CN103333376B - Compatibilizer of water-swelling nitrile rubber and preparation method of compatibilizer - Google Patents
Compatibilizer of water-swelling nitrile rubber and preparation method of compatibilizer Download PDFInfo
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- CN103333376B CN103333376B CN201310320046.7A CN201310320046A CN103333376B CN 103333376 B CN103333376 B CN 103333376B CN 201310320046 A CN201310320046 A CN 201310320046A CN 103333376 B CN103333376 B CN 103333376B
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- paracril
- water
- maleic anhydride
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Abstract
The invention relates to a compatibilizer of a water-swelling nitrile rubber and a preparation method of the compatibilizer. The preparation method comprises the following steps of: respectively dissolving nitrile rubber, maleic anhydride and an initiator in a solvent, and raising the temperature of a nitrile rubber solution to 55-75 DEG C; slowly adding a mixed solution of the maleic anhydride and the initiator to be subjected to a constant temperature reaction for 8-12h and then discharging; adding a precipitating agent to separate a graft product of the nitrile rubber and the maleic anhydride, and washing the product with distilled water; drying and cutting the washed graft product into pieces, and removing the initiator, the maleic anhydride and a maleic anhydride homopolymer by extraction; and drying to obtain the compatibilizer of the water-swelling nitrile rubber. The matrix of the water-swelling nitrile rubber prepared by the method has strong interaction with a water-absorbent resin, the water-absorbent resin does not easily fall off, the absorbency is increased, the mass loss rate of the water-absorbent resin is reduced, and the cost is saved and the preparation method is simple.
Description
Technical field
The invention belongs to functional high polymer material field, be specifically related to a kind of expanding material for water-swelling paracril and preparation method thereof.
Background technology
Water swelling rubber (Water swelling Rubber 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.Since beginning of the eighties late 1970s comes out, water swelling rubber has caused the attention of people because of the resilient seal sealing of its uniqueness and the dual water stopping function of water-swelling sealing.Can extensively 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 with the effect of water sealing again, and easy construction, saving material, reduce construction costs.WSR is a kind of substituted type waterproof and sealing material, and therefore, it has good application prospect and huge market.
Water swelling rubber mainly by rubber and water-absorbing resin two component by the blended gained of preparing of physical mechanical, because the wetting ability of rubber is poor, and water-absorbing resin good hydrophilic property, cause both poor compatibility.Industrial the most frequently used method utilizes physical blending process to prepare water swelling rubber (namely hydrophilic component and rubber matrix carry out blended), because the character between hydrophilic component with rubber differs larger, 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 the polyvinyl alcohol graft copolymerized butyl polyacrylate amphipathic graft copolymer of PVA-g-PBA() 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%, mass loss rate is still comparatively large, and physical and mechanical properties is poor.
Wang Caiqi etc. are with amphipathic nature block polymer PEO-b-PBA(poly-ethylene oxide block butyl polyacrylate) improve the consistency of absorption resin of sodium polyacrylate and natural rubber, mass loss rate is larger, and expanding material synthesis technique is complicated, equipment requirements is higher.
Summary of the invention
It is simple that the object of the invention is to provide a kind of preparation method, the low expanding material that paracril is effective and increase-volume absorbs water of equipment requirements.
The technical scheme adopted is as follows:
An expanding material for water-swelling paracril, the effective constituent wherein contained is the grafts of paracril and maleic anhydride, and all the other are paracril.
By such scheme, the expanding material of described water-swelling paracril is the product that following method prepares:
Paracril, maleic anhydride and initiator are dissolved in respectively in solvent, nitrile rubber solution is warming up to 55 ~ 75 DEG C; The mixing solutions of slow dropping maleic anhydride and initiator, isothermal reaction 8 ~ 12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and with distilled water wash; Grafts after washing is dried, shredded, extracting removing initiator, maleic anhydride and maleic anhydride homopolymers; The expanding material of water-swelling paracril is obtained after drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1 ~ 2:0.08 ~ 0.2 by weight, paracril containing nitrile amount be 30wt% ~ 45wt%.
By such scheme, described solvent select in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, chlorobenzene any one.
By such scheme, described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) any one.
By such scheme, described precipitation agent select in dehydrated alcohol, methyl alcohol, distilled water any one.
By such scheme, the extract selected in extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, sherwood oil.
By such scheme, the preparation method of water-swelling paracril expanding material, comprises the following steps:
Paracril, maleic anhydride and initiator are dissolved in respectively in solvent, nitrile rubber solution is warming up to 55 ~ 75 DEG C; The mixing solutions of slow dropping maleic anhydride and initiator, isothermal reaction 8 ~ 12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and with distilled water wash; Grafts after washing is dried, shredded, extracting removing initiator, maleic anhydride and maleic anhydride homopolymers; The expanding material of water-swelling paracril is obtained after drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1 ~ 2:0.08 ~ 0.2 by weight, paracril containing nitrile amount be 30wt% ~ 45wt%; The extract selected in extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, sherwood oil.
By such scheme, described solvent select in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, chlorobenzene any one.
By such scheme, described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) any one.
By such scheme, described precipitation agent select in dehydrated alcohol, methyl alcohol, distilled water any one.
The present invention utilizes the activity of α-H on butadiene segment on paracril, what under initiator effect, adopt maleic anhydride graft paracril to prepare obtains reactive compatibilizer, the divinyl contained in its molecule on the one hand, propenyl segment can with the divinyl in rubber matrix, propenyl segment generation physical entanglement effect, form strong chemical bond between the maleic anhydride moities energy contained in its molecule on the other hand and water-absorbing resin; Together with firmly rubber matrix being strapped in water-absorbing resin on this basis, the interfacial tension of Reinforced Rubber matrix and absorbent composition, increase the consistency of matrix and absorbent composition, reduce absorbent composition and come off from matrix, the water sucting rubber physical and mechanical properties of preparation is excellent.
Maleic anhydride graft paracril preparation principle is as follows:
Beneficial effect of the present invention:
Compared with traditional preparation water-swelling paracril, the water-swelling paracril rubber that the expanding material adopting the present invention to prepare obtains, reactive force between its rubber matrix and water-absorbing resin is strong, water-absorbing resin difficult drop-off, water absorbent rate increases, and water-absorbing resin mass loss rate lowers, and can reach and make itself and the blended uniform object of absorbent composition, thus cost-saving, preparation method is simple.
Accompanying drawing explanation
Fig. 1: the contrast infared spectrum of maleic anhydride graft paracril product and paracril.
Fig. 2: the thermal weight loss comparison diagram of maleic anhydride graft paracril product and paracril.
Embodiment
For a better understanding of the present invention, embodiment further illustrates of the present invention, but content of the present invention is not limited to the following examples.
Embodiment 1:
After the tetrahydrofuran (THF) of the paracril 30mL of 1g is all dissolved, slowly drip the tetrahydrofuran solution of 1g maleic anhydride and 0.16g benzoyl peroxide, be warming up to 65 DEG C, isothermal reaction 12h.Reaction terminates rear alcohol settling and goes out grafts, then, with a large amount of distilled water washs several, is placed on room temperature in vacuum drying oven and dries, in Soxhlet extractor acetone soln extracting 12h after oven dry, obtain maleic anhydride graft paracril.Expanding material is obtained for subsequent use after abundant drying.Do infrared test, thermal weight loss test.
Can obviously find out in Fig. 1 (a), near 2890-2920cm-1, a series of absorption peak is-CH
3with-CH
2in the stretching vibration peak of C-H, 2240cm
-1neighbouring is-C ≡ N charateristic avsorption band, 1640cm
-1for alkene-C=C-stretching vibration peak, 1440cm
-1, 968cm
-1for the vibration of alkene-C-H in-plane deformation.Obviously can be derived as the characteristic peak of butadiene segment and vinyl cyanide segment, be the absorption peak of paracril.
Fig. 1 (b) is the paracril infared spectrum after maleic anhydride graft, 3357cm
-1broad peak is-OH stretching vibration, 1779,1721cm
-1corresponding to acid anhydrides charateristic avsorption band (bimodal), be positioned at 1651cm
-1for fat lactones-C=O formation vibration, 1446cm
-1for the vibration of alkene-C-H in-plane deformation, 1261,1046cm
-1be respectively acid anhydrides-C-O-C and become ring, acyclic stretching vibration peak, 920cm
-1for formation vibration outside carboxylic acid-OH face.Thus drawn acid anhydrides, and olefinic double bonds peak is also clearly, and-C ≡ N peak does not have considerable change yet.
Comparison diagram 1 (a), (b) are known, and maleic anhydride graft has successfully been grafted on paracril, and then provide feasibility for the water-swelling paracril that preparation consistency is good.
In Fig. 2, can obviously find out, pure paracril (NBR) is obvious thermal weight loss for once, when occurring in 360 DEG C, is the thermal weight loss of paracril; Maleic anhydride/paracril grafts (MAH-g-NBR) has twice obvious thermal weight loss, first paragraph occurs in 152 DEG C time, mainly because the carbonyl of maleic anhydride is unstable, easily decarboxylic reaction occurs, at about 360 DEG C, the decarboxylic reaction of maleic anhydride completes substantially.Another time thermal weight loss is similar to pure paracril temperature, and after 500 DEG C, quality remains unchanged substantially.Can show that maleic anhydride has been grafted on paracril molecule really thus.
Be applied in water-swelling paracril by the expanding material of preparation in embodiment 1, 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 2 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 add the water-absorbing resin (sodium polyacrylate 100 order) of 50 parts 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, then 0 is added, 5, 10, 15, after 20 parts of expanding materials mix, finally the accelerator CZ of the accelerator DM of 2 parts and 2 parts is added in rubber matrix 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.
Wherein, 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 (consumption is counted by weight) and test result are as table 1.
Table 1
Embodiment 2
After the toluene of the paracril 30mL of 1g is all dissolved, slowly drip the toluene solution of 2.0g maleic anhydride and 0.2g benzoyl peroxide, be warming up to 55 DEG C, isothermal reaction 10h.Reaction terminates rear distilled water and is settled out grafts, then, with a large amount of distilled water washs several, is placed on room temperature in vacuum drying oven and dries, dry at Soxhlet extractor spent glycol, Glacial acetic acid mixing solutions extracting 12h, obtain expanding material for subsequent use after oven dry.
Be applied in water-swelling paracril by gained expanding material in embodiment 2, embodiment is with embodiment 1.
Formula (consumption is counted by weight) and test result are in table 2.
Table 2
Embodiment 3
After the tetrahydrofuran (THF) of the paracril 30mL of 1g is all dissolved, slowly drip the tetrahydrofuran solution of 1.2g maleic anhydride and 0.08g benzoyl peroxide, be warming up to 63 DEG C, isothermal reaction 8h.Reaction terminates rear distilled water and is settled out grafts, then, with a large amount of distilled water washs several, is placed on room temperature in vacuum drying oven and dries, dry at Soxhlet extractor acetone soln extracting 12h, obtain expanding material maleic anhydride graft paracril after oven dry.
Be applied in water-swelling paracril by gained expanding material in embodiment 3, embodiment is with embodiment 1.
Formula (consumption is counted by weight) and test result are in table 3.
Table 3
Claims (9)
1. an expanding material for water-swelling paracril, it is characterized in that the effective constituent wherein contained is the grafts of paracril and maleic anhydride, all the other are paracril; Described expanding material is that following method prepares:
Paracril, maleic anhydride and initiator are dissolved in respectively in solvent, nitrile rubber solution is warming up to 55 ~ 75 DEG C; The mixing solutions of slow dropping maleic anhydride and initiator, isothermal reaction 8 ~ 12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and with distilled water wash; Grafts after washing is dried, shredded, extracting removing initiator, maleic anhydride and maleic anhydride homopolymers; The expanding material of water-swelling paracril is obtained after drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1 ~ 2:0.08 ~ 0.2 by weight, paracril containing nitrile amount be 30wt% ~ 45wt%.
2. the expanding material of water-swelling paracril as claimed in claim 1, it is characterized in that described solvent selects in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, chlorobenzene any one.
3. the expanding material of water-swelling paracril as claimed in claim 1, is characterized in that described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) any one.
4. the expanding material of water-swelling paracril as claimed in claim 1, it is characterized in that described precipitation agent selects in dehydrated alcohol, methyl alcohol, distilled water any one.
5. the expanding material of water-swelling paracril as claimed in claim 1, is characterized in that the extract selected in extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, sherwood oil.
6. the preparation method of water-swelling paracril expanding material according to claim 1, is characterized in that comprising the following steps:
Paracril, maleic anhydride and initiator are dissolved in respectively in solvent, nitrile rubber solution is warming up to 55 ~ 75 DEG C; The mixing solutions of slow dropping maleic anhydride and initiator, isothermal reaction 8 ~ 12h discharging; Add precipitation agent, isolate the graft product of paracril and maleic anhydride, and with distilled water wash; Graft product after washing is dried, shredded, extracting removing initiator, maleic anhydride and maleic anhydride homopolymers; The expanding material of water-swelling paracril is obtained after drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1 ~ 2:0.08 ~ 0.2 by weight, paracril containing nitrile amount be 30wt% ~ 45wt%; The extract selected in extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, sherwood oil.
7. the preparation method of water-swelling paracril expanding material as claimed in claim 6, it is characterized in that described solvent selects in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, chlorobenzene any one.
8. the preparation method of water-swelling paracril expanding material as claimed in claim 6, is characterized in that described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) any one.
9. the preparation method of water-swelling paracril expanding material as claimed in claim 6, it is characterized in that described precipitation agent selects in dehydrated alcohol, methyl alcohol, distilled water any one.
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| 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 |
| CN105037639A (en) * | 2015-09-11 | 2015-11-11 | 古道尔工程塑胶（深圳）有限公司 | Compatible type toughening agent, preparation method and composite material applying the same |
| CN109360676A (en) * | 2018-09-17 | 2019-02-19 | 江苏亨通电力电缆有限公司 | Tunnel the manufacturing process of Suporting structure oil resistant cable |
| CN114133921B (en) * | 2020-09-04 | 2023-06-30 | 中国石油天然气集团有限公司 | Modified high-water-absorption high-strength rubber particle plugging agent, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204357A1 (en) * | 1985-05-03 | 1986-12-10 | Stamicarbon B.V. | Polymer composition |
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| JPS6056742B2 (en) * | 1982-09-29 | 1985-12-11 | 旭化成株式会社 | resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0204357A1 (en) * | 1985-05-03 | 1986-12-10 | Stamicarbon B.V. | Polymer composition |
Non-Patent Citations (2)
| Title |
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| "P(AM-g-NBR)改性共混型吸水膨胀丁腈橡胶制备与性能研究";谢静思等;《广州化工》;20100415;第38卷(第4期);第90页第1.2节 * |
| "吸水膨胀橡胶的研究进展";张群等;《世界橡胶工业》;20100320;第37卷(第3期);第19页第1节 * |
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