CN101983980A - Method for improving performances of water-swelling rubber - Google Patents
Method for improving performances of water-swelling rubber Download PDFInfo
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- CN101983980A CN101983980A CN 201010523867 CN201010523867A CN101983980A CN 101983980 A CN101983980 A CN 101983980A CN 201010523867 CN201010523867 CN 201010523867 CN 201010523867 A CN201010523867 A CN 201010523867A CN 101983980 A CN101983980 A CN 101983980A
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Abstract
The invention discloses a method for improving the performances of water-swelling rubber and relates to a nano-composite material technology, which comprises the following steps: mixing a mesoporous molecular sieve with the water-swelling rubber according to the weight ratio of 100:0.1-10, leading the mesoporous molecular sieve to be uniformly dispersed in a matrix of the water-swelling rubber and preparing a water-swelling rubber composite material product, wherein the mesoporous molecular sieve is divided into the structure without pore canals and the structure with the pore canals and mainly in the shape of regular spheres, and the average particle size is 80-100nm; and the water-swelling rubber is a novel functional polymer material which is prepared by introducing hydrophilic groups or hydrophilic components into the matrix of the rubber, and the water-swelling rubber can expand to a plurality of times and hundreds of times of the weight or the volume of the water-swelling rubber after absorbing water and produce greater expansion pressure. The water-swelling rubber formed by modification through the mesoporous molecular sieve has strong chemical stability, high water swelling ratio, high strength, durability and reusability, and can overcome the deficiencies of the existing water-swelling rubber.
Description
Technical field
The present invention relates to the nano composite material technology, particularly relate to the method that a kind of mesopore molecular sieve is used for water swelling rubber, improves the water swelling rubber performance.
Background technology
Water swelling rubber (Water-Swellable Rubber, be called for short WSR) be a kind of new functional macromolecule material, it is introduced hydrophilic radical or hydrophilic component and makes in rubber matrix, suction back inflatable to sole mass or volume several times so that hundreds of times, and produce the big swelling pressure.
Since coming out the seventies in 20th century, with its unique resilient seal sealing and water-swelling dual nature with the water sealing, being subjected to people generally payes attention to, can be widely used in civil engineering work, the military project facility, civilian capital construction, aspects such as industrial equipments manufacturing, water swelling rubber has replaced traditional cementation process gradually aspect stoppage engineering, ways such as potassium-sodium water glass grouting and Resins, epoxy leak stopping, it has been successfully applied to the engineering project deformation seam, construction joint, various pipeline connections, the hermetic seal that dam etc. are located, and the anti-hydrosphere of quilt is described as " super seal material " and " double insurance sealing material ".There is the report of water swelling rubber in China since the eighties, is applied to the earliest in the Shanghai Underground shield construction.Abroad starting has early been produced a large amount of high-quality product aspect WSR research, and has been successfully applied in the large scale civil engineering construction.Domestic also have analogous products to come out, but quality and performance all with the certain gap of external existence, the further research of still needing is with perfect.Rubber constitutes the matrix of WSR, and its elasticity and intensity can have influence on the mechanical property of WSR.Simultaneously, because in structure and qualitative difference, the problem of traditional water sucting rubber ubiquity hydroaropic substance bad dispersibility in rubber matrix.Hydroaropic substance comes off from rubber network easily, thereby influences water-swelling property and the physicals of WSR, weakens its long-term water-retentivity and reusability.
Summary of the invention
The object of the present invention is to provide a kind of mesopore molecular sieve to be used to prepare the method for water swelling rubber.The water swelling rubber chemical stability that forms is strong, and has high expansion rate of water absorption, high strength, weather resistance and reusability; Overcome the deficiency of existing water swelling rubber.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method that improves the water swelling rubber performance, this method comprises: water swelling rubber mixes on the General Purpose Rubber mixing facilities by the 100:0.1-10 mass ratio with mesopore molecular sieve or modification mesopore molecular sieve, vulcanize by common sulfuration process and equipment then, mesopore molecular sieve is dispersed in the water swelling rubber matrix, forms the water swelling rubber composite product.
Described a kind of method that improves the water swelling rubber performance, described water swelling rubber matrix comprises natural rubber and synthetic rubber, as styrene-butadiene rubber(SBR) (SBR), polyisoprene (IR), isoprene-isobutylene rubber (IIR), polybutadiene rubber (PBR), acrylonitrile butadiene copolymer (NBR), and one or more the mixture in the thermoplastic elastomer.
Described a kind of method that improves the water swelling rubber performance, described water swelling rubber absorbent composition comprises the high sodium bentonite of modification, white carbon black and polyvinyl alcohol, maleic anhydride grafts, hydrophilic polyurethane performed polymer: by oxyethane or tetrahydrofuran (THF) water soluble polyether and isocyanate reaction makes, polyacrylic: contain one or more mixtures in polyacrylic acid, polyacrylate, polyacrylamide and the acrylic acid modified thing.
Described a kind of method that improves the water swelling rubber performance, described mesopore molecular sieve comprise according to the chemical constitution difference, are divided into silica-based and non-silica-based two big classes, and the metal of a series of mesopore molecular sieves and metal oxide series.
Described a kind of method that improves the water swelling rubber performance, described mesopore molecular sieve are divided into no duct and pore passage structure are arranged, and shape is based on regular spherical, and median size is 80～100 nm.
Described a kind of method that improves the water swelling rubber performance, described mesopore molecular sieve:
(1) no duct structure is, through the mesopore molecular sieve of high-temperature calcination, soft material, i.e. template are not being filled in inside, duct.
(2) have pore passage structure to be, through the mesopore molecular sieve of high-temperature calcination, no template in the duct, the duct is that rule has the duct or random pore passage structure arranged, and the aperture is 2～10 nm.
Described a kind of method that improves the water swelling rubber performance, its modification mesopore molecular sieve adopts surface-modifying agent that nano mesoporous molecular sieve material is carried out surface treatment, the consumption of surface-modifying agent accounts for the mass ratio 0.5-5 of nano mesoporous molecular screen, surface-modifying agent is a methyl acrylic ester series, coupling agent class series and surfactant-based series.
Described a kind of method that improves the water swelling rubber performance, described methyl acrylic ester series comprises methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate.
Described a kind of method that improves the water swelling rubber performance, described coupling agent series comprises silane coupling agent γ-An Jibingjisanyiyangjiguiwan KH550(NH(CH
2)
3Si(OC
2H
5)
3), γ-(methacryloxy) propyl trimethoxy silicane KH57O(CH
2=C (CH
3) COO (CH
3)
3Si (OCH
3)
3), tetra-sulfurized pair (triethoxy propyl group) silane Si-69((H
5C
2O)
3Si(CH
2)
3S
4(CH
2)
3Si(OC
2H
5)
3), sec.-propyl three (dioctyl pyrophosphoryl oxygen base) titanate coupling agent NDZ-201(C
51H
112O
22P
6Ti).
Described a kind of method that improves the water swelling rubber performance, described surfactants comprises sodium stearate (C
17H
35COONa), Sodium dodecylbenzene sulfonate (C
18H
29NaO
3S), sodium lauryl sulphate (C
12H
25SO
4Na).
The present invention has following advantage and beneficial effect:
1, the invention provides a compatilizer addition less than 10% blend preparation method, addition is little, and complete processing is simple, and cost is low.
2, the invention belongs to the modified water absorbent expanded rubber.Can be applicable to job facilities such as tunnel, subway, culvert, building, underground works, offshore oil production, also is simultaneously desirable waterproof, the moisture sealed packing of automobile, freight container, precision instrument, medicine, food etc.Application prospect is extensive.
3, the modified water absorbent rubber of the present invention's preparation, chemical stability is strong, and has high expansion rate of water absorption, high strength, weather resistance and reusability.
Embodiment
The method that nano mesoporous molecular screen of the present invention is used to prepare water swelling rubber comprises: nano mesoporous molecular screen mixes by the 100:0.1-10 mass ratio with polymkeric substance, nano mesoporous molecular screen is dispersed in the water swelling rubber, and moulding obtains the water sucting rubber composite product then.Mesopore molecular sieve according to the chemical constitution difference, is divided into silica-based and non-silica-based two big classes.According to different tensio-active agents and different assembling routes, silica-based molecular sieve can be divided into M41S series, SBA series, HMS series, MSU series, KIT series and ZSM series etc. and the mesoporous material of metal oxide thereof.Main silicon-based mesoporous molecular sieve is as follows:
(1) M41S series such as MCM-41, MCM-48, MCM-50, MCM-56 and MCM-22 and MCM-49 molecular sieve.
(2) SBA series such as SBA-1, SBA-16, SBA-2, SBA-3, SBA-15 molecular sieve.
(3) MSU molecular sieve series such as MSU-X, MSU-V, MSU-G, MSU-H, MSU-S molecular sieve
(4) other serial molecular sieves are as ZSM-5, ZSM-23, ZSM-35, HZSM series and FSM-16 etc.
(5) novel molecular sieve is used P123-SDS-C
nThe triple tensio-active agents of TMAB are as the spherical silica-based molecular sieve in template synthetic a kind of novel mesopore cavity.
Non-silicon-based mesoporous molecular sieve comprises: carbonaceous molecular sieve: CMK-1, CMK-2, CMK-3, CMK-5, SUN-2.
The molecular sieve of above-mentioned various series includes duct and no duct structure, and the median size particle diameter is 80～100nm.Nano mesoporous molecular screen mixes with water swelling rubber and moulding can be adopted general mixing equipment of prior art and molding device.For example mill, Banbury mixer, stirrer or the like.
Embodiment 1
The first step: 1 gram γ-An Jibingjisanyiyangjiguiwan is dissolved in the small amount of acetone, and it is porose evenly to be sprayed on mesopore molecular sieve MCM-41(then) in, treat that acetone volatilizees naturally after, the mesopore molecular sieve MCM-41 of modification was dried 4 hours under 80 ℃ of conditions.
Second step: modified molecular screen and water sucting rubber are pressed following prescription blend: NR 100, stearic acid 1.0, zinc oxide 5.0, polyacrylamide 20, modified molecular screen MCM-41 (porose) 2, antioxidant D 1.0, accelerant CZ 0.4, promotor TT 0.15, Sulfur 2.0.
2min plasticates natural rubber in mill, it is mixing evenly to add stearic acid, polyacrylamide, modified molecular screen MCM-41 (porose), zinc oxide, antioxidant D, accelerant CZ, TT and Sulfur etc. then successively, obtain dispersiveness rubber mixture preferably, on ODR-100E type vulkameter, survey vulcanization curve, again with 145 ℃ of sulfurations down of MV-90E type vulcanizing press.Take out cut-parts, standby analysis.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing molecular sieve is dispersed in the water swelling rubber matrix with nano-scale, illustrates to have made expansion water sucting rubber/mesopore molecular sieve (porose) nano composite material.
Embodiment 2
The first step: 1 gram ethenylphenyl Edamine propyl trimethoxy silicane mono-hydrochloric salts is dissolved in the small amount of ethanol, hydrolysis evenly is sprayed on after 3 minutes in the mesoporous molecular sieve SBA-15 (atresia), after treating that ethanol is waved naturally, with the SBA-15(atresia of modification) under 90 ℃ of conditions, dried 5 hours.
Second step: modified molecular screen and water sucting rubber are pressed following prescription blend: EPDM 100, stearic acid 1.0, zinc oxide 5.0, sodium polyacrylate 20, modified molecular screen SBA-15 (atresia) 2, antioxidant D 1.0, accelerant CZ 0.4, promotor TT 0.15, DCP 2.0.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing molecular sieve is dispersed in the water swelling rubber matrix with nano-scale, illustrates to have made expansion water sucting rubber/mesopore molecular sieve (atresia) nano composite material.
Embodiment 3
The first step: the modified MC M-41 (porose) that 10 examples one that restrain are obtained joins in the proper amount of acetone, adds 3 gram Isooctyl acrylate monomers and 0.1 gram photoinitiator then, stirs 10 minutes.Place pallet then, treat that acetone volatilizees naturally, the treatment with ultraviolet light certain hour is used in oven dry, and it is porose to make modified MC M-41().
Second step: with water-absorbing resin monomer 15 gram (N; each 5g of N '-methylene-bisacrylamide, ammonium persulphate and S-WAT) solves homogeneously in the distilled water; the MCM-41(that adds 1 ~ 3 g is porose); its complete aquation is dispersed in the reaction system; add 30 g natural rubber latexes at last; under nitrogen protection,, obtain intermediate in 60 ℃ of reaction 4 ~ 5 h.Intermediate drying, pulverizing, sulfuration are obtained two-pack interpenetrating(polymer)networks water sucting rubber.Sulfurizing formula: glue 100 g, ZnO 5 g, stearic acid 1 g, protective agent RD 1.5 g, accelerant CZ 1.2 g, sulphur 2.5 g; 143 ℃ of curing temperatures, time 10min.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing molecular sieve is dispersed in the water swelling rubber matrix with nano-scale, illustrates to have made expansion water sucting rubber/mesopore molecular sieve (porose) nano composite material.In normal temperature (23 ℃) distilled water, soak 16 h, take out the back, be put into again and soak 16 h in the water, dry 8h again at 70 ℃ of oven dry 8 h down, immersion so repeatedly, dry 4 loop cycles after, survey its hardness, tensile strength, tensile yield.
The MCM-41 of modification has good enhancement to water swelling rubber as can be seen from Table 1, and this is because the enhancing network structure of nano molecular sieve MCM-41 one-dimensional tunnel structure densification.Therefore mesopore molecular sieve has improved tensile strength.This mainly is because the silicon hydroxyl generation Chemical bond on properties-correcting agent and molecular sieve (porose) surface, form stable bonding action, and when vulcanizing, system forms good cross-linked network, improve the reactive force at mesopore molecular sieve and water sucting rubber interface, formed physical and mechanical properties water swelling rubber/modified MC M-41 nano composite material preferably.
The physical and mechanical properties of table 1 water swelling rubber/modified MC M-41 (porose) matrix material
| Mechanical property | Unmodified water swelling rubber | Water swelling rubber/modified MC M-41(is porose) (1wt%) | Water swelling rubber/modified MC M-41(is porose) (3wt%) |
| Tensile strength, MPa | 10.1 | 13.5 | 14.3 |
| Tensile yield, % | 570 | 610 | 600 |
| Hardness (Shao Er A), degree | 70 | 73 | 74 |
Embodiment 4
The first step: 1 gram propenoic acid beta-hydroxy propyl ester and 0.5 gram tolylene diisocyanate mixing are dissolved in the small amount of acetone, it is porose evenly to be sprayed on 100 gram mesopore molecular sieve MCM-48(then) in, treat that acetone volatilizees naturally, the mesopore molecular sieve MCM-48 after the modification was dried 4 hours under 80 ℃ of conditions.
Second step: preparation modified water absorbent expanded rubber, the mixing order of addition(of ingredients) of sizing material is: NR plasticates → and NR/SBR blend → small powder (promotor, zinc oxide, stearic acid, anti-aging agent) → modified molecular screen → water-absorbing resin, tenderizer → Sulfur, logical thin 6 times of the reinforced back that finishes, slice, park 24 h postcure samples, curing temperature is 150 ℃.
Recipe ingredient is: NR/SBR 50/50; ZnO 5; SA 2; Accelerant CZ 1; Captax 1; Antioxidant D 1; Paraffin 0.5; Machine oil 8, modified molecular screen 1-3; Sodium polyacrylate 20; Sulphur 2.
The gained matrix material finds that with scanning electron microscope and transmission electron microscope observing molecular sieve is dispersed in the water swelling rubber matrix with nano-scale, illustrates to have made expansion water sucting rubber/mesopore molecular sieve (porose) nano composite material.The mensuration of expansion rate of water absorption: sample is put into 50 ℃ of thermostatic drying chambers be dried to constant weight, weigh its dry weight in the balance, be immersed into then in 23 ℃ of constant temperature distilled water, take out sample every half an hour, blot surface-moisture, weigh in the balance heavily with filter paper, up to the suction balance, weight no longer increases.Expansion rate of water absorption increases percentage with weight and represents calculation formula: before expansion rate of water absorption=(dry weight before sample suction back weight-sample suction)/sample suction after the dry weight * 100%.
As can be seen from Table 2, it is porose to add MCM-48(in water swelling rubber) can improve the expansion rate of water absorption of water swelling rubber greatly, especially add the MCM-48(2 phr of modification) time.Sodium polyacrylate is easy to reunite, and is difficult in homodisperse in the rubber matrix, has more sodium polyacrylate and does not have water sorption; And irregular torsional deformation takes place in entire sample easily behind the water-swellable, and sodium polyacrylate has much and separates out.Help sodium polyacrylate and in matrix, disperse and add MCM-48,, have more sodium polyacrylate suction by capillary action.Thereby improve the expansion rate of water absorption of water swelling rubber.
The water-swelling property of table 2 water swelling rubber/modified MC M-48 (porose) matrix material
| Properties-correcting agent | Do not have | Unmodified MCM-48(is porose) (2 phr) | Modified MC M-48(is porose) (2 phr) |
| Expansion rate of water absorption, % | 281 | 390 | 450 |
Claims (10)
1. method that improves the water swelling rubber performance, it is characterized in that this method comprises: water swelling rubber mixes on the General Purpose Rubber mixing facilities by the 100:0.1-10 mass ratio with mesopore molecular sieve or modification mesopore molecular sieve, vulcanize by common sulfuration process and equipment then, mesopore molecular sieve is dispersed in the water swelling rubber matrix, forms the water swelling rubber composite product.
2. according to the described a kind of method that improves the water swelling rubber performance of claim 1, it is characterized in that described water swelling rubber matrix comprises natural rubber and synthetic rubber, as styrene-butadiene rubber(SBR) (SBR), polyisoprene (IR), isoprene-isobutylene rubber (IIR), polybutadiene rubber (PBR), acrylonitrile butadiene copolymer (NBR), and one or more the mixture in the thermoplastic elastomer.
3. according to the described a kind of method that improves the water swelling rubber performance of claim 1, it is characterized in that described water swelling rubber absorbent composition comprises the high sodium bentonite of modification, white carbon black and polyvinyl alcohol, maleic anhydride grafts, hydrophilic polyurethane performed polymer: by oxyethane or tetrahydrofuran (THF) water soluble polyether and isocyanate reaction makes, polyacrylic: contain one or more mixtures in polyacrylic acid, polyacrylate, polyacrylamide and the acrylic acid modified thing.
4. according to the described a kind of method that improves the water swelling rubber performance of claim 1, it is characterized in that described mesopore molecular sieve comprises according to the chemical constitution difference, be divided into silica-based and non-silica-based two big classes, and the metal of a series of mesopore molecular sieves and metal oxide series.
5. a kind of method that improves the water swelling rubber performance according to claim 1 is characterized in that described mesopore molecular sieve is divided into no duct and pore passage structure is arranged, and shape is based on regular spherical, and median size is 80～100 nm.
6. a kind of method that improves the water swelling rubber performance according to claim 1 is characterized in that described mesopore molecular sieve:
(1) no duct structure is, through the mesopore molecular sieve of high-temperature calcination, soft material, i.e. template are not being filled in inside, duct;
(2) have pore passage structure to be, through the mesopore molecular sieve of high-temperature calcination, no template in the duct, the duct is that rule has the duct or random pore passage structure arranged, and the aperture is 2～10 nm.
7. a kind of method that improves the water swelling rubber performance according to claim 1, it is characterized in that the modification mesopore molecular sieve adopts surface-modifying agent that nano mesoporous molecular sieve material is carried out surface treatment, the consumption of surface-modifying agent accounts for the mass ratio 0.5-5 of nano mesoporous molecular screen, surface-modifying agent is a methyl acrylic ester series, coupling agent class series and surfactant-based series.
8. according to the described a kind of method that improves the water swelling rubber performance of claim 7, it is characterized in that described methyl acrylic ester series comprises methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate.
9. according to the described a kind of method that improves the water swelling rubber performance of claim 7, it is characterized in that described coupling agent series comprises silane coupling agent γ-An Jibingjisanyiyangjiguiwan KH550(NH(CH
2)
3Si(OC
2H
5)
3), γ-(methacryloxy) propyl trimethoxy silicane KH57O(CH
2=C (CH
3) COO (CH
3)
3Si (OCH
3)
3), tetra-sulfurized pair (triethoxy propyl group) silane Si-69((H
5C
2O)
3Si(CH
2)
3S
4(CH
2)
3Si(OC
2H
5)
3), sec.-propyl three (dioctyl pyrophosphoryl oxygen base) titanate coupling agent NDZ-201(C
51H
112O
22P
6Ti).
10. a kind of method that improves the water swelling rubber performance according to claim 7 is characterized in that described surfactants comprises sodium stearate (C
17H
35COONa), Sodium dodecylbenzene sulfonate (C
18H
29NaO
3S), sodium lauryl sulphate (C
12H
25SO
4Na).
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| CN102863667A (en) * | 2012-10-12 | 2013-01-09 | 武汉工程大学 | Preparation method for water swelling nitrile butadiene rubber |
| CN104059192A (en) * | 2014-07-04 | 2014-09-24 | 青岛科技大学 | Non-blending type ACM water swelling rubber and mass polymeriatio preparing method thereof |
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| CN102863667A (en) * | 2012-10-12 | 2013-01-09 | 武汉工程大学 | Preparation method for water swelling nitrile butadiene rubber |
| CN102863667B (en) * | 2012-10-12 | 2014-04-30 | 武汉工程大学 | Preparation method for water swelling nitrile butadiene rubber |
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| CN104693665A (en) * | 2015-04-07 | 2015-06-10 | 华东理工大学 | Thermoplastic water-swellable elastomer and preparing method and application thereof |
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| CN108841322B (en) * | 2018-07-10 | 2020-05-19 | 武汉露能科技有限公司 | Low surface energy coating and preparation method thereof |
| CN110938237A (en) * | 2019-12-18 | 2020-03-31 | 中铝山东新材料有限公司 | 4A zeolite treatment method and product thereof |
| CN110938237B (en) * | 2019-12-18 | 2021-10-22 | 中铝山东新材料有限公司 | 4A zeolite treatment method and product thereof |
| CN111234116A (en) * | 2019-12-25 | 2020-06-05 | 青岛科技大学 | Preparation method of trans-polyisoprene-maleic anhydride copolymer and thermoplastic high-strength water-absorbing rubber |
| CN111234116B (en) * | 2019-12-25 | 2023-04-21 | 青岛科技大学 | Preparation method of trans-polyisoprene-maleic anhydride copolymer and thermoplastic high-strength water-absorbing rubber |
| CN113773562A (en) * | 2021-10-25 | 2021-12-10 | 上安实业江苏有限公司 | Putty type water-swelling rubber water-stop material |
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