CN1307248C - Method for preparing SOS/clay nano composite material - Google Patents
Method for preparing SOS/clay nano composite material Download PDFInfo
- Publication number
- CN1307248C CN1307248C CNB2004100228368A CN200410022836A CN1307248C CN 1307248 C CN1307248 C CN 1307248C CN B2004100228368 A CNB2004100228368 A CN B2004100228368A CN 200410022836 A CN200410022836 A CN 200410022836A CN 1307248 C CN1307248 C CN 1307248C
- Authority
- CN
- China
- Prior art keywords
- clay
- sbs
- mixed solution
- rubber
- organification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004927 clay Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002114 nanocomposite Substances 0.000 title claims description 38
- 239000000463 material Substances 0.000 title description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000002525 ultrasonication Methods 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 3
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052621 halloysite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 34
- 229920001971 elastomer Polymers 0.000 description 29
- 239000005060 rubber Substances 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000005728 strengthening Methods 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229940080314 sodium bentonite Drugs 0.000 description 7
- 229910000280 sodium bentonite Inorganic materials 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 229920013649 Paracril Polymers 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- UOQDKQOXSLQEOJ-UHFFFAOYSA-N 2-methylprop-2-enoate;trimethylazanium Chemical compound C[NH+](C)C.CC(=C)C([O-])=O UOQDKQOXSLQEOJ-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000013339 polymer-based nanocomposite Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FFAASCFOKLNICD-UHFFFAOYSA-N COC.[S] Chemical compound COC.[S] FFAASCFOKLNICD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Abstract
The present invention provides a method for preparing SBS/clay nanometer composite materials. In the method, clay with a layered crystal-layer overlapping structure is prepared into 1 to 20% of clay water solution, the clay water solution is centrifugated and dewatered after organic long-carbon chain quaternary ammonium salt is added in the clay water solution to be treated with organification, and organification clay is obtained; the organification clay is mixed with SBS cyclohexane solution which is obtained after polyreaction in the process of SBS production, and high-shear treatment or ultrasonic treatment are carried out for the mixed solution to form uniform mixed solution. The adding amount of the organification clay accounts for 1 to 10 wt% of the SBS. The dissolvent in the mixed solution is removed to obtain the SBS/clay nanometer composite materials. The method has the advantages of simple operation, low cost, wide application range and easy industrialization. Compared with the tensile strength of common SBS, the tensile strength of the product is increased by more than 30%.
Description
Technical field
The present invention relates to a kind of preparation method of SBS/ clay nanocomposites.
Background technology
The strengthening agent that rubber industry is traditional is carbon black and white carbon black always, and particularly the former is seized of critical role in rubber industry.The size of these two kinds of strengthening agent primary particals is very little, and as the carbon black before the N600 rank, its particle diameter is all less than 60nm, and the particle diameter of precipitated silica is generally also between 20-40nm.We can say, the size of size of particles is to influence its first factor to reinforcing rubber ability height, size of particles promptly uses the surface-treated method to make the two produce outstanding interfacial adhesion after surpassing 1000nm, also is difficult to reach the level of carbon black and white carbon black reinforcement again.Research to a large amount of mineral fillers has convincingly demonstrated this point, even to this day, also fails to find a kind of reinforcement ability to surpass the new packing of these two kinds of strengthening agents, and reason is that the particle diameter of weighting agent of new development is all bigger.
Yet people were never interrupted the effort to novel reinforcement mode of rubber and strengthening agent exploitation.This is because traditional strengthening agent has following shortcoming: (1) processing pollution is big.Because these two kinds of volume densities that strengthening agent is very low, thereby when in rubber, dosing, very easily produce and fly upward, even thereby use internal rubber mixer, also be difficult to guarantee the cleaning in mixing workshop, avoid infringement to workers ' health.(2) long processing time, mixing energy consumption is big.Because the powder of these two kinds of strengthening agents is extremely tiny, be easy to assemble, thereby in rubber, disperse the needed time longer, the time that extremely low volume density of while causes it to sneak into (or claiming wedging) in rubber is also longer, almost accounts for 1/2 of compounding rubber whole process.(3) the goods tone is single.This mainly is meant black-reinforced.High level carbon black generally has better synthesis reinforcement ability than white carbon black, thereby more is usually used in rubber industry.But the black tone of goods can't be changed.(4) some performances still are weak.All be difficult to give rubber item higher hardness as these two kinds of strengthening agents, better saturating performance of gasproof or the like.(5) owing to the dependency to oil, thereby the sooty resource is reducing gradually.White carbon black can not replace carbon black fully, and price is more expensive, and as (many time require) after using silane coupling agent to carry out surface treatment, price is just higher.
Therefore, the development trend of novel strengthening agent is, have good processing properties, and comprehensive preferably reinforcement ability be arranged, preferably light filler, and price is low.The achievement in research of relevant clay polymer based nano composite material makes people see dawn in the solution of this problem.
The research of clay/polymer based nanocomposites, it is the focus of current polymeric material field research, it has showed a series of excellent physical and mechanical performance that this class material is had to people, and existing industrialized achievement, as clay/nylon 6 nano-composite that company of Ube Industries Ltd. produces, have high rigidity, very high heat-drawn wire and tensile strength.People in prepared in laboratory the clay nanocomposites of a series of polymeric matrixs, comprise nylon 6, Resins, epoxy, polystyrene or the like.Obtaining of these nano composite materials, be to use suitable technical approach, laminated structure with the uniqueness that contained in the clay particle structure, be evenly dispersed in and obtain in the macromolecule matrix, because the thickness of clay layer is about 1nm, thereby in the final matrix material, the gauge of disperse phase (clay layer individual layer or lamella aggregate) all can remain on below the 100nm, so claim that this material is a nano composite material.These nano composite materials not only have good strength and extension property and processing characteristics, and because the existence of clay layer, also with the anti-gas permeability energy of excellence, nearest studies show that matrix material, the flame retardant properties of matrix material is also very outstanding.In a word, these researchs are sought new type rubber reinforcement mode and strengthening agent provides a kind of good idea for people.
Most polymer-based carbon/clay nanocomposites are by the method preparation of in-situ polymerization.The method of in-situ polymerization is meant, obtains external phase and nano grade discontinuous phase in the process of chemical reaction simultaneously.For example, Fukushima etc. utilize the positively charged ion of 12 1 aminoundecane-earboxylic acids to embed between the clay crystal layer, obtain organic clay, cause the monomer caprolactam polymerization of infiltration then between crystal layer, have successfully made nylon 6/ clay nanocomposites.96105362.3 patents that Chinese Academy of Sciences's chemistry is applied for have also disclosed a kind of once-through method in-situ polymerization method for preparing of nanometer composite polyamide-clay material.But, in many cases, can not find the easy monomer that carries out in-situ polymerization between clay seam that enters as hexanolactam, form nano composite material.Therefore this preparation method has certain limitation on applicable surface, and this method cost height, the complex process instability.Be difficult to realize suitability for industrialized production.
Same plastic base/clay nanocomposites is compared, and the research of rubber-based/clay nanocomposites also seldom.US4889885 (document 1) discloses two kinds of methods that prepare clay-rubber nm-class composite material.First situ aggregation method, promptly at first the character of clay layer is carried out modification with the quaternary ammonium salt of end-vinyl, then this modified clay is dispersed in N, in the dinethylformamide solvent, adds the initiator of the free radical type of a large amount of isoprene monomers and corresponding proportion.Isoprene just between clay layer initiated polymerization become polyisoprene rubber, slough solvent, so just obtained synthetic polyisoprene/clay nanocomposites.It two is, the liquid end amido paracril that molecular weight is lower is dispersed in the mixed solvent of being made up of water and dimethyl oxygen sulphur, adding acid then makes it form amine salt, mix with the aqeous suspension of clay again, slough water and solvent at last, just formed liquid butyronitrile rubber/clay nanocomposites.Chinese patent application No. 94192043.7 (documents 2) discloses the method that a kind of preparation is used for the liquid acrylonitrile butadiene rubber/clay nanocomposites of the tyre airtight layer and the inner tube of a tyre.Specifically be, at first clay is evenly dispersed in the water, add acid and make its sheet surfaces absorption hydrogen ion, toluene solution with liquid end amido paracril mixes then, in mixing process, the end amido of hydrogen ion on the lamella and paracril reacts, and clay layer just is dispersed in the liquid acrylonitrile butadiene rubber like this, sloughs solvent and just forms nano composite material.Chinese patent application 98101496.8 (document 3) utilizes the aqeous suspension of clay and rubber latex to carry out blend, adds flocculation agent and flocculates, and sloughs moisture, thereby obtains rubber/clay nanocomposites.
Theoretically, the dispersiveness of clay layer in rubber is high more, and the hardness of gained material is just high more, and elongation is low more, and intensity is high more, and elasticity is poor more, and flame retardant resistance is good more, and anti-gas permeability is good more.Therefore, for most of rubber items, clay layer also there is no need to form individual layer dispersion state completely, although the strength and extension property of the matrix material that obtains is very good.If clay layer is dispersed in the rubber with certain aggregate (as which floor even tens layers), several-ten nanometers that it is of a size of several nanometers can obtain the extraordinary clay-rubber nm-class composite material of over-all properties.Two kinds of methods of document 1 are compared with the method for document 2, and the former clay has higher dispersity, but resulting elastic properties of materials will differ from.Document 2 has overcome this point, and in the clay rubber nano composite material that is obtained, clay layer is to exist with to a certain degree aggregate, has both satisfied needed anti-gas permeability, and elasticity is also better.From the enforcement of method, the in-situ polymerization that document 1 is mentioned is too complicated, is difficult to realize industrialization.Though the second method technology of document 2 and document 1 is slightly simplified, but still complicated, and needed end amido paracril price is more expensive, and technological process needs a large amount of more expensive solvents of price.The more important thing is that the nano composite material that is obtained is because the intensity and the price problem of liquid acrylonitrile butadiene rubber, use and must carry out blend with other solid rubber, and the consistency of liquid butyronitrile rubber and many solid rubber (as natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber, ethylene-propylene rubber(EPR) etc.) is very poor, thereby makes final composite property impaired.Though document 3 is simple to operate than document 1,2, owing to inorganic clay is difficult to be uniformly dispersed in rubber, so performance is not good.
Summary of the invention
The objective of the invention is to propose a kind of simple to operate, cost is low, widely applicable, the preparation method that is easy to industrialized SBS/ clay nanocomposites, makes clay disperse equably with nano level form in SBS matrix.
The preparation method of SBS/ clay nanocomposites of the present invention in turn includes the following steps:
1, the clay that will have a stratiform crystal layer overlay structure is made into 1%～20% clay water solution, adds the back centrifuge dehydration that organises of long carbochain organic quaternary ammonium salt, obtains the soil that organises;
2, the SBS cyclohexane solution that polyreaction obtains after finishing in soil and the SBS production process that will organise mixes, and carries out high-shear earlier, and ultrasonication forms uniform mixed solution again; The native add-on that organises is 1%～10% of a SBS weight;
3, remove solvent in the mixed solution, make the SBS/ clay nanocomposites.
The used clay of the present invention need have stratiform crystal layer overlay structure, so that can and be dispersed among the SBS with the nano-scale separation, it can be natural or the synthetic clay, comprise terre verte, polynite, talcum powder, beidellite, hectorite, silica and halloysite, wherein the present invention preferably interlayer cation be the clay of sodium ion, as sodium bentonite.
The number of carbon atom is 12～20 in the long carbochain organic quaternary ammonium salt that is adopted in the method for the present invention.
In the process of the clay water solution of preparation 1%～20%, clay is with after water mixes, can suitably leave standstill for some time after stirring, some bigger extremely difficult dispersive clay particle of proportion and the gravel that contains band are settled down, resulting like this clay water suspension is finer and smoother.Can decide according to the quality and the character of clay but whether leave standstill with time of repose length.
SBS is that number-average molecular weight is 80,000～300,000, block than S/B is 20/80～48/52 line style or star-like product.
The dispersion spacing of clay layer in hexanaphthene depends on its concentration, and concentration can not be excessive, and concentration is high more, disperses spacing more little, and SBS is difficult more to intert isolation to it, and the size of nano-dispersed phase will increase.And concentration is low excessively, and energy consumption is too high in the time of can making final desolventizing.The weight content of soil in SBS cyclohexane solution system that organise should be controlled at 0.1%～2%.
Principle of the present invention is that the adjacent crystal layer of clay has negative charge, is generally adsorbing positively charged ion between the clay crystal layer, and this structure makes water and other polar molecule can enter between the clay crystal layer, and the exchange interaction between extraneous positively charged ion and inner positively charged ion can take place.Clay and water are mixed, just can form a stable clay water suspensoid, clay crystal layer wherein is under the hydration of interlayer cation, and is separated from one another.After organising, organic amine salt replaces hydrogen ion and enters interlayer, according to the similar compatibility principle, makes that clay is easier to be dispersed in the organic solvent uniformly.The SBS glue is sneaked into, and the clay crystal layer just can intert to each other and isolate mutually with micelle.Slough solvent with water vapour this moment, and the microcosmic nano composite structure of the two just can remain, thereby form the SBS/ clay nanocomposites.
The present invention prepares the method for SBS/ clay nanocomposites, and technology is simple, cost is low, production process is pollution-free.The SBS/ clay nanocomposites that utilizes method of the present invention to make, its disperse phase is the aggregate of clay monolithic layer or lamella, thickness is below 100nm, the more common SBS of its tensile strength improves more than 30%, other performances are suitable substantially, both can directly add vulcanization system, softening system etc. and be applied, the rubber or the strengthening agent (as: carbon black, white carbon black, lime carbonate, potter's clay etc.) that also can add other types again are applied.
The present invention prepares the method for SBS/ clay nanocomposites, because clay layer is scattered in the SBS matrix as toughener in advance equably, compare with the method for document 2 with document 1, technology is simple, does not need expensive liquid acrylonitrile butadiene rubber as " matrix " of matrix material and then disperse in SBS matrix again; Compare with document 3, the performance of product improves greatly.
Embodiment
Embodiment 1: halloysite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with trimethylammonium-methacrylate based ammonium chloride, obtains organophilic clay; This organophilic clay is joined S/B than 40/60, the type SBS cyclohexane solution of molecular weight 8-10 ten thousand (the SBS weight content is 15%), the add-on of organophilic clay is 1% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 30nm.Performance data sees Table 1.
Embodiment 2: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2.5% (weight), handles with trimethylammonium-methacrylate based ammonium chloride, obtains organophilic clay; This organophilic clay is joined S/B than 40/60, the type SBS cyclohexane solution of molecular weight 8-10 ten thousand (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 30nm.Performance data sees Table 1.
Embodiment 3: beidellite is stirred in water, and the time is 5 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 1.5% (weight), handles with trimethylammonium-methacrylate based ammonium chloride, obtains organophilic clay; This organophilic clay is joined S/B than 40/60, the type SBS cyclohexane solution of molecular weight 8-10 ten thousand (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 100nm.Performance data sees Table 1.
Corresponding S/B is than 40/60, and the pure colloidality of the type SBS of molecular weight 8-10 ten thousand can data see Table 3 in 1
#
Embodiment 4: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with the octadecyl alkyl dimethyl ammonium chloride, obtains organophilic clay; This organophilic clay is joined S/B than 20/80, the type SBS cyclohexane solution of molecular weight 8-10 ten thousand (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 50nm.Performance data sees Table 1.
Corresponding S/B is than 20/80, and the pure colloidality of the type SBS of molecular weight 8-10 ten thousand can data see Table 4 in 1
#
Embodiment 5: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with the octadecyl alkyl dimethyl ammonium chloride, obtains organophilic clay; This organophilic clay is joined S/B than 48/52, the type SBS cyclohexane solution of molecular weight 8-10 ten thousand (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 50nm.Performance data sees Table 1.
Corresponding S/B is than 48/52, and the pure colloidality of the type SBS of molecular weight 8-10 ten thousand can data see Table 5 in 1
#
Embodiment 6: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with cetyl trimethylammonium bromide, obtains organophilic clay; This organophilic clay is joined S/B than 40/60, the star-shaped sbs cyclohexane solution of molecular weight about 300,000 (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 50nm.Performance data sees Table 1.
Corresponding S/B is than 40/60, and the pure colloidality of the star-shaped sbs of molecular weight about 300,000 can data see Table 6 in 1
#
Embodiment 7: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with cetyl trimethylammonium bromide, obtains organophilic clay; This organophilic clay is joined S/B than 20/80, the star-shaped sbs cyclohexane solution of molecular weight about 300,000 (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 50nm.Performance data sees Table 1.
Corresponding S/B is than 20/80, and the pure colloidality of the star-shaped sbs of molecular weight about 300,000 can data see Table 7 in 1
#
Embodiment 8: sodium bentonite is stirred in water, and the time is 4 hours, leaves standstill after mixing 24 hours, and ultimate density (solid content) is controlled at about 2% (weight), handles with cetyl trimethylammonium bromide, obtains organophilic clay; This organophilic clay is joined S/B than 48/52, the star-shaped sbs cyclohexane solution of molecular weight about 300,000 (the SBS weight content is 15%), the add-on of organophilic clay is 4% of a SBS weight; Elder generation's high-shear, ultrasonication makes it to form uniform mixed solution again; Slough solvent with water vapour then, make the SBS/ clay nanocomposites.Under transmission electron microscope, observe, the gauge of clay layer more than 80% below 50nm.Performance data sees Table 1.
Corresponding S/B is than 48/52, and the pure colloidality of the star-shaped sbs of molecular weight about 300,000 can data see Table 8 in 1
#
Table 1
| Sample number into spectrum | 300% stress at definite elongation (MPa) | Tensile strength (MPa) | Tensile yield (%) | Tension set (%) | Hardness (Shao Er A) | MFR (g/10min) |
| 1 | 3.8 | 32.1 | 780 | 40 | 88 | 0.70 |
| 2 | 3.8 | 32.5 | 780 | 40 | 88 | 0.70 |
| 3 | 3.8 | 32.2 | 780 | 40 | 88 | 0.02 |
| 3 # | 3.8 | 24.7 | 770 | 32 | 88 | 1.24 |
| 4 | 1.4 | 10.4 | 810 | 40 | 65 | 0.50 |
| 4 # | 1.4 | 8.0 | 800 | 25 | 65 | 0.61 |
| 5 | 1.8 | 15.6 | 960 | 70 | 80 | 4.02 |
| 5 # | 1.8 | 12.0 | 950 | 60 | 80 | 5.00 |
| 6 | 4.0 | 30.0 | 710 | 40 | 94 | 0.01 |
| 6 # | 3.6 | 22.6 | 710 | 36 | 92 | 0.03 |
| 7 | 2.0 | 13.2 | 700 | 30 | 62 | 0.4 |
| 7 # | 1.8 | 10.0 | 700 | 26 | 60 | 0.5 |
| 8 | 1.6 | 21.5 | 700 | 60 | 78 | 0.5 |
| 8 # | 1.4 | 16.5 | 700 | 55 | 75 | 0.6 |
Rubber sampling and method for making sample are pressed GB/T15340-94;
The rubbery sample environment is regulated and standard temperature, humidity and the time of sample are pressed GB/T2941-91;
GB/T9352-88 is pressed in the preparation of thermoplastics compression moulding sample;
The mensuration of stretching performance is by GB/T528-1998;
The shore a hardness test method is pressed GB/T531-1999;
The melt flow rate (MFR) test method is pressed GB/T3682-83.
Claims (4)
1, a kind of preparation method of SBS/ clay nanocomposites is characterized in that in turn including the following steps:
A, will have being stained with of stratiform crystal layer overlay structure and be made into 1%～20% clay water solution, add the back centrifuge dehydration that organises of long carbochain organic quaternary ammonium salt, obtain the soil that organises;
The SBS cyclohexane solution that polyreaction obtains after finishing in b, organise soil and the SBS production process mixes, and carries out first high-shear, and ultrasonication forms uniform mixed solution again; The native add-on that organises is 1%～10% of a SBS weight;
C, remove the solvent in the mixed solution, make the SBS/ clay nanocomposites.
2, method according to claim 1 is characterized in that: clay is terre verte, polynite, talcum powder, beidellite, hectorite, silica or halloysite.
3, method according to claim 1, the number of carbon atom is 12～20 in the long carbochain organic quaternary ammonium salt of its feature.
4, according to claim 1 or 2 or 3 described methods, it is characterized in that: SBS is that number-average molecular weight is 80,000～300,000, block than S/B is 20/80～48/52 line style or star-like product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100228368A CN1307248C (en) | 2004-01-08 | 2004-01-08 | Method for preparing SOS/clay nano composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100228368A CN1307248C (en) | 2004-01-08 | 2004-01-08 | Method for preparing SOS/clay nano composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1640920A CN1640920A (en) | 2005-07-20 |
| CN1307248C true CN1307248C (en) | 2007-03-28 |
Family
ID=34868381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100228368A Expired - Lifetime CN1307248C (en) | 2004-01-08 | 2004-01-08 | Method for preparing SOS/clay nano composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1307248C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304860B (en) * | 2013-06-16 | 2015-08-05 | 北京化工大学 | A kind of tire tread glue of non-oxidation zinc |
| CN104945827B (en) * | 2015-06-26 | 2017-11-03 | 台橡（上海）实业有限公司 | A kind of case and bag overlay film thermoplastic elastic material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238353A (en) * | 1998-06-04 | 1999-12-15 | 北京化工大学 | Process for preparing clay-rubber nm-class composite material |
| CN1397572A (en) * | 2002-08-20 | 2003-02-19 | 华南理工大学 | Nano-class rubber-laminated inorganic substance composition and its preparing process |
-
2004
- 2004-01-08 CN CNB2004100228368A patent/CN1307248C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1238353A (en) * | 1998-06-04 | 1999-12-15 | 北京化工大学 | Process for preparing clay-rubber nm-class composite material |
| CN1397572A (en) * | 2002-08-20 | 2003-02-19 | 华南理工大学 | Nano-class rubber-laminated inorganic substance composition and its preparing process |
Non-Patent Citations (3)
| Title |
|---|
| 微纳米级粘土/橡胶复合材料 王益庆 张立群，北京化工大学学报，第27卷第1期 2000 * |
| 微纳米级粘土/橡胶复合材料 王益庆 张立群，北京化工大学学报，第27卷第1期 2000;有机蒙脱土的制备与表征 武保华 王一中 余鼎声，石油化工，第28卷第3期 1999 * |
| 有机蒙脱土的制备与表征 武保华 王一中 余鼎声，石油化工，第28卷第3期 1999 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1640920A (en) | 2005-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1079409C (en) | Process for preparing clay-rubber nm-class composite material | |
| Leblanc | Filled polymers: science and industrial applications | |
| Sun et al. | Improvement of silica dispersion in solution polymerized styrene–butadiene rubber via introducing amino functional groups | |
| Zhang et al. | Morphology and mechanical properties of clay/styrene‐butadiene rubber nanocomposites | |
| CN104072827B (en) | A kind of oil-filled carbon nano-tube solution of filling is total to beta-rubber and preparation method thereof | |
| CN100491452C (en) | Silane coupling agent modified clay and butadiene styrene rubber nanometer composite material preparation method | |
| US9631069B1 (en) | Poly (cyclic butylene terephthalate) / silicon dioxide nanocomposite | |
| CN102382338A (en) | Isoprene rubber blend and its preparation method | |
| CN102153794A (en) | Method for preparing polymer/clay nano-composite | |
| Jia et al. | Organic interfacial tailoring of styrene butadiene rubber–clay nanocomposites prepared by latex compounding method | |
| Fang et al. | Notably improved dispersion of carbon black for high-performance natural rubber composites via triazolinedione click chemistry | |
| CN100436527C (en) | Process for preparing organic modified clay and styrene butadiene rubber nano composite material | |
| Chu et al. | Constructing chemical interface layers by using ionic liquid in graphene oxide/rubber composites to achieve high-wear resistance in environmental-friendly green tires | |
| CN101704967A (en) | Preparation method of white carbon black/clay/rubber nanocomposite | |
| CN101225228A (en) | Fiber glass, elastomer and inorganic nano-particle synergistic modified nylon and preparation thereof | |
| CN106554528B (en) | Butadiene-styrene rubber/white carbon black/lignocellulosic/montmorillonite rubber composite material and preparation method thereof | |
| CN109627502B (en) | Composite material of natural rubber and preparation method thereof | |
| CN1763127A (en) | Modified clay and rubber composite material preparation method | |
| CN1307248C (en) | Method for preparing SOS/clay nano composite material | |
| CN1194998C (en) | Nano-class rubber-laminated inorganic substance composition and its preparing process | |
| CN106496698A (en) | Enhanced butadiene-styrene rubber of a kind of superfined flyash and preparation method thereof | |
| CN106496658A (en) | A kind of natural rubber of superfined flyash filling and preparation method thereof | |
| CN104650303B (en) | A kind of preparation method for being modified oil-filled high-performance powder butadiene-styrene rubber | |
| CN109796646A (en) | A kind of oil-filled type complex solution of carbon nano-tube modification phyllosilicate collaboration enhancing is total to gel rubber and preparation method thereof | |
| CN104650421A (en) | Preparation of butadiene styrene rubber modified by rice hull ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINA PETROCHEMICAL CORPORATION; BALING PETROCHEM Free format text: FORMER OWNER: BALING PETROCHEMICAL CO., LTD., SINOPEC Effective date: 20070615 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070615 Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Co-patentee after: China Petrochemical Group Baling Petroleum Co.,Ltd. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 414014 Yunxi District, Hunan, Yueyang Patentee before: China Petrochemical Group Baling Petroleum Co.,Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: YUEYANG YADA PLASTIC Co.,Ltd. Assignor: China Petrochemical Group Baling Petroleum Co.,Ltd.|CHINA PETROLEUM & CHEMICAL Corp. Contract record no.: 2010430000052 Denomination of invention: Method for preparing SBS/ clay nano composite material Granted publication date: 20070328 License type: Exclusive License Open date: 20050720 Record date: 20100525 |
|
| CX01 | Expiry of patent term |
Granted publication date: 20070328 |
|
| CX01 | Expiry of patent term |