CN103333376A - 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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- CN103333376A CN103333376A CN2013103200467A CN201310320046A CN103333376A CN 103333376 A CN103333376 A CN 103333376A CN 2013103200467 A CN2013103200467 A CN 2013103200467A CN 201310320046 A CN201310320046 A CN 201310320046A CN 103333376 A CN103333376 A CN 103333376A
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- paracril
- water
- maleic anhydride
- initiator
- swelling
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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 the water-swelling paracril and preparation method thereof.
Background technology
Water swelling rubber (Water swelling Rubber is called for short WSR) is to introduce hydrophilic radical or absorbent composition and a kind of new functional macromolecule material of making in the matrix of rubber.Since coming out beginning of the eighties late 1970s, water swelling rubber has caused people's attention because of the dual sealing function of its unique resilient seal sealing and water-swelling sealing.Can be extensively in the joint waterproofing sealing of pipeline such as building deformation seam, construction joint waterproof, the water-tight of instrument and war industry's weapon, and metal under water, concrete, pottery, plastics, iron and steel and box culvert.Compare with traditional pressurized joint seal material, water swelling rubber had both possessed the sealing function of conventional sealing material, can play the effect with the water sealing again, and easy construction, saving material, reduced construction costs.WSR is a kind of substituted type waterproof and sealing material, and therefore, it has good application prospects and huge market.
Water swelling rubber mainly prepares gained by rubber and water-absorbing resin two components by the physical mechanical blend, because the wetting ability of rubber is poor, and the water-absorbing resin good hydrophilic property causes both consistencies poor.Industrial the most frequently used method is to utilize the physical blending method to prepare water swelling rubber (being that hydrophilic component and rubber matrix carry out blend), because the character between hydrophilic component and the rubber differs bigger, make that hydrophilic component is easy to separate out, thereby lowered water absorbing properties and the mechanical property of water swelling rubber.Therefore use expanding material to improve bonding force between absorbent composition and the rubber, improve hydrophilic component and separate out problem.
Zhang Zhi persons of outstanding talent etc. are with the polyvinyl alcohol graft copolymerized butyl polyacrylate amphipathic graft copolymer of PVA-g-PBA() as expanding material, utilize chlorohydrin rubber and crosslinked salt polyacrylate to prepare WSR, mass loss rate after the immersion 18.82% drops to 14.32% by what do not add, mass loss rate is still bigger, and physical and mechanical properties is relatively 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 bigger, and expanding material synthesis technique complexity, equipment requirements is higher.
Summary of the invention
The object of the invention is to provide a kind of preparation method simple, the low and effective expanding material of increase-volume suction paracril of equipment requirements.
The technical scheme that adopts is as follows:
A kind of expanding material of water-swelling paracril, the effective constituent that wherein contains are the grafts of paracril and maleic anhydride, and all the other are paracril.
Press 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 the solvent, and nitrile rubber solution is warming up to 55～75 ℃; Slowly drip the mixing solutions of maleic anhydride and initiator, isothermal reaction 8～12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and use distilled water wash; Grafts after the washing is dried, shredded, and initiator, maleic anhydride and maleic anhydride homopolymer are removed in extracting; Obtain the expanding material of water-swelling paracril after the drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1～2:0.08～0.2 by weight, and the nitrile amount that contains of paracril is 30wt%～45wt%.
Press such scheme, described solvent is selected any one in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, the chlorobenzene for use.
Press such scheme, described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile) any one for use.
Press such scheme, described precipitation agent is selected any one in dehydrated alcohol, methyl alcohol, the distilled water for use.
Press such scheme, the extract of selecting for use in the extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, the sherwood oil.
Press such scheme, the preparation method of water-swelling paracril expanding material may further comprise the steps:
Paracril, maleic anhydride and initiator are dissolved in respectively in the solvent, and nitrile rubber solution is warming up to 55～75 ℃; Slowly drip the mixing solutions of maleic anhydride and initiator, isothermal reaction 8～12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and use distilled water wash; Grafts after the washing is dried, shredded, and initiator, maleic anhydride and maleic anhydride homopolymer are removed in extracting; Obtain the expanding material of water-swelling paracril after the drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1～2:0.08～0.2 by weight, and the nitrile amount that contains of paracril is 30wt%～45wt%; The extract of selecting for use in the extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, the sherwood oil.
Press such scheme, described solvent is selected any one in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, the chlorobenzene for use.
Press such scheme, described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile) any one for use.
Press such scheme, described precipitation agent is selected any one in dehydrated alcohol, methyl alcohol, the distilled water for use.
The present invention utilizes on the paracril activity of α-H on the divinyl segment, under the initiator effect, adopt the reactive compatibilizer that obtains that the maleic anhydride graft paracril prepares, on the one hand the divinyl that contains in its molecule, propenyl segment can with rubber matrix in divinyl, propenyl segment generation physical entanglement effect, the maleic anhydride that contains in its molecule on the other hand part can and water-absorbing resin between form strong chemical bond; Firmly rubber matrix is 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 from matrix, come off the water sucting rubber physical and mechanical properties excellence of preparation.
Maleic anhydride graft paracril preparation principle is as follows:
Beneficial effect of the present invention:
Compare with traditional preparation water-swelling paracril, adopt the water-swelling paracril rubber of the expanding material acquisition of the present invention's preparation, reactive force between its rubber matrix and the water-absorbing resin is strong, the water-absorbing resin difficult drop-off, water absorbent rate increases, and the water-absorbing resin mass loss rate lowers, and can reach to make itself and the uniform purpose of absorbent composition blend, thereby the saving cost, the preparation method is simple.
Description of drawings
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 specifies of the present invention, but content of the present invention is not limited to the following examples.
Embodiment 1:
After the paracril of 1g being used the whole dissolvings of tetrahydrofuran (THF) of 30mL, slowly drip the tetrahydrofuran solution of 1g maleic anhydride and 0.16g benzoyl peroxide, be warming up to 65 ℃, isothermal reaction 12h.Reaction finishes the back ethanol sedimentation and goes out grafts, then, with a large amount of distilled water washs for several times, is placed on room temperature oven dry in the vacuum drying oven, and the oven dry back with acetone soln extracting 12h, obtains the maleic anhydride graft paracril in Soxhlet extractor.It is standby fully to get expanding material after the drying.Do infrared test, thermal weight loss test.
Can find out obviously among Fig. 1 (a) that a series of absorption peaks are-CH near the 2890-2920cm-1
3With-CH
2In the stretching vibration peak of C-H, 2240cm
-1Near be-C ≡ N charateristic avsorption band 1640cm
-1Be alkene-C=C-stretching vibration peak, 1440cm
-1, 968cm
-1Be alkene-C-H face internal strain vibration.Can obviously be derived as the characteristic peak of divinyl segment and vinyl cyanide segment, be the absorption peak of paracril.
Fig. 1 (b) is the paracril infared spectrum behind the maleic anhydride graft, 3357cm
-1Broad peak is-the OH stretching vibration, 1779,1721cm
-1Corresponding to acid anhydrides charateristic avsorption band (bimodal), be positioned at 1651cm
-1Be fat lactones-C=O formation vibration, 1446cm
-1Be alkene-C-H face internal strain vibration, 1261,1046cm
-1Be respectively acid anhydrides-C-O-C and become ring, acyclic stretching vibration peak, 920cm
-1Be the outer formation vibration of carboxylic acid-OH face.Thereby drawn acid anhydrides, and the olefinic double bonds peak also clearly ,-C ≡ N peak does not have considerable change yet.
Comparison diagram 1 (a) and (b) as can be known, maleic anhydride graft successfully has been grafted on the paracril, and then provides feasibility for preparation consistency good water-swelling paracril.
Among Fig. 2, can find out obviously that pure paracril (NBR) is tangible thermal weight loss for once, when occurring in 360 ℃, is the thermal weight loss of paracril; Maleic anhydride/paracril grafts (MAH-g-NBR) has tangible thermal weight loss twice, first section occurs in the time of 152 ℃, mainly is because decarboxylic reaction easily takes place the carbonyl instability of maleic anhydride, about 360 ℃, the decarboxylic reaction of maleic anhydride is finished substantially.Another time thermal weight loss is similar to pure paracril temperature, and quality remains unchanged substantially after 500 ℃.Can draw maleic anhydride thus has been grafted on the paracril molecule really.
The expanding material of preparation among the embodiment 1 is applied in the water-swelling paracril, and its step is as follows:
1) with 100 parts of paracrils after thin-pass bag roller in the mill is plasticated 1min, the stearic acid that adds 1.5 parts successively, 5 parts ZnO, 2 parts sublimed sulphur, 1 part antioxidant D, 10 parts PEG-6000, after roll spacing is to open refining evenly under the 2mm (about 3min), add then 50 parts water-absorbing resin (sodium polyacrylate 100 orders) mixing evenly after, add the carbon black of 20 parts of reinforced fillings and 20 parts white carbon black again, roll spacing be 3mm open the refining 10min, then add 0,5,10,15, after 20 parts of expanding materials mix, be added in the rubber matrix 2 parts accelerator DM and 2 parts accelerator CZ mixing even at last, be under the 0.4mm in roll spacing, play the triangle bag 6 times, thin-pass, following sheet, leave standstill 4 hours standby.
2) paracril that mixes is placed compression mold, on the vulcanizing press in 160 ℃ down (pressure is 10Mpa) behind the sulfuration 15min, the water-swelling paracril that vulcanizates is taken out in die sinking, leaves standstill 24h, cuts out sample.
Wherein, the account form of the weight water-intake rate of water-swelling paracril and rate of weight loss is as follows:
The water-swelling paracril that adds the paracril preparation of expanding material is cut into the sample of certainweight, and in the salt solution with its immersion tap water or other different concns, take out at regular intervals at a certain temperature and weigh, want when weighing to inhale the moisture that removes specimen surface with filter paper rapidly at every turn, after suction reaches capacity, be dried to constant weight in 50 ℃.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.
Prescription (consumption is counted by weight) and test result such as table 1.
Table 1
After the paracril of 1g being used the whole dissolvings of toluene of 30mL, slowly drip the toluene solution of 2.0g maleic anhydride and 0.2g benzoyl peroxide, be warming up to 55 ℃, isothermal reaction 10h.Reaction end back distilled water is settled out grafts, then, with a large amount of distilled water washs for several times, is placed on room temperature oven dry in the vacuum drying oven, and oven dry is at Soxhlet extractor spent glycol, Glacial acetic acid mixing solutions extracting 12h, and it is standby to get expanding material after the oven dry.
Gained expanding material among the embodiment 2 is applied in the water-swelling paracril, and embodiment is with embodiment 1.
Prescription (consumption is counted by weight) and test result see Table 2.
Table 2
Embodiment 3
After the paracril of 1g being used the whole dissolvings of tetrahydrofuran (THF) of 30mL, slowly drip the tetrahydrofuran solution of 1.2g maleic anhydride and 0.08g benzoyl peroxide, be warming up to 63 ℃, isothermal reaction 8h.Reaction finishes back distilled water and is settled out grafts, then, with a large amount of distilled water washs for several times, is placed on room temperature oven dry in the vacuum drying oven, and oven dry with acetone soln extracting 12h, obtains expanding material maleic anhydride graft paracril at Soxhlet extractor after the oven dry.
Gained expanding material among the embodiment 3 is applied in the water-swelling paracril, and embodiment is with embodiment 1.
Prescription (consumption is counted by weight) and test result see Table 3.
Table 3
Claims (10)
1. the expanding material of a water-swelling paracril is characterized in that the effective constituent that wherein contains is the grafts of paracril and maleic anhydride, and all the other are paracril.
2. the expanding material of water-swelling paracril as claimed in claim 1 is characterized in that described expanding material is the product that following method prepares:
Paracril, maleic anhydride and initiator are dissolved in respectively in the solvent, and nitrile rubber solution is warming up to 55～75 ℃; Slowly drip the mixing solutions of maleic anhydride and initiator, isothermal reaction 8～12h discharging; Add precipitation agent, isolate the grafts of paracril and maleic anhydride, and use distilled water wash; Grafts after the washing is dried, shredded, and initiator, maleic anhydride and maleic anhydride homopolymer are removed in extracting; Obtain the expanding material of water-swelling paracril after the drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1～2:0.08～0.2 by weight, and the nitrile amount that contains of paracril is 30wt%～45wt%.
3. the expanding material of water-swelling paracril as claimed in claim 2 is characterized in that described solvent selects any one in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, the chlorobenzene for use.
4. the expanding material of water-swelling paracril as claimed in claim 2 is characterized in that described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile) any one for use.
5. the expanding material of water-swelling paracril as claimed in claim 2 is characterized in that described precipitation agent selects any one in dehydrated alcohol, methyl alcohol, the distilled water for use.
6. the expanding material of water-swelling paracril as claimed in claim 2 is characterized in that the extract of selecting for use in the extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, the sherwood oil.
7. the preparation method of the described water-swelling paracril of claim 1 expanding material is characterized in that may further comprise the steps:
Paracril, maleic anhydride and initiator are dissolved in respectively in the solvent, and nitrile rubber solution is warming up to 55～75 ℃; Slowly drip the mixing solutions of maleic anhydride and initiator, isothermal reaction 8～12h discharging; Add precipitation agent, isolate the graft product of paracril and maleic anhydride, and use distilled water wash; Graft product after the washing is dried, shredded, and initiator, maleic anhydride and maleic anhydride homopolymer are removed in extracting; Obtain the expanding material of water-swelling paracril after the drying;
Wherein, paracril: maleic anhydride: initiator is calculated as 1:1～2:0.08～0.2 by weight, and the nitrile amount that contains of paracril is 30wt%～45wt%; The extract of selecting for use in the extractive process is any one in acetone, ethylene glycol Glacial acetic acid mixed solution, the sherwood oil.
8. the preparation method of water-swelling paracril expanding material as claimed in claim 7 is characterized in that described solvent selects any one in tetrahydrofuran (THF), acetone, toluene, dimethylbenzene, the chlorobenzene for use.
9. the preparation method of water-swelling paracril expanding material as claimed in claim 7 is characterized in that described initiator is radical initiator; Select in benzoyl peroxide, tertbutyl peroxide, Diisopropyl azodicarboxylate, the 2,2'-Azobis(2,4-dimethylvaleronitrile) any one for use.
10. the preparation method of water-swelling paracril expanding material as claimed in claim 7 is characterized in that described precipitation agent selects any one in dehydrated alcohol, methyl alcohol, the distilled water for use.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017254A (en) * | 2014-06-20 | 2014-09-03 | 武汉工程大学 | Method for preparing reactive compatibilization-type nitrile 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 |
| CN114133921A (en) * | 2020-09-04 | 2022-03-04 | 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 |
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2013
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| JPS5958046A (en) * | 1982-09-29 | 1984-04-03 | Asahi Chem Ind Co Ltd | Resin composition |
| EP0204357A1 (en) * | 1985-05-03 | 1986-12-10 | Stamicarbon B.V. | Polymer composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017254A (en) * | 2014-06-20 | 2014-09-03 | 武汉工程大学 | Method for preparing reactive compatibilization-type nitrile water-swelling 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 |
| 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 |
| CN114133921A (en) * | 2020-09-04 | 2022-03-04 | 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 |
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