CN103724736B - The original position of rubber/clay nano composite material is organically-modified-preexpanding preparation method - Google Patents
The original position of rubber/clay nano composite material is organically-modified-preexpanding preparation method Download PDFInfo
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Abstract
The present invention be a kind of original position of rubber/clay nano composite material organically-modified-preexpanding preparation method, simultaneously the method organic modifiers and certain proportioning organic solvent is added in inorganic clay, by three-roll grinder, it is ground, realize the organically-modified and preexpanding of the original position of clay; Then by rubber and original position is organically-modified and the clay of preexpanding joins in mill, substep adds Synergist S-421 95 simultaneously, final obtained rubber/clay nano composite material.Result shows when consumption of organic solvent is 20%, and the performance of obtained nano composite material and structure all reach optimum, and nano composite material Micro-Structure and mechanical property, be all obviously better than " single stage method " simultaneously.The present invention, by quantitatively with an organic solvent, avoids the drying and processing to clay, decreases the pollution to environment, reduce cost, simplify pretreatment process simultaneously.The inventive method is easy to suitability for industrialized production, has more wide application prospect.
Description
Technical field
The present invention relates to the novel preparation technology of a kind of rubber and clay nanocomposites, specifically a kind of original position of rubber/clay nano composite material organically-modified-preexpanding preparation method.
Background technology
Clay is aboundresources and cheap natural materials, and access approaches, without the need to oil, is used as applying filler already in rubber industry.As serial fillers such as kaolin, polynite, red clay and potter's clay.Wherein the most frequently used is polynite, also claims wilkinite.
The main component of polynite is montmorillonite, and chemical formula is 4SiO2Al2O3H2O.Mineral montmorillonite belongs to oblique system, is to be sandwiched in by two-layer silicon-oxy tetrahedron and one deck the 2:1 type layer silicate mineral that aluminium (magnesium) oxygen (hydroxyl) octahedral sheet therebetween forms, and intercalation the positively charged ion occurred with hydrated state.
According to the dominant cation kind of montmorillonite contained by polynite, sodium matter polynite (alkaline soil), Ca-montmorillonite (alkaline soil) and three kinds, natural bleaching soil (sour earth) can be divided into.
Because polynite is at China's rich reserves, current annual production reaches tens thousand of ton, low price, therefore the strengthening agent as rubber is developed, replace part carbon black, not only can reduce the demand of carbon black, and rubber over-all properties can be improved due to the performance of its uniqueness, and likely prepare other filler and to be beyond one's reach performance.
Layered silicate/polymer nanocomposites is the intercalation synthesis preparation science of its uniqueness with conventional composite materials difference in preparation.So-called intercalation synthesis is exactly be inserted in the nano-space of laminated silicate interlayer by monomer or polymer molecule, utilizes heat of polymerization or shearing force layered silicate are peeled off into nano based body structure unit or microcell and evenly spread in polymeric matrix.Because the layer silicate minerals such as polynite, kaolin, rectorite leng have larger initial separation and tradable interlayer cation, make people that the mode of ion-exchange can be utilized their interlamellar spacing to be expanded to the degree allowing polymer molecule to insert, thus utilize the nano composite material of this organic layered silicate salt processability excellence.
As filler, it strengthens poor ability to the inorganic claies such as natural montmorillonite, only can be used in traditional micro-composites.Polynite has laminated structure, and some ions between layers can exchange with other organic ion, therefore, can carry out exchange prepare organic clay with the ion of organic ion and inorganic clay interlayer.Be prepared from by ion exchange reaction as adopted cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride etc.In " organic MMT is to high-density polyethylene modified research ", (engineering plastics are applied, 6th phase 23-25 page in 2005) in report preparation method about organo montmorillonite, concrete operation step is as follows: take 20g sodium base MMT and be scattered in 1000mL deionized water, produce MMT suspension liquid under strong mixing; Take the palmityl trimethyl ammonium chloride being greater than MMT loading capacity, be mixed with solution.Above-mentioned suspension liquid is placed in 80 DEG C of waters bath with thermostatic control, drips palmityl trimethyl ammonium chloride solution under strong agitation, reaction 2h, static 24h, obtains white depositions.There is (AgNO3 solution test) to white depositions without chlorion with deionized water wash, the constant temperature oven putting into 70 DEG C is dried, and then grinds, and crosses 0.071mm sieve, for subsequent use.Adopt identical experimental procedure, with Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, distearyl dimethyl ammonium chloride, organic-treating is carried out to sodium base MMT.
Be prepared from by ion exchange reaction as adopted hexadecyl brometo de amonio.At " EPDM/montmorillonite nanocomposites preparation, sign and rheological property " (elastomerics, 6th phase 14-18 page in 2002) in report preparation method about organo montmorillonite, concrete operation step is as follows: adopt 50g sodium-based montmorillonite (Na-MMT) to be under agitation dispersed in 2000ml, the hot water of 80 DEG C and form uniform montmorillonite suspension liquid; Be uniformly mixed after two (2-hydroxyethyl) methyl lauryl ammonium chlorides and saturated mixed in hydrochloric acid with montmorillonite suspension liquid, obtain organo montmorillonite through filtration, washing, drying.Characteristic diffraction peak is there is in sodium-based montmorillonite at 2 θ=7o, going out its lamella interlamellar spacing by Bragg Equation for Calculating is 1.26nm, characteristic diffraction peak is there is in the organo montmorillonite (OMMT) obtained at 2 θ=3.3o, after the Na+ showing in sodium-based montmorillonite (Na-MMT) is replaced by alkyl phosphate ion, interlamellar spacing rises to 2.67nm.Ion exchange property and the swelling property of people's general clay prepare composite nano polymer/clay material.By the laminated structure of uniqueness contained in clay particle structure, be evenly dispersed in macromolecule matrix, because the thickness of clay layer is at about 1nm, thus finally in the composite, the gauge of disperse phase (clay layer individual layer or lamella aggregate) all can remain on below 100nm, and such obtained material is just nano composite material.
For improving the mechanical property of rubber composite, thermal stability and gas barrier property, people have prepared the multiple rubber matrix nanocomposites such as natural rubber/clay, paracril/clay, ethylene-propylene rubber(EPR)/clay, styrene-butadiene rubber(SBR)/clay, isoprene-isobutylene rubber/clay by various method.
Rubber/clay nano composite material generally adopts following 6 kinds of methods preparation:
(1) solution intercalation method
Same organic solvent dispersed clay and dissolving rubber respectively can be adopted, subsequently slurry and rubber solutions are uniformly mixed; Also organic solvent dispersion clay can first be used, subsequently rubber is joined in slurry and be uniformly mixed, by the effect of solvent, rubber macromolecule intercalation is made to enter between the lamella of clay, then organic solvent is removed in volatilization under vacuum, rubber macromolecule chain is just sandwiched between clay layer, forms rubber/clay nano composite material.
" preparation of silastic/clay matrix material, Structure and Properties " (polymer journal, second phase 149-153 page in 1998) that such as Wang Sheng outstanding person waits people to deliver reports and adopts solution intercalation legal system for silastic/clay nanometer composite material.
(2) situ aggregation method
Polymer monomer is embedded into the interlayer of organic clay, then trigger monomer polymerization under suitable conditions.By the thermopositive reaction of in-situ polymerization, stratiform organic clay is peeled off and is distributed in polymer matrix.
Patent " COMPOSITEMATERIALCONTAININGALAYEREDSILICATE " (USP4,889,885) reports and utilizes situ aggregation method to prepare clay/synthetic polyisoprene nano composite material.
(3) melting intercalation method
Organic clay is directly mixing on a mill until with rubber, utilize mill consumingly shearing force rubber macromolecular chain is inserted into the sheet interlayer of organic clay, thus formation rubber/clay nano composite material.
Melting intercalation method does not need that solvent, efficiency are high, the preparation that is suitable for most polymers matrix material, be easy to industrial applications, but the dispersed texture of its matrix material, mechanical property, air-tightness etc. are all not as good as the excellent property of the matrix material adopting solution intercalation method to obtain.
(4) emulsion method
The suspension of the clay and water with stratiform crystal layer overlay structure is mixed with rubber latex, form uniform mixed solution, then add and the flocculation agent of rubber latex breakdown of emulsion can be made to flocculate, whole system co-precipitation, finally throw out is dewatered, dry obtained rubber/clay nano composite material.
(5) preexpanding organic clay and mechanical blending method
First that inorganic clay is organically-modified, then organic solvent and organic clay are pre-mixed by 1ml:1g obtain preexpanding organic clay, preexpanding organic clay is mixed to get rubber/clay nano composite material with rubber and Synergist S-421 95 again.
Patent " prepares the method for rubber and clay nanocomposites ", and (ZL200410008452.0) reports by preexpanding organic clay and the mechanical blending legal system method for rubber/clay nano composite material with preexpanding organic clay.And apply this technology and prepared the multiple nano composite materials such as styrene-butadiene rubber(SBR)/clay, paracril/clay, isoprene-isobutylene rubber/clay.
(6) rubber and clay nanocomposites preparation method
Add in inorganic clay and to add organic solvent preexpanding while organic modifiers modification becomes organic clay and be prepared into organically-modified and preexpanding clay, organically-modified and preexpanding clay is mixed to get rubber/clay nano composite material with rubber and Synergist S-421 95 again.
Patent " preparation method of rubber and clay nanocomposites " (ZL201110096667.2) reports the method preparing rubber/clay nano composite material by organically-modified and preexpanding clay and melting method.And prepared the multiple nano composite material such as paracril/clay, styrene-butadiene rubber(SBR)/clay by this technology.
Summary of the invention
The object of the invention is the preparation method in order to provide a kind of brand-new rubber/clay nano composite material, specifically a kind of original position of rubber/clay nano composite material organically-modified-preexpanding preparation method.The inventive method is on the basis of patent " rubber and clay nanocomposites preparation method " (calling in the following text " single stage method "), adopt three-roll grinder by inorganic clay, organic modifiers, ORGANIC SOLVENT MIXTURES grinding, realize the novel preparation technology of the organically-modified of inorganic clay preexpanding, production process is simplified, raise the efficiency, reduce the pollution to environment.
The present invention is achieved by the following technical solutions:
The original position of rubber/clay nano composite material is organically-modified-a preexpanding preparation method, comprise the steps:
1) inorganic clay, organic modifiers and organic solvent are mixed according to a certain ratio, the mass ratio of inorganic clay and organic modifiers is 2.8:1, and the mass ratio of inorganic clay and organic solvent is 10:1.5-10:9; Then the soil mixed is left standstill 1h; Then the composite soil after leaving standstill is placed in three-roll grinder and grinds 5min, finally obtain the organically-modified and preexpanding organic clay (hereinafter referred to as original position organic clay) of original position; Wherein, described organic modifiers be in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide a kind of or arbitrary proportion mixing several, described organic solvent be in vinylformic acid, dehydrated alcohol, propyl carbinol a kind of or arbitrary proportion mixing several; Inorganic clay also can adopt multiple known material, as sodium-based montmorillonite etc.;
2) in mass ratio for 10:1 to get in rubber and step 1) the organically-modified and preexpanding organic clay of obtained original position respectively, and be placed on mixing 15-60min in mill, three steps are divided to add Synergist S-421 95 subsequently, mixing evenly rear sizing material lower roll, vulcanizer carries out sulfuration sample preparation, finally namely obtains rubber/clay nano composite material; Wherein, when described rubber is styrene-butadiene rubber(SBR), the addition means of each Synergist S-421 95 and parts by weight following (calculating by 100 parts by weight of rubber): the first step adds 5 parts, zinc oxide, stearic acid 2 parts, mixing evenly after, second step adds dibenzothiazyl disulfide 0.5 part, tetramethyl-thiuram disulfide 0.2 part, vulkacit D 0.5 part, N-sec.-propyl-N '-diphenyl-para-phenylene diamine 1.0 parts, mixing evenly after, the 3rd step adds 2 parts, sulphur; When described rubber is paracril, the addition means of each Synergist S-421 95 and parts by weight following (calculating by 100 parts by weight of rubber): the first step adds 5 parts, zinc oxide, stearic acid 1 part, mixing evenly after, second step adds dibenzothiazyl disulfide 1.5 parts, N-sec.-propyl-N '-diphenyl-para-phenylene diamine 2.0 parts, mixing evenly after, the 3rd step adds 2 parts, sulphur.
The inventive method utilizes inorganic clay organically-modified while, add suitable organic solvent, then utilize three-roll grinder to ground material, realize preexpanding, cause the lattice spacing of layered silicate to strengthen further even to peel off, then utilize the strong shearing force of mill to be inserted between clay layer by rubber macromolecular chain, form rubber and clay nanocomposites; Clay is cheap, and the rubber of preparation and clay nanocomposites are that one can meet performance requriements, can reduce costs again, and can simplified processing process, and raising the efficiency, reduce the pollution to environment, is a kind of nano composite material of environment-friendly type.
Organic solvent in the present invention can adopt vinylformic acid, dehydrated alcohol or this kind of organic solvent that human body and environment are safe from harm of propyl carbinol, substitute in the past conventional in prepared by rubber and clay nanocomposites toluene, tetracol phenixin, the noxious solvents such as chloroform, not only be conducive to protection of the environment, and the amount to add because of organic solvent is quantitatively (in organic clay, content is 20% in position), therefore, " single stage method " that the inventive method is compared in background technology adopts appropriate organic solvent, avoid the waste of raw material and the pollution of environment, and operation is more simple, obtained nano composite material has better Micro-Structure and mechanical property, therefore, the preparation method that the present invention proposes is easier to suitability for industrialized production.
The beneficial effect of the inventive method is:
(1) the present invention is compared with single stage method, has better Micro-Structure and mechanical property, and avoids the waste of raw material and the drying and processing to clay, decrease the pollution to environment, reduce cost, simplify pretreatment process simultaneously, therefore, suitability for industrialized production is easier to;
(2) the present invention prepares rubber compared with clay nanocomposites with traditional melting intercalation method, has better dispersed texture, higher mechanical property;
(3) the present invention and emulsion method prepare rubber compared with clay nanocomposites, and operation is simple, and the cycle is short, especially suitable for not having the isoprene-isobutylene rubber of emulsion form.
Accompanying drawing explanation
Fig. 1 is be the infrared spectrum of the organically-modified organic clay of inorganic clay and cetyl trimethylammonium bromide.
The paracril that Fig. 2 is embodiment 4, embodiment 5 and embodiment 6 are prepared by novel processing step of the present invention and the X ray diffracting spectrum of organic clay nano composite material.
The X ray diffracting spectrum of Fig. 3 paracril that to be embodiment 5 prepare with comparative example 2 and organic clay nano composite material.
Fig. 4 is scanning electronic microscope (SEM) photo of embodiment 5 paracril that adopts the organic clay of novel processing step process of the present invention to prepare and organic clay nano composite material.
Fig. 5 is scanning electronic microscope (SEM) photo of the paracril prepared of organic clay that comparative example 2 adopts " single stage method " to process and organic clay nano composite material.
Embodiment
The inorganic clay used in following examples and comparative example is for sodium-based montmorillonite:
Embodiment 1
Inorganic clay, cetyl trimethylammonium bromide are mixed according to a certain ratio with propyl carbinol; Inorganic clay and cetyl trimethylammonium bromide mass ratio are 2.8g:1g, inorganic clay and propyl carbinol mass ratio be 10g:2.4g(wherein the mass fraction of propyl carbinol in obtained original position organophilic clay be 15% i.e. ω
propyl carbinol=15%, lower same); The soil mixed leaves standstill 1h; Above-mentioned mixed clay is ground 5min in three-roll grinder, obtains the organically-modified and preexpanding organic clay of original position (being called for short original position organic clay), for subsequent use.By 100 parts of paracrils and 10 parts of original position organic clay mixing 30min in two roller mill, divide three steps to add following various Synergist S-421 95 subsequently, the first step adds 5 parts, zinc oxide, stearic acid 1 part; Second step adds dibenzothiazyl disulfide 1.5 parts (promotor), N-sec.-propyl-N '-diphenyl-para-phenylene diamine 2.0 parts (protective agent); 3rd step adds 2 parts, sulphur, obtains paracril and organic clay mixture.Then at 160 DEG C, measure its sulfurizing time (T90), carry out sulfuration sample preparation, finally namely obtain NBR/clay nano by sulfurizing time on vulcanizing press, its mechanical property is as shown in table 1.
Embodiment 2
Change inorganic clay and propyl carbinol mass ratio into 10g:3.4g(ω
propyl carbinol=20%), all the other operation stepss are with embodiment 1, and finally obtained NBR/clay nano, its mechanical property is as shown in table 1.
Embodiment 3
Change inorganic clay and propyl carbinol mass ratio into 10g:5.9g(ω
propyl carbinol=30%), all the other operation stepss are with embodiment 1, and finally obtained NBR/clay nano, its mechanical property is as shown in table 1.
Embodiment 4
Be that 10g:2.4g changes inorganic clay into and vinylformic acid mass ratio is 10g:2.4g(ω by inorganic clay and propyl carbinol mass ratio
vinylformic acid=15%), all the other operation stepss are with embodiment 1, and finally obtained NBR/clay nano, as shown in Figure 4, mechanical property is as shown in table 2 for its scanning electron microscope Photomicrograph, and XRD figure spectrum as shown in Figure 2.
Embodiment 5
Be that 10g:2.4g changes inorganic clay into and vinylformic acid mass ratio is 10g:3.4g(ω by inorganic clay and propyl carbinol mass ratio
vinylformic acid=20%), all the other operation stepss are with embodiment 1, and finally obtained NBR/clay nano, its mechanical property is as shown in table 2, and XRD figure spectrum as shown in Figure 2.
Embodiment 6
Be that 10g:2.4g changes inorganic clay into and vinylformic acid mass ratio is 10g:5.9g(ω by inorganic clay and propyl carbinol mass ratio
vinylformic acid=30%), all the other operation stepss are with embodiment 1, and finally obtained NBR/clay nano, its mechanical property is as shown in table 2, and XRD figure spectrum as shown in Figure 2.
Embodiment 7
Inorganic clay, cetyl trimethylammonium bromide are mixed according to a certain ratio with propyl carbinol; Inorganic clay and cetyl trimethylammonium bromide mass ratio are 2.8g:1g, and inorganic clay and propyl carbinol mass ratio are 10g:1.5g(ω
propyl carbinol=10%); The soil mixed leaves standstill 1h; The clay of above-mentioned mixing is ground 5min on three-roll grinder, obtains the organically-modified and preexpanding organic clay of original position (being called for short original position organic clay), for subsequent use.The mixing 60min in two roller mill by 100 weight part styrene-butadiene rubber(SBR) and 10 weight part original position organic claies, divide three steps to add following various Synergist S-421 95 subsequently, the first step adds 5 parts, zinc oxide, stearic acid 2 parts; Second step adds dibenzothiazyl disulfide 0.5 part (promotor), tetramethyl-thiuram disulfide 0.2 part (promotor), vulkacit D 0.5(promotor), N-sec.-propyl-N '-diphenyl-para-phenylene diamine 1.0 parts (protective agent); 3rd step adds 2 parts, sulphur, obtains styrene-butadiene rubber(SBR) and organic clay mixture.Then at 160 DEG C, measure its sulfurizing time (T90), carry out sulfuration sample preparation by sulfurizing time on vulcanizing press, finally namely obtain styrene-butadiene rubber(SBR)/clay nanocomposites, its mechanical property is as shown in table 3.
Embodiment 8
Change inorganic clay and propyl carbinol mass ratio into 10g:3.4g(ω
propyl carbinol=20%), all the other operation stepss are with embodiment 9, and finally obtained styrene-butadiene rubber(SBR)/clay nanocomposites, its mechanical property is as shown in table 3.
Embodiment 9
Change inorganic clay and propyl carbinol mass ratio into 10g:5.9g(ω
propyl carbinol=30%), all the other operation stepss are with embodiment 9, and finally obtained styrene-butadiene rubber(SBR)/clay nanocomposites, its mechanical property is as shown in table 3.
Embodiment 10
Change organic solvent into vinylformic acid, inorganic clay and acrylic acid mass ratio are 10g:3.4g(ω
vinylformic acid=20%), all the other operation stepss are with embodiment 9, and finally obtained styrene-butadiene rubber(SBR)/clay nanocomposites, its mechanical property is as shown in table 7.
Embodiment 11
Change organic modifiers into Cetyltrimethylammonium bromide, organic solvent changes dehydrated alcohol into, and inorganic clay and dehydrated alcohol mass ratio are 10g:9g, and all the other operation stepss, with embodiment 9, finally obtain styrene-butadiene rubber(SBR)/clay nanocomposites.
Embodiment 12
Change organic modifiers into palmityl trimethyl ammonium chloride, organic solvent changes dehydrated alcohol into, and inorganic clay and dehydrated alcohol mass ratio are 10g:1.5g, and all the other operation stepss, with embodiment 9, finally obtain styrene-butadiene rubber(SBR)/clay nanocomposites.
Embodiment 13
Change organic modifiers into Cetyltrimethylammonium bromide, organic solvent changes dehydrated alcohol into, and inorganic clay and dehydrated alcohol mass ratio are 10g:1.5g, and all the other operation stepss, with embodiment 1, finally obtain NBR/clay nano.
Embodiment 14
Change organic modifiers into palmityl trimethyl ammonium chloride, organic solvent changes dehydrated alcohol into, and inorganic clay and dehydrated alcohol mass ratio are 10g:9g, and all the other operation stepss, with embodiment 1, finally obtain NBR/clay nano.
Comparative example 1
Be that 1g:10mL prepares slurry liquid in the ratio of inorganic clay and deionized water, be warming up to 65 DEG C in a water bath, adjust slurry liquid pH=7, be that cetyl trimethylammonium bromide is configured to solution by 1g:2.8g by the quality of cetyl trimethylammonium bromide and the mass ratio of inorganic clay, drop under vigorous stirring in slurry liquid, simultaneously in inorganic clay: the ratio of propyl carbinol=1g:1mL adds propyl carbinol, at constant temperature 65 DEG C, stir 12h.Suction filtration is carried out again, with the AgNO of 0.1mol/L after solution being cooled to room temperature
3solution is titrated to without bromide anion in filtrate to filtrate, dries and obtain preexpanding organic clay under room temperature, grinding, for subsequent use.All the other operation stepss are with embodiment 1.As shown in Figure 5, mechanical property is as shown in table 4 for the electron scanning micrograph of paracril prepared by " single stage method " and organic clay nano composite material, and the XRD of paracril and organic clay nano composite material as shown in Figure 4.
Comparative example 2
Change propyl carbinol into vinylformic acid, all the other operation stepss are with comparative example 1.The mechanical property of organic clay prepared by " single stage method " and nitrile rubber nanocomposites is as shown in table 5.
Comparative example 3
Be that 1g:10mL prepares slurry liquid in the ratio of inorganic clay and deionized water, be warming up to 65 DEG C in a water bath, adjust slurry liquid pH=7, be that cetyl trimethylammonium bromide is configured to solution by 1g:2.8g by the quality of cetyl trimethylammonium bromide and the mass ratio of inorganic clay, drop under vigorous stirring in slurry liquid, simultaneously in inorganic clay: the ratio of propyl carbinol=1g:1mL adds propyl carbinol, at constant temperature 65 DEG C, stir 12h.Suction filtration is carried out again, with the AgNO of 0.1mol/L after solution being cooled to room temperature
3solution is titrated to without bromide anion in filtrate to filtrate, dries and obtain preexpanding organic clay under room temperature, grinding, for subsequent use.All the other operation stepss are with embodiment 7.The mechanical property of organic clay prepared by " single stage method " and nitrile rubber nanocomposites is as shown in table 7.
Comparative example 4
Change propyl carbinol into vinylformic acid, all the other operation stepss are with comparative example 3, and the mechanical property of organic clay prepared by " single stage method " and butadiene styrene rubber nanometer composite material is as shown in table 7.
Below each performance comparison table:
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
What adopt novel processing step of the present invention to prepare take propyl carbinol as paracril and the organic clay nano composite material of organosilicon prepolymer swelling agent, and the mechanical performance compare that its material is relevant is listed in table 1; What adopt novel processing step of the present invention to prepare take vinylformic acid as paracril and the organic clay nano composite material of organosilicon prepolymer swelling agent, and the mechanical performance compare that its material is relevant is listed in table 2; What adopt novel processing step of the present invention to prepare take propyl carbinol as styrene-butadiene rubber(SBR) and the organic clay nano composite material of organosilicon prepolymer swelling agent, and the mechanical performance compare that its material is relevant is listed in table 3; Adopt novel processing step of the present invention and " single stage method " prepare with vinylformic acid to be paracril and the organic clay nano composite material of organosilicon prepolymer swelling agent, the mechanical performance compare that its material is correlated with is listed in table 4; Adopt novel processing step of the present invention and " single stage method " prepare with propyl carbinol to be paracril and the organic clay nano composite material of organosilicon prepolymer swelling agent, the mechanical performance compare that its material is correlated with is listed in table 5; Adopt novel processing step of the present invention and " single stage method " prepare with propyl carbinol to be styrene-butadiene rubber(SBR) and the organic clay nano composite material of organosilicon prepolymer swelling agent, the mechanical performance compare that its material is correlated with is listed in table 6.As can be seen from table 1-3, the paracril adopting the organic clay of novel processing step process of the present invention to prepare and organic clay nano composite material and styrene-butadiene rubber(SBR) and organic clay nano composite material, its mechanical property such as tensile strength, tear strength all changes along with the content of organosilicon prepolymer swelling agent in organic clay, can show that the performance of rubber nano composite material is best when content is 20% in organosilicon prepolymer swelling agent in position organic clay simultaneously, as can be seen from Table 4, the paracril adopting the organic clay of novel processing step process of the present invention to prepare and organic clay nano composite material, except stress at definite elongation, its mechanical property such as tensile strength, tear strength is all better than nano composite material prepared by " single stage method ", as can be seen from Table 5, propyl carbinol is adopted to be the paracril prepared of the organic clay of organosilicon prepolymer swelling agent novel processing step process of the present invention and organophilic clay nano composite material, its mechanical property such as tensile strength, tear strength is all better than nano composite material prepared by " single stage method ", and the organic solvent that therefore the present invention adopts can be propyl carbinol, vinylformic acid, dehydrated alcohol etc., as can be seen from Table 6, the styrene-butadiene rubber(SBR) adopting the organic clay of novel processing step process of the present invention to prepare and organic clay nano composite material, its tensile strength, the mechanical properties such as tear strength are all better than nano composite material prepared by " single stage method ", therefore rubber matrix of the present invention can be paracril isopolarity rubber, also can be the non-polar rubbers such as styrene-butadiene rubber(SBR), therefore, novel processing step of the present invention not only avoid the waste of raw material and the drying and processing to clay, decrease the pollution to environment, simplify operation simultaneously, and ensure that the mechanical property of nano composite material has corresponding raising in various degree.
In Fig. 1, curve 1 is the infrared spectrum of organic clay, and curve 2 is the infrared spectrum of inorganic clay, and in curve 1, the strong absorption peak of CH2 appears in 2920cm-1 place; CH3 vibration peak is there is at 2850cm-1 place; There is C-N stretching vibration absorption peak in 1467cm-1 place, these characteristic peaks are all the vibrational bands having base group (-CH2 ,-CH3, C-N) of cetyl trimethylammonium bromide.Prove that cetyl trimethylammonium bromide has group to enter into the structure of inorganic clay, replace the tradable positively charged ion of inorganic clay interlayer, form inorganic clay interlayer compound, i.e. the organically-modified success of inorganic clay, has prepared organic clay.
In Fig. 2, curve 1 is the organic clay that processes of embodiment 1 and the nano composite material (ω for preparing of paracril
vinylformic acid=15%) XRD curve, curve 2 is organic clay and the nano composite material (ω for preparing of paracril of process
vinylformic acid=20%) XRD curve, curve 3 is organic clay and the nano composite material (ω for preparing of paracril of process
vinylformic acid=30%) XRD curve.As shown in Figure 2, when acrylic acid content is 15%, going out peak angle is 1.92 °; Content is 20%, and going out peak angle is 1.72 °; Content is 30%, and going out peak angle is 1.82 °.Namely, when acrylic acid content is 20%, go out peak angle and shift to an earlier date compared with other two, the interlamellar spacing of corresponding clay increases 0.57nm and 0.29nm respectively.When the acrylic acid content illustrating in clay is 20%, in matrix material, clay layer spacing is maximum, and organic solvent vinylformic acid has entered into organic clay sheet interlayer and expanded organic clay sheet interlayer spacing, and the intercalation effect of rubber macromolecule is best, and material property is best.
In Fig. 3, curve 1 is the XRD curve of nano composite material prepared by the organic clay that processes of embodiment 1 and paracril, and curve 2 is XRD curves of nano composite material prepared by organic clay that in comparative example 1 prepared by " single stage method " and paracril.As shown in Figure 3, rubber macromolecular chain is inserted between clay layer by the strong shearing force of mill, form rubber/clay nano composite material, it is 1.72 ° that organic clay prepared by the inventive method and nitrile rubber nanocomposites go out peak angle, and matrix material prepared by " single stage method " goes out peak angle is 2.34 °, compare " single stage method ", nano composite material prepared by the inventive method goes out peak angular advance 0.62 °, the interlamellar spacing of organic clay increases 1.36nm, namely the inventive method expands the interlamellar spacing of clay layer further, demonstrate superiority and feasibility that the inventive method prepares clay-rubber nm-class composite material.
Comparison diagram 4 and Fig. 5 known, the dispersion of paracril prepared by the organic clay of the inventive method process and organic clay nano composite material is more careful, even, significantly better than " single stage method ".
Claims (1)
1. the original position of rubber/clay nano composite material organically-modified-a preexpanding preparation method, it is characterized in that, comprise the steps:
1) inorganic clay, organic modifiers and organic solvent are mixed according to a certain ratio, the mass ratio of inorganic clay and organic modifiers is 2.8:1, and the mass ratio of inorganic clay and organic solvent is 10:1.5-10:9; Then the soil mixed is left standstill 1h; Then the composite soil after leaving standstill is placed in three-roll grinder and grinds 5min, finally obtain the organically-modified and preexpanding organic clay of original position; Wherein, described organic modifiers be in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Cetyltrimethylammonium bromide a kind of or arbitrary proportion mixing several, described organic solvent be in vinylformic acid, dehydrated alcohol, propyl carbinol a kind of or arbitrary proportion mixing several;
2) in mass ratio for 10:1 to get in rubber and step 1) the organically-modified and preexpanding organic clay of obtained original position respectively, and be placed on mixing 15-60min in mill, three steps are divided to add Synergist S-421 95 subsequently, mixing evenly rear sizing material lower roll, vulcanizer carries out sulfuration sample preparation, finally namely obtains rubber/clay nano composite material; Wherein, when described rubber is styrene-butadiene rubber(SBR), addition means and the parts by weight of each Synergist S-421 95 are as follows, calculate by 100 parts by weight of rubber: the first step adds 5 parts, zinc oxide, stearic acid 2 parts, mixing evenly after, second step adds dibenzothiazyl disulfide 0.5 part, tetramethyl-thiuram disulfide 0.2 part, vulkacit D 0.5 part, N-sec.-propyl-N '-diphenyl-para-phenylene diamine 1.0 parts, mixing evenly after, the 3rd step adds 2 parts, sulphur; When described rubber is paracril, addition means and the parts by weight of each Synergist S-421 95 are as follows, calculate by 100 parts by weight of rubber: the first step adds 5 parts, zinc oxide, stearic acid 1 part, mixing evenly after, second step adds dibenzothiazyl disulfide 1.5 parts, N-sec.-propyl-N '-diphenyl-para-phenylene diamine 2.0 parts, mixing evenly after, the 3rd step adds 2 parts, sulphur.
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