CN104017254A - Method for preparing reactive compatibilization-type nitrile water-swelling rubber - Google Patents
Method for preparing reactive compatibilization-type nitrile water-swelling rubber Download PDFInfo
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Abstract
The invention relates to a method for preparing reactive compatibilization-type nitrile water-swelling rubber. The method comprises the following steps: sequentially adding an active agent A, an active agent B, a vulcanizing agent, an anti-aging agent, a water absorbing additive and a bulking agent after plastifying nitrile rubber on an open mill by adopting a thinning coating roll; adding water-absorbing resin to evenly mix after mixing evenly, and then adding reinforcing filler carbon black and white carbon black; milling, and finally adding a vulcanization accelerator A and a vulcanization accelerator B to evenly mix; packaging into a triangular packet; thinning, batching off and standing for later use; putting the mixed nitrile rubber into a tabletting mold; vulcanizing, opening the mold, taking out the vulcanized water-swelling nitrile rubber, standing and cutting. The method has the advantages and beneficial effects that the preparation method is simple, and low in requirement on equipment, so as to save the cost. The method can be widely applied to tunnels, culverts, swimming pools, basements, underwater engineering, downhole oil recovery, water supply facilities, civil construction and the like.
Description
Technical field
The preparation method who the present invention relates to a kind of increasing reaction type butyronitrile water swelling rubber, belongs to sealing material field.
Technical background
Water swelling rubber (Water swelling Rubber is called for short WSR) is in the matrix of rubber, to introduce hydrophilic radical or absorbent composition and a kind of new functional macromolecule material of making.From the new functional macromolecule material of 20 century 70s exploitations, the inflatable several times to sole mass and even hundreds of times after water suction.And in keeping caoutchouc elasticity, also there is water-retentivity.Can be widely used in the water-tight of building deformation seam, construction joint waterproof, underwater instrument and war industry's weapon, 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 the effect with 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 method to prepare water swelling rubber (being that hydrophilic component and rubber matrix carry out blend), be easy to because hydrophilic component particle diameter is little reunite, character between hydrophilic component and rubber differs larger, hydrophilic component disperses inhomogeneous in rubber, make hydrophilic component be easy to separate out, thereby lowered water absorbing properties and the mechanical property of water swelling rubber.Therefore improve the bonding force between absorbent composition and rubber with expanding material, improve hydrophilic component and separate 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, utilize chlorohydrin rubber and crosslinked salt polyacrylate to prepare WSR, mass loss rate after immersion 18.82% drops to 14.32% by what do not add, 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 complexity, equipment requirements is higher.
The employing solution graftings such as Xie Jingsi have been prepared expanding material P (AM-g-NBR) and have been come increase-volume paracril, SAR-PA water-absorbing resin system, and expanding material preparation method complexity, need to consume a large amount of solvents.
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 from this water swelling rubber, to have added reactive compatibilizer, method is simple, without consuming a large amount of solvents, aftertreatment is easy), can finely improve the dispersion of absorbent composition in rubber matrix, 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 umber of the shared weight of each raw material be: 100 parts of paracrils, 4～12 parts of expanding materials, promoting agent A1.5 part, promoting agent B5 part, 1 part, anti-aging agent, 20 parts of carbon blacks, 20 parts of white carbon blacks, vulcanization accelerator A2 part, vulcanization accelerator B2 part, 1.5 parts of vulcanizing agents, 30～70 parts of water-absorbing resins, 0～12 part of water suction auxiliary agent, 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) paracril thin-pass bag roller in mill is plasticated after 1min, add successively promoting agent A, promoting agent B, vulcanizing agent, anti-aging agent, water suction auxiliary agent, expanding material, be under 2mm, to open after refining evenly in roll spacing, adding water-absorbing resin mixing evenly, then add reinforced filling carbon black and white carbon black, is on 3mm, to open refining 10min in roll spacing, finally add vulcanization accelerator A and vulcanization accelerator B mixing evenly, be under 0.4mm in roll spacing, play triangle bag 6 times, thin-pass, lower, standing 4 hours for subsequent use;
3) by step 2) paracril mixing that obtains is placed in compression mold, on vulcanizing press, under 160 DEG C, 10Mpa pressure, vulcanizes after 15min, and die sinking, takes out the water-swelling paracril vulcanizating, and leaves standstill 24h, cuts out sample.
Press such scheme, the preparation method of described expanding material comprises the following steps: 30gNBR is joined in torque rheometer, then add 0.15～0.75g maleic anhydride, the mixture of 1.5～4.5g initiator, three sections of Temperature Settings of torque rheometer are 80～110 DEG C of first paragraphs, 80～110 DEG C of second segments, the 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 homopolymer, obtain expanding material maleic anhydride/paracril graft copolymer.
Press such scheme, described promoting agent A is stearic acid, and promoting agent B is ZnO.
Press 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 '-bis--betanaphthyl Ursol D).
Press such scheme, described carbon black is natural gas-based channel black.
Press such scheme, described vulcanization accelerator A is altax or captax.
Press such scheme, described vulcanization accelerator B is accelerant CZ (N-cyclohexyl-2-benzothiazole sulfonamide).
Press such scheme, described vulcanizing agent is sulphur (sublimed sulphur).
Press such scheme, described water-absorbing resin is sodium polyacrylate or Lithium polyacrylate.
Press such scheme, described water suction auxiliary agent is PEG-6000 or PEG-8000.
Press such scheme, described white carbon black is gas-phase silica.
Press such scheme, described paracril is the paracril containing nitrile amount 30%～45%.
Press such scheme, described initiator is benzoyl peroxide, dicumyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
Press such scheme, described extract is acetone, tetrahydrofuran (THF), ethylene glycol Glacial acetic acid mixed solution or sherwood oil.
Water swelling rubber is mainly prepared gained by rubber and absorbent composition, additive etc. by physical mechanical blend, and because character between rubber and absorbent composition differs larger, both consistencies are poor; Absorbent composition particle diameter is little, in mixing process, easily reunites; The present invention passes through maleic anhydride graft to the divinyl segment of paracril, obtain reactive compatibilizer maleic anhydride/paracril graft copolymer, can tangle with rubber matrix in one end of expanding material molecule, can there is strong physics, chemical action with water-absorbing resin, additive in maleic anhydride part, thereby water-absorbing resin, additive are firmly strapped in rubber matrix, improve absorbent composition, additive separating out from 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 to utilize in paracril molecule the activity of α-H on divinyl segment, 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 difficult for separating out, water absorbent rate increases, and water-absorbing resin mass loss rate lowers.This preparation method is simple, and equipment requirements is low, thereby 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.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of the paracril section of use in the embodiment of the present invention 1.
Embodiment
For a better understanding of the present invention, the following examples are to 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:
30gNBR is joined in torque rheometer, then add the mixture of 0.3g maleic anhydride, 3g dicumyl peroxide, three sections of Temperature Settings of torque rheometer are 100 DEG C of first paragraphs, 100 DEG C of second segments, 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 homopolymer are removed in extracting, obtain expanding material maleic anhydride/paracril graft copolymer.
Expanding material maleic anhydride graft paracril prepared by upper step is applied in water-swelling paracril, and its step is as follows:
1) 100 parts of paracrils thin-pass bag roller in mill is plasticated after 1min, add successively the stearic acid of 1.5 parts, the ZnO of 5 parts, the sublimed sulphur of 1.5 parts, the antioxidant D of 1 part, the PEG-6000 of 10 parts, after roll spacing is to open refining evenly under 2mm (about 3min), then add the sodium polyacrylate of 50 parts, then after adding 4～12 parts of expanding materials to mix, add again the carbon black of 20 parts of reinforced fillings and the white carbon black of 20 parts, be on 3mm, to open refining 10min in roll spacing, finally add the accelerator CZ of the accelerator DM of 2 parts and 2 parts mixing evenly, be under 0.4mm in roll spacing, play triangle bag 6 times, thin-pass, lower, standing 4 hours for subsequent use.
2) paracril mixing is placed in to compression mold, vulcanizes (pressure is 10Mpa) after 15min on vulcanizing press at 160 DEG C, die sinking, takes out the water-swelling paracril vulcanizating, and leaves standstill 24h, cuts out sample.
3) sample is immersed in the container that liquid nitrogen is housed, after submergence 10min, takes out sample brittle rupture, utilize its cross-section morphology of HitachiS-530 sem observation.
Fig. 1 is the SEM figure that adds expanding material front and back butyronitrile water sucting rubber section.Fig. 1 a, Fig. 1 b are respectively the scanning electron microscope (SEM) photograph that does not add expanding material, adds the butyronitrile water sucting rubber section of expanding material.On unmodified butyronitrile water sucting rubber section, have many places particle to peel off the pit of formation, the butyronitrile water swelling rubber section pit of modification is less, and section is fuzzy, shows that water-absorbing resin and paracril consistency are better.
Note: the weight water-intake rate of water-swelling paracril and the account form of rate of weight loss are as follows:
Water-swelling paracril prepared by the paracril that adds expanding material is cut into the sample of certainweight, and immersed in the salt solution of tap water or other different concns, take out and weigh at regular intervals at a certain temperature, while weighing, want to suck with filter paper rapidly the moisture of specimen surface at every turn, after reaching capacity until absorb water, be dried to constant weight in 50 DEG C.Wherein weight water-intake rate and the rate of weight loss of water-swelling paracril calculate as follows:
The hardness of the sulfuration sample 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) 100 parts of paracrils thin-pass bag roller in mill is plasticated after 1min, add successively the stearic acid of 1.5 parts, the ZnO of 5 parts, the sublimed sulphur of 1.5 parts, the antioxidant D of 1 part, the PEG-8000 of 10 parts, after roll spacing is to open refining evenly under 2mm (about 3min), then add the sodium polyacrylate of 30～70 parts, 8 parts of expanding materials mixing evenly after, add again the carbon black of 20 parts of reinforced fillings and the white carbon black of 20 parts, be on 3mm, to open refining 10min in roll spacing, finally, add the accelerator CZ of the accelerator DM of 2 parts and 2 parts mixing evenly, be under 0.4mm in roll spacing, play triangle bag 6 times, thin-pass, lower, standing 4 hours for subsequent use.
2) paracril mixing is placed in to compression mold, vulcanizes (pressure is 10Mpa) after 15min on vulcanizing press at 160 DEG C, die sinking, takes out the water-swelling paracril vulcanizating, and leaves standstill 24h, cuts out sample.Sulfuration sample performance testing method is identical with embodiment 1～5.
Formula and test result are as table 2.
Embodiment 11～15
1) 100 parts of paracrils thin-pass bag roller in mill is plasticated after 1min, add successively the stearic acid of 1.5 parts, 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, after roll spacing is to open refining evenly under 2mm (about 3min), then add the polypropylene lithium of 50 parts, 8 parts of expanding materials (in embodiment 1 prepared expanding material) mixing evenly after, add again the carbon black of 20 parts of reinforced fillings and the white carbon black of 20 parts, be on 3mm, to open refining 10min in roll spacing, finally, add the accelerator CZ of the accelerator DM of 2 parts and 2 parts mixing evenly, be under 0.4mm in roll spacing, play triangle bag 6 times, thin-pass, lower, standing 4 hours for subsequent use.
2) paracril mixing is placed in to compression mold, vulcanizes (pressure is 10Mpa) after 10min on vulcanizing press at 160 DEG C, die sinking, takes out the water-swelling paracril vulcanizating, and leaves standstill 24h, cuts out sample.Sulfuration sample performance testing method is identical with embodiment 1～5.
Formula and test result are as table 3
Table 1
Table 2
Table 3
Each raw material that the present invention is cited, and the bound of the 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 (14)
1. the preparation method of increasing reaction type butyronitrile water swelling rubber, comprises the steps:
1) by the umber of the shared weight of each raw material be: 100 parts of paracrils, 4～12 parts of expanding materials, promoting agent A1.5 part, promoting agent B5 part, 1 part, anti-aging agent, 20 parts of carbon blacks, 20 parts of white carbon blacks, vulcanization accelerator A2 part, vulcanization accelerator B2 part, 1.5 parts of vulcanizing agents, 30～70 parts of water-absorbing resins, 0～12 part of water suction auxiliary agent, 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) paracril thin-pass bag roller in mill is plasticated after 1min, add successively promoting agent A, promoting agent B, vulcanizing agent, anti-aging agent, water suction auxiliary agent, expanding material, be under 2mm, to open after refining evenly in roll spacing, adding water-absorbing resin mixing evenly, then add reinforced filling carbon black and white carbon black, is on 3mm, to open refining 10min in roll spacing, finally add vulcanization accelerator A and vulcanization accelerator B mixing evenly, be under 0.4mm in roll spacing, play triangle bag 6 times, thin-pass, lower, standing 4 hours for subsequent use;
3) by step 2) paracril mixing that obtains is placed in compression mold, on vulcanizing press, under 160 DEG C, 10Mpa pressure, vulcanizes after 15min, and die sinking, takes out the water-swelling paracril vulcanizating, and leaves standstill 24h, cuts out sample.
2. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1, the preparation method who it is characterized in that described expanding material comprises the following steps: 30gNBR is joined in torque rheometer, then add 0.15～0.75g maleic anhydride, the mixture of 1.5～4.5g initiator, three sections of Temperature Settings of torque rheometer are 80～110 DEG C of first paragraphs, 80～110 DEG C of second segments, the 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 homopolymer, obtain expanding material maleic anhydride/paracril graft copolymer.
3. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described promoting agent A is stearic acid, and promoting agent B is ZnO.
4. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described anti-aging agent is antioxidant D, antioxidant 4010NA or antioxidant D NP.
5. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described carbon black is natural gas-based channel black.
6. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described vulcanization accelerator A is altax or captax.
7. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described vulcanization accelerator B is accelerant CZ.
8. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described vulcanizing agent is sulphur.
9. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described water-absorbing resin is sodium polyacrylate or Lithium polyacrylate.
10. the preparation method of increasing reaction type butyronitrile water swelling rubber according to claim 1 and 2, is characterized in that described water suction auxiliary agent is PEG-6000 or PEG-8000.
The preparation method of 11. increasing reaction type butyronitrile water swelling rubbers according to claim 1 and 2, is characterized in that described white carbon black is gas-phase silica.
The preparation method of 12. increasing reaction type butyronitrile water swelling rubbers according to claim 2, is characterized in that: described paracril is the paracril containing nitrile amount 30%～45%.
The preparation method of 13. increasing reaction type butyronitrile water swelling rubbers according to claim 2, is characterized in that: described initiator is benzoyl peroxide, dicumyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
The preparation method of 14. increasing reaction type butyronitrile water swelling rubbers according to claim 2, is characterized in that: described extract is acetone, tetrahydrofuran (THF), ethylene glycol Glacial acetic acid mixed solution or sherwood oil.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104277258A (en) * | 2014-09-28 | 2015-01-14 | 苏州长盛机电有限公司 | Method for preparing water swelling rubber with good weather resistance |
| CN104974390A (en) * | 2015-07-07 | 2015-10-14 | 徐州工业职业技术学院 | Rubber water-absorption composite material containing modified wood meal |
| CN106117664A (en) * | 2016-07-01 | 2016-11-16 | 武汉工程大学 | A kind of water swelling rubber using hydrophilic fibre to make and preparation method thereof |
| CN107061872A (en) * | 2017-06-15 | 2017-08-18 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104277258A (en) * | 2014-09-28 | 2015-01-14 | 苏州长盛机电有限公司 | Method for preparing water swelling rubber with good weather resistance |
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| CN106117664A (en) * | 2016-07-01 | 2016-11-16 | 武汉工程大学 | A kind of water swelling rubber using hydrophilic fibre to make and preparation method thereof |
| CN107061872A (en) * | 2017-06-15 | 2017-08-18 | 李江 | A kind of easy-to-mount stainless steel tube |
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| 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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