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- CN104017254B CN104017254B CN201410279755.XA CN201410279755A CN104017254B CN 104017254 B CN104017254 B CN 104017254B CN 201410279755 A CN201410279755 A CN 201410279755A CN 104017254 B CN104017254 B CN 104017254B
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Abstract
The present invention relates to a kind of preparation method of increasing reaction type butyronitrile water swelling rubber, after comprising the steps: that thin-pass bag roller is plasticated on a mill until by paracril, add promoting agent A, promoting agent B, vulcanizing agent, anti-aging agent, water suction auxiliary agent successively, expanding material, after opening refining evenly, it is evenly mixing to add water-absorbing resin, then adds reinforced filling carbon black and white carbon black, open refining, finally add vulcanization accelerator A and vulcanization accelerator B is evenly mixing, play triangle bag, thin-pass, bottom sheet, stand for standby use; The paracril mixed obtained is placed in compression mold, sulfuration, die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill, and cuts out sample.Tool of the present invention has the following advantages and useful effect: this preparation method is simple, and equipment requirements is low, thus cost-saving, can be widely used in the aspects such as tunnel, culvert, swimming pool, vault, underwater engineering, down-hole oil production, water facilities, civilian construction.
Description
Technical field
The present invention relates to a kind of preparation method of increasing reaction type butyronitrile water swelling rubber, belong to sealing material field.
Technical background
Water swelling rubber (WaterswellingRubber is called for short WSR) in the matrix of rubber, introduces hydrophilic radical or absorbent composition and a kind of new functional macromolecule material made.From the new functional macromolecule material of 20 century 70 exploitations, absorb water the rear inflatable several times to sole mass and even hundreds of times.And while maintenance caoutchouc elasticity, also there is water-retentivity.The water-tight of building deformation seam, construction joint waterproof, underwater instrument and war industry's weapon can be widely used in, and the joint waterproofing sealing of the pipeline such as metal, concrete, pottery, plastics, iron and steel and box culvert.Compared with traditional pressurized joint seal material, water swelling rubber had both possessed the sealing function of conventional sealing material, can play again with the effect of water sealing.WSR is a kind of substituted type waterproof and sealing material, and therefore, it has good application prospect and huge market.
The most frequently used preparation method utilizes physical blending process to prepare water swelling rubber (namely hydrophilic component and rubber matrix carry out blended), be easy to because hydrophilic component particle diameter is little reunite, character between hydrophilic component with rubber differs larger, hydrophilic component disperses uneven in rubber, make hydrophilic component be easy to separate out, thus reduce water absorbing properties and the mechanical property of water swelling rubber.Therefore use expanding material improves the bonding force between absorbent composition and rubber, improves hydrophilic component and separates out problem.
Zhang Zhi person of outstanding talent waits using PVA-g-PBA (polyvinyl alcohol graft copolymerized butyl polyacrylate amphipathic graft copolymer) as expanding material, chlorohydrin rubber and crosslinked salt polyacrylate is utilized to prepare WSR, mass loss rate after immersion drops to 14.32% by do not add 18.82%, but mass loss rate is still larger.
Wang Caiqi etc. improve the consistency of absorption resin of sodium polyacrylate and natural rubber with amphipathic nature block polymer PEO-b-PBA (poly-ethylene oxide block butyl polyacrylate), mass loss rate is larger, and expanding material synthesis technique is complicated, equipment requirements is higher.
The employing such as Xie Jingsi solution grafting has been prepared expanding material P (AM-g-NBR) and has been come increase-volume paracril, SAR-PA water-absorbing resin system, and expanding material preparation method is complicated, needs to consume a large amount of solvent.
Summary of the invention
The object of the invention is to prepare a kind of increasing reaction type butyronitrile water swelling rubber, (reactive compatibilizer adopts melt grafting to be prepared to add reactive compatibilizer in this water swelling rubber, method is simple, without the need to consuming a large amount of solvent, aftertreatment is easy), the dispersion of absorbent composition in rubber matrix can be improved very well, the interfacial tension between enhancing and absorbent composition, increase the consistency of matrix and absorbent composition, reduce absorbent composition and come off from matrix.
The technological line that the present invention solves the problems of the technologies described above employing is: the preparation method of increasing reaction type butyronitrile water swelling rubber, comprises the steps:
1) by the number of weight shared by each raw material be: paracril 100 parts, expanding material 4 ~ 12 parts, promoting agent A1.5 part, promoting agent B5 part, 1 part, anti-aging agent, carbon black 20 parts, white carbon black 20 parts, vulcanization accelerator A2 part, vulcanization accelerator B2 part, vulcanizing agent 1.5 parts, water-absorbing resin 30 ~ 70 parts, water suction auxiliary agent 0 ~ 12 part, choose promoting agent, anti-aging agent, carbon black, vulcanization accelerator, vulcanizing agent, water-absorbing resin, water suction auxiliary agent, white carbon black, expanding material, water swelling rubber matrix, for subsequent use;
2) by paracril on a mill until thin-pass bag roller plasticate after 1min, add promoting agent A, promoting agent B, vulcanizing agent, anti-aging agent, water suction auxiliary agent successively, expanding material, open refining evenly under roll spacing is 2mm after, adding water-absorbing resin evenly mixing, then add reinforced filling carbon black and white carbon black, is 3mm opens refining 10min in roll spacing, finally add vulcanization accelerator A and vulcanization accelerator B is evenly mixing, under roll spacing is 0.4mm, play triangle bag 6 times, thin-pass, bottom sheet, standing 4 hours are for subsequent use;
3) by step 2) paracril mixed that obtains is placed in compression mold, on vulcanizing press in 160 DEG C, under 10Mpa pressure after sulfuration 15min, die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill 24h, cuts out sample.
By such scheme, the preparation method of described expanding material comprises the following steps: joined by 30gNBR in torque rheometer, then 0.15 ~ 0.75g maleic anhydride is added, the mixture of 1.5 ~ 4.5g initiator, torque rheometer three sections of temperature are set as first paragraph 80 ~ 110 DEG C, second segment 80 ~ 110 DEG C, 3rd section 80 ~ 110 DEG C, reaction 3 ~ 10min, after graft reaction completes, taking-up graft product is placed in the extracting of Soxhlet extractor extract and removes the complete initiator of unreacted, maleic anhydride, maleic anhydride homopolymers, obtain expanding material maleic anhydride/paracril graft copolymer.
By such scheme, described promoting agent A is stearic acid, and promoting agent B is ZnO.
By such scheme, described anti-aging agent is antioxidant D (N-phenyl-2-naphthylamine), antioxidant 4010NA (N-sec.-propyl-N '-diphenyl-para-phenylene diamine) or antioxidant D NP (N, N '-two-betanaphthyl Ursol D).
By such scheme, described carbon black is natural gas-based channel black.
By such scheme, described vulcanization accelerator A is altax or captax.
By such scheme, described vulcanization accelerator B is accelerant CZ (N-cyclohexyl-2-benzothiazole sulfonamide).
By such scheme, described vulcanizing agent is sulphur (sublimed sulphur).
By such scheme, described water-absorbing resin is sodium polyacrylate or Lithium polyacrylate.
By such scheme, described water suction auxiliary agent is PEG-6000 or PEG-8000.
By such scheme, described white carbon black is gas-phase silica.
By such scheme, described paracril is the paracril containing nitrile amount 30% ~ 45%.
By such scheme, described initiator is benzoyl peroxide, dicumyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
By such scheme, described extract is acetone, tetrahydrofuran (THF), ethylene glycol Glacial acetic acid mixed solution or sherwood oil.
Water swelling rubber mainly by rubber and absorbent composition, additive etc. by the blended gained of preparing of physical mechanical, because character between rubber with absorbent composition differs comparatively large, both poor compatibility; Absorbent composition particle diameter is little, easily reunites in mixing process; The present invention passes through maleic anhydride graft on the butadiene segment of paracril, obtain reactive compatibilizer maleic anhydride/paracril graft copolymer, can tangle with rubber matrix in one end of expanding material molecule, strong physics, chemical action can be there is in maleic anhydride moities with water-absorbing resin, additive, thus water-absorbing resin, additive are firmly strapped in rubber matrix, improve absorbent composition, additive from the precipitation rubber matrix.
The maleic anhydride graft paracril principle that the present invention uses is as follows;
Tool of the present invention has the following advantages and useful effect:
Reactive compatibilizer maleic anhydride/paracril graft copolymer prepared by the present invention is the activity utilizing α-H on butadiene segment in paracril molecule, under initiator effect, with maleic anhydride generation graft reaction.Compared with traditional preparation water-swelling paracril, water-swelling paracril prepared by the method, absorbent composition is dispersed in rubber matrix, and reactive force between base rubber and water-absorbing resin is strong, water-absorbing resin is not easily separated out, water absorbent rate increases, and water-absorbing resin mass loss rate lowers.This preparation method is simple, and equipment requirements is low, thus cost-saving, can be widely used in the aspects such as tunnel, culvert, swimming pool, vault, underwater engineering, down-hole oil production, water facilities, civilian construction.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram (SEM) of the paracril section used in the embodiment of the present invention 1.
Embodiment
For a better understanding of the present invention, the following examples further illustrate of the present invention, but content of the present invention is not only confined to the following examples.
Embodiment 1 ~ 5
Reactive compatibilizer preparation process is as follows:
Joined by 30gNBR in torque rheometer, then add the mixture of 0.3g maleic anhydride, 3g dicumyl peroxide, torque rheometer three sections of temperature are set as first paragraph 100 DEG C, second segment 100 DEG C, the 3rd section 110 DEG C, reaction 5min.After graft reaction completes, take out graft product and be placed in Soxhlet extractor tetrahydrofuran (THF) extracting 24h, the complete initiator of unreacted, maleic anhydride, maleic anhydride homopolymers are removed in extracting, obtain expanding material maleic anhydride/paracril graft copolymer.
The expanding material maleic anhydride graft paracril upper step prepared is applied in water-swelling paracril, and its step is as follows:
1) by 100 parts of paracrils on a mill until thin-pass bag roller plasticate after 1min, add the stearic acid of 1.5 parts successively, the ZnO of 5 parts, the sublimed sulphur of 1.5 parts, the antioxidant D of 1 part, the PEG-6000 of 10 parts, refining evenly rear (about 3min) is opened under roll spacing is 2mm, then the sodium polyacrylate of 50 parts is added, then add after 4 ~ 12 parts of expanding materials mix, add the carbon black of reinforced filling 20 parts and the white carbon black of 20 parts again, roll spacing be 3mm opens refining 10min, the accelerator CZ finally adding the accelerator DM of 2 parts and 2 parts is evenly mixing, under roll spacing is 0.4mm, play triangle bag 6 times, thin-pass, bottom sheet, standing 4 hours for subsequent use.
2) paracril mixed is placed in compression mold, on vulcanizing press at 160 DEG C after sulfuration 15min (pressure is 10Mpa), die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill 24h, cuts out sample.
3) sample is immersed in is equipped with in the container of liquid nitrogen, after submergence 10min, take out sample brittle rupture, utilize its cross-section morphology of HitachiS-530 sem observation.
Fig. 1 is the SEM figure adding butyronitrile water sucting rubber section before and after expanding material.Fig. 1 a, Fig. 1 b are respectively the scanning electron microscope (SEM) photograph not adding expanding material, add the butyronitrile water sucting rubber section of expanding material.Unmodified butyronitrile water sucting rubber section has many places particle to peel off the pit of formation, and the butyronitrile water swelling rubber section pit of modification is less, and section is fuzzy, show water-absorbing resin and paracril consistency better.
Note: the weight water-intake rate of water-swelling paracril and the account form of rate of weight loss as follows:
Water-swelling paracril prepared by the paracril adding expanding material is cut into the sample of certainweight, and immersed in the salt solution of tap water or other different concns, take out at regular intervals at a certain temperature and weigh, want rapid filter paper to suck the moisture of specimen surface when weighing at every turn, after reaching capacity until absorb water, be dried to constant weight in 50 DEG C.Wherein the weight water-intake rate of water-swelling paracril and rate of weight loss calculate as follows:
The hardness of the vulcanized test specimens of water-swelling paracril is according to standard GB/T531 test, and tensile strength and tensile yield are tested according to standard GB/T528-2009.
Formula and test result are as table 1.
Embodiment 6 ~ 10
1) by 100 parts of paracrils on a mill until thin-pass bag roller plasticate after 1min, add the stearic acid of 1.5 parts successively, the ZnO of 5 parts, the sublimed sulphur of 1.5 parts, the antioxidant D of 1 part, the PEG-8000 of 10 parts, refining evenly rear (about 3min) is opened under roll spacing is 2mm, then the sodium polyacrylate of 30 ~ 70 parts is added, 8 parts of expanding materials mixing evenly after, add the carbon black of reinforced filling 20 parts and the white carbon black of 20 parts again, roll spacing be 3mm opens refining 10min, finally, the accelerator CZ adding the accelerator DM of 2 parts and 2 parts is evenly mixing, under roll spacing is 0.4mm, play triangle bag 6 times, thin-pass, bottom sheet, standing 4 hours for subsequent use.
2) paracril mixed is placed in compression mold, on vulcanizing press at 160 DEG C after sulfuration 15min (pressure is 10Mpa), die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill 24h, cuts out sample.Vulcanized test specimens performance test methods is identical with embodiment 1 ~ 5.
Formula and test result are as table 2.
Embodiment 11 ~ 15
1) by 100 parts of paracrils on a mill until thin-pass bag roller plasticate after 1min, add the stearic acid of 1.5 parts successively, the ZnO of 5 parts, the sublimed sulphur of 1.5 parts, the antioxidant 4010NA of 1 part, the PEG-6000 of 0 ~ 12 part, refining evenly rear (about 3min) is opened under roll spacing is 2mm, then the polypropylene lithium of 50 parts is added, 8 parts of expanding materials (expanding material prepared in embodiment 1) mixing evenly after, add the carbon black of reinforced filling 20 parts and the white carbon black of 20 parts again, roll spacing be 3mm opens refining 10min, finally, the accelerator CZ adding the accelerator DM of 2 parts and 2 parts is evenly mixing, under roll spacing is 0.4mm, play triangle bag 6 times, thin-pass, bottom sheet, standing 4 hours for subsequent use.
2) paracril mixed is placed in compression mold, on vulcanizing press at 160 DEG C after sulfuration 10min (pressure is 10Mpa), die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill 24h, cuts out sample.Vulcanized test specimens performance test methods is identical with embodiment 1 ~ 5.
Formula and test result are as table 3
Table 1
Table 2
Table 3
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (9)
1. the preparation method of increasing reaction type butyronitrile water swelling rubber, comprises the steps:
1) by the number of weight shared by each raw material be: paracril 100 parts, expanding material 4 ~ 12 parts, promoting agent A1.5 part, promoting agent B5 part, 1 part, anti-aging agent, carbon black 20 parts, white carbon black 20 parts, vulcanization accelerator A2 part, vulcanization accelerator B2 part, vulcanizing agent 1.5 parts, water-absorbing resin 30 ~ 70 parts, water suction auxiliary agent 0 ~ 12 part, chooses promoting agent, anti-aging agent, carbon black, vulcanization accelerator, vulcanizing agent, water-absorbing resin, water suction auxiliary agent, white carbon black, expanding material, paracril, for subsequent use, the preparation method of described expanding material comprises the following steps: joined by 30gNBR in torque rheometer, then adds 0.15 ~ 0.75g maleic anhydride, the mixture of 1.5 ~ 4.5g initiator, torque rheometer three sections of temperature are set as first paragraph 80 ~ 110 DEG C, second segment 80 ~ 110 DEG C, 3rd section 80 ~ 110 DEG C, reaction 3 ~ 10min, after graft reaction completes, taking-up graft product is placed in the extracting of Soxhlet extractor extract and removes the complete initiator of unreacted, maleic anhydride, maleic anhydride homopolymers, obtains expanding material maleic anhydride/paracril graft copolymer, described promoting agent A is stearic acid, and promoting agent B is ZnO, described vulcanization accelerator A is altax or captax, described vulcanization accelerator B is accelerant CZ,
2) by paracril on a mill until thin-pass bag roller plasticate after 1min, add promoting agent A, promoting agent B, vulcanizing agent, anti-aging agent, water suction auxiliary agent successively, expanding material, open refining evenly under roll spacing is 2mm after, adding water-absorbing resin evenly mixing, then add reinforced filling carbon black and white carbon black, is 3mm opens refining 10min in roll spacing, finally add vulcanization accelerator A and vulcanization accelerator B is evenly mixing, under roll spacing is 0.4mm, play triangle bag 6 times, thin-pass, bottom sheet, standing 4 hours are for subsequent use;
3) by step 2) paracril mixed that obtains is placed in compression mold, on vulcanizing press in 160 DEG C, under 10MPa pressure after sulfuration 15min, die sinking, takes out the water-swelling paracril vulcanizated, and leaves standstill 24h, cuts out sample.
2. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described anti-aging agent is antioxidant D, antioxidant 4010NA or antioxidant D NP.
3. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described carbon black is natural gas-based channel black.
4. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described vulcanizing agent is sulphur.
5. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described water-absorbing resin is sodium polyacrylate or Lithium polyacrylate.
6. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described water suction auxiliary agent is PEG-6000 or PEG-8000.
7. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that described white carbon black is gas-phase silica.
8. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that: described initiator is benzoyl peroxide, dicumyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
9. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, is characterized in that: described extract is acetone, tetrahydrofuran (THF), ethylene glycol Glacial acetic acid mixed solution or sherwood oil.
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| CN104277258B (en) * | 2014-09-28 | 2016-07-27 | 苏州长盛机电有限公司 | A kind of preparation method of the water swelling rubber of good weatherability |
| CN104974390B (en) * | 2015-07-07 | 2017-11-28 | 徐州工业职业技术学院 | A kind of rubber water absorbent composite material containing modified wood powder |
| CN106117664B (en) * | 2016-07-01 | 2017-12-12 | 武汉工程大学 | One kind uses water swelling rubber and preparation method thereof made of hydrophilic fibre |
| CN107061872B (en) * | 2017-06-15 | 2018-04-10 | 李江 | A kind of easy-to-mount stainless steel tube |
| CN108892205A (en) * | 2018-07-30 | 2018-11-27 | 刘玉友 | A kind of application method of the no filtrate sewage-treatment plant of oil field gathering and transportation |
| CN109666199A (en) * | 2018-11-23 | 2019-04-23 | 陶伟珍 | A kind of high-strength absorbing rubber and preparation method thereof |
| CN109777125A (en) * | 2019-01-31 | 2019-05-21 | 潍坊硕邑化学有限公司 | A kind of water-swellable chlorosulfonated polyethylene rubber composition and preparation method thereof |
| CN111171409A (en) * | 2020-02-25 | 2020-05-19 | 广州机械科学研究院有限公司 | High-temperature-resistant, high-strength and high-expansion-rate rubber and preparation method thereof |
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| CN103333376A (en) * | 2013-07-26 | 2013-10-02 | 武汉工程大学 | Compatibilizer of water-swelling nitrile rubber and preparation method of compatibilizer |
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| CN102432954A (en) * | 2011-08-16 | 2012-05-02 | 南京工业大学 | Water-absorbing expanded rubber containing polyaspartic-acid water-absorbing material and preparation method thereof |
| CN103333377A (en) * | 2013-07-26 | 2013-10-02 | 武汉工程大学 | Water-swelling nitrile rubber and preparation method thereof |
| CN103333376A (en) * | 2013-07-26 | 2013-10-02 | 武汉工程大学 | Compatibilizer of water-swelling nitrile rubber and preparation method of compatibilizer |
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