CN100457814C - Chloroprene rubber/montmorillonite nano-composite material and its preparation method - Google Patents
Chloroprene rubber/montmorillonite nano-composite material and its preparation method Download PDFInfo
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- CN100457814C CN100457814C CNB2006101454581A CN200610145458A CN100457814C CN 100457814 C CN100457814 C CN 100457814C CN B2006101454581 A CNB2006101454581 A CN B2006101454581A CN 200610145458 A CN200610145458 A CN 200610145458A CN 100457814 C CN100457814 C CN 100457814C
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Abstract
This invention relates to a stripping chloronorgutta(CR)/ montmorillonite nanometer composite which is of high mechanical performance and fine antistatic static electricity performance and its preparation. The preparation includes: purify montmorillonite and carry out natrium change; carry out montmorillonite Organification; prepare nanometer composite of chloronorgutta crude rubber /montmorillonite; and prepare nanometer composite of chloronorgutta/montmorillonite.
Description
Technical field
The present invention relates to the good nano composite material of a kind of strong mechanical performance and antistatic property, particularly, the present invention relates to a kind of exfoliated chloroprene rubber (CR)/montmorillonite nano-composite material and preparation method thereof.
Background technology
At present, with respect to plastics/laminated nm-silicate composite material, less to the research of rubber/lamellar silicate nanometer composite material.Domesticly mainly contain people such as Chinese Academy of Sciences chemistry institute QiZongNeng, the Zhang Liqun of Beijing University of Chemical Technology and carrying out the work aspect the development of rubber/lamellar silicate nanometer composite material.Its research method has emulsion polymerization, melt intercalated method, blending method, blend coagulation method and solution intercalation method etc., and it is comparatively general wherein to adopt melt intercalated method to prepare such material.Though melt intercalated method technology is simple and convenient, for macromolecular intercalation effect and bad, mainly obtain intercalation and intermingling material, performance of composites does not reach expected effect.
The constructional feature of rubber/lamellar silicate nanometer composite material is that dispersed phase size reaches nano level.Because the surface-area and the volume ratio of disperse phase sharply increase, and cause two alternate interactions to strengthen greatly.For exfoliated nano-composite, owing to limited the distortion of rubber and hindered crack propagation with nano level dispersive inorganic sheet, therefore has good reinforcing effect, can replace the reinforcement of traditional carbon black and white carbon black, thereby save energy, reduce and pollute, can be widely used in light goods, change the single black of original most of rubber item; Because the specific surface area of clay layer is bigger, homodisperse lamella has stopped the diffusion of gas molecule in sizing material, thereby has prolonged its movement path greatly simultaneously; Also reduced the thermal motion of rubber macromolecule simultaneously, reduce diffusion and the permeability coefficient of gas in rubber, made prepared rubber/lamellar silicate nanometer composite material that excellent performance all be arranged at aspects such as winter hardiness, reinforcement, thermal characteristics, barrier property, ventilation property and light color and the transparencys.In addition, because there is surface charge in the phyllosilicate nano lamella, is equivalent to the numerous charged particle that in polymeric matrix, is scattered here and there, thereby makes such material have good antistatic performance.
Chloroprene rubber (CR) is a kind of unsaturated carbon chains rubber that is got by the chloroprene polymerization, per 4 carbon atoms just have a two key on the macromolecular chain, but in fact it does not possess the characteristics of normal unsaturated polymer, and its performance is between saturated and unsaturated polymer.Its structural formula is:
Chloroprene rubber has the good mechanical performance, resistance to fatigue, elasticity and oil-proofness and higher crystallinity preferably, can be applicable to automobile, light industry, building, railroad tie pad, tunnel component, compartment sealing member, mining and shipboard cable sheath, electric wire coatings layer, fuel tanker, printing rubber roll and other industrial or agricultural with sebific duct, adhesive tape, V-type band, places such as band, travelling belt and rubber dam synchronously, and can be used as fabric and be coated with application coating and be extensive use of.
Montmorillonite is a kind of aqueous layer silicate mineral, and its crystal-chemical formula is: E
X(H
2O)
n{ (Al
2-XMg
X)
2[(Si, Al)
4O
10] (OH)
2; its structural unit layer is the TOT type; bigger space makes montmorillonite can adsorb big water gaging and interchangeability positively charged ion between the charged character of montmorillonite and structural sheet thereof; thereby have good adsorption and cation exchange property, this performance is that polymer macromolecule enters the condition that provides the foundation between montmorillonite layer.In order to make polymer molecular chain can be inserted into the sheet interlayer of polynite, generally need be to the montmorillonite processing that organises, go to change the polarity of montmorillonite lamella with organic ion, reduce montmorillonite sheet surfaces energy, make the hydrophilic environments of interlayer be transformed into the lipophilicity environment, thereby help the sheet interlayer that polymkeric substance enters montmorillonite.
The cationic exchange synoptic diagram as shown in Figure 1 between montmorillonite layer.
In recent years, begin the montmorillonite reinforced rubber both at home and abroad and improve aspects such as rubber functional performance and study, but raw material mostly is nonpolar rubber, as ethylene-propylene rubber(EPR) etc., therefore be still waiting to further develop relevant for preparing nano composite material by polar polymer and montmorillonite intercalation.
Look into newly according to domestic and international science and technology and to show (novelty assessment report numbering: 2006110010005), at present existing researchist prepares sovprene/montmorillonite matrix material by blending method, prepare non-exfoliated chloroprene rubber latex/clay nanocomposites by the blend coagulation method, and there is the researchist to prepare a series of chlorinated polymer (sovprenes by melt intercalated method, polyvinyl chloride, chlorinated polyvinyl chloride etc.)/clay nanocomposites, but do not see that the bibliographical information that adopts the polymers soln graft process to prepare exfoliated chloroprene rubber/montmorillonite nano-composite material is arranged both at home and abroad.
The report of at present domestic also not relevant chloroprene rubber/laminated nm-silicate composite material patent exists patent or patent application such as ethylene-propylene rubber(EPR) (CN1683449A), fluid rubber (CN1760301A), terpolymer EP rubber (CN1425712A), rubber (CN1194998C), cis-1,4-polybutadiene rubber (CN1233719C) silicon rubber (CN1233746C)/montmorillonite nano-composite material.By comparison, the selection of different polymer molecular structures, molecular polarity, intercalation method is even and the intercalation method is identical but the factors such as selection of different dispersion all can directly cause intercalation effect and gained nano composite material aspect of performance there are differences.
Summary of the invention
The invention provides a kind of exfoliated chloroprene rubber/montmorillonite nano-composite material and preparation method thereof.Owing to adopted the solvent graft process, make a spot of modified montmorillonite used can being evenly dispersed in the chloroprene rubber matrix.By intercalation, finally obtain the good chloroprene rubber/montmorillonite nano-composite material of mechanical property and antistatic property.
The method for preparing exfoliated chloroprene rubber/montmorillonite nano-composite material may further comprise the steps:
A. purifying montmorillonite and carry out sodium: comprise the montmorillonite of pulverizing is purified by formulated suspension, with containing sodium solution the montmorillonite after purifying is carried out sodium then;
B. montmorillonite is organised: na-montmorillonite is organised with montmorillonite properties-correcting agent;
C. prepare chloroprene rubber rubber/montmorillonite nano-composite material: organic solvent is soaked into and the dispersive montmorillonite that organises mixes with chloroprene rubber rubber in being dissolved in solvent, be warming up to 30-90 ℃ and isothermal reaction, obtain chloroprene rubber rubber/montmorillonite nano-composite material behind the separation solvent;
D. prepare chloroprene rubber/montmorillonite nano-composite material: to chloroprene rubber rubber/montmorillonite nano-composite material plasticate, mixing, the sulfuration, obtain chloroprene rubber/montmorillonite nano-composite material.
The CR that the present invention adopts is the general chloroprene rubber of W type.
The montmorillonite properties-correcting agent that the present invention adopts is the reagent that organises, be preferably quaternary ammonium salt, pyridine derivatives and other cationic surfactant etc., described quaternary ammonium salt is preferably alkylammonium salt etc., for example dodecyl bromination ammonium, octadecyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride (technical grade), stearyl dimethyl benzyl ammonium chloride (technical grade), palmityl trimethyl ammonium chloride (CTAB)), cetyltrimethyl ammonium salt, octadecyl leptodactyline etc.
The solvent that the present invention adopts can be the independent solvent or the mixture of solvent.Under single solvent composition situation, can use ethyl acetate, tetrahydrofuran (THF), chloroform, toluene, dimethylbenzene or chloroform etc.Under multi-solvent component situation, can use the mixture of above-mentioned solvent, perhaps use toluene and vinyl acetate, vinyl acetate and gasoline, toluene and acetic acid, vinyl acetate and gasoline, vinyl acetate and hexanaphthene and gasoline, vinyl acetate and acetone and gasoline, or the like.
40-90h is carried out in isothermal reaction among the step C.
The vulcanizing agent that the present invention adopts is a metal oxide, as zinc oxide, magnesium oxide, silver suboxide etc.Add vulcanization aid when mixing, described vulcanization aid is preferably stearic acid, antioxidant D or white carbon black etc., and described antioxidant D is a nonox.
In a word, the chloroprene rubber that makes by the inventive method with the montmorillonite modification, it is chloroprene rubber/montmorillonite nano-composite material, its mechanical property is greatly increased, antistatic property also obtains raising to a certain degree, so chloroprene rubber/montmorillonite nano-composite material will have Application Areas widely than general chloroprene rubber.
Description of drawings
Fig. 1: cationic exchange synoptic diagram between montmorillonite layer.
Fig. 2: the XRD figure spectrum of sample, wherein, (a) O-MMT; (b) CR rubber/OMMT; (c) CR.
Fig. 3: the XRD figure spectrum of chloroprene rubber/montmorillonite nano-composite material, wherein, (a) O-MMT; (b) CR; (c) CR/OMMT.
Fig. 4: the TEM collection of illustrative plates of sulfuration chloroprene rubber/montmorillonite nano-composite material sample.
Fig. 5: the TEM collection of illustrative plates of sulfuration chloroprene rubber/montmorillonite nano-composite material sample.
Embodiment
Particularly, according to the present invention, the method for preparing exfoliated chloroprene rubber/montmorillonite nano-composite material may further comprise the steps:
1. purifying montmorillonite and carry out sodium:
(1) purification of montmorillonite
1. with ball mill original montmorillonoid soil is pulverized, crossed 200 mesh sieves, get montmorillonite powder;
2. take by weighing the 80g montmorillonite and be dissolved in the 8L distilled water and (use barreled), the electricity consumption agitator stirred 20 minutes, and montmorillonite is made into the suspension that " concentration " is no more than 10g/L, continued to leave standstill the part of taking out d＜10cm with siphon pipe under room temperature state 8 hours;
3. get upper strata 10cm suspension liquid, centrifugal, vacuum-drying (70 ℃) gets the redistilled calcium base montmorillonite;
4. Sheng Xia part adds distilled water again, volume is returned to continue behind the original volume to stir 20 minutes, makes not " taking apart " and the residual particle greater than 2um disperses, after 8 hours again with it taking-up.So repeatedly several times, till the suspension of gained is relatively clarified after remainder adds distilled water again.
(2) sodium of montmorillonite:
1. configuration concentration is the NaCl solution of 1mol/L, is added in the montmorillonite after the purification, makes it abundant hydration swelling;
2. measure pH value with pH meter, and is 6, left standstill again 12 hours after stirring for some time then with the pH value of HCl and NaOH accent solution;
3. supernatant liquid is outwelled, repeating step 1., 2.;
4. adding distilled water in through the precipitation that obtains after the above-mentioned steps stirs and eccentric cleaning;
5. clean to solution and use AgNO
3Detect no Cl
-Till;
6. the good montmorillonite of sodium is placed baking oven,, grind standby 60 ℃ of oven dry.
2. organising of montmorillonite:
After being dispersed in na-montmorillonite in the deionized water, allow it mix, stir with CTAB (hexadecyl trimethyl ammonium bromide): HCl (1: 1) solution, be warming up to 70 ℃, in water-bath, be incubated 6h, centrifuging, with deionized water thorough washing precipitation, until the no Br of check
-Till, in 80 ℃ of loft drier, carry out drying, standby after grinding.
3. the preparation of chloroprene rubber rubber/montmorillonite nano-composite material:
Fully soak into the organic montmorillonite of above step gained with organic solvent, under magnetic agitation, be allowed to condition at homodisperse in the organic solvent (A liquid);
Fully dissolve the neoprene rubber raw rubber with solvent;
Under agitation, A liquid is poured in the chloroprene rubber rubber solution, made its thorough mixing, be warming up to 30-90 ℃ and isothermal reaction 40-90h;
With separated from solvent, thereby obtain chloroprene rubber rubber/montmorillonite nano-composite material.
4. the preparation of chloroprene rubber/montmorillonite nano-composite material:
Plasticate, mixing: at room temperature, use mixing roll (open), chloroprene rubber rubber/montmorillonite nano-composite material plasticated and mixing, the sizing material of the chloroprene rubber rubber/montmorillonite nano-composite material that obtains mixing with vulcanization aid.Its technology is with reference to the complete processing (seeing " modern rubber technology " Sinopec press, the Yang Qingzhi chief editor) of general chloroprene rubber rubber;
Sulfuration: with reference to standard GB 6038-1993, use vulcanizing press,, thereby obtain chloroprene rubber/montmorillonite nano-composite material with chloroprene rubber rubber/montmorillonite nano-composite material sulfuration.
At first, with XRD the chloroprene rubber rubber/montmorillonite nano-composite material that makes according to the present invention is carried out analysis and characterization, the results are shown in Figure 2, among Fig. 2, figure line b is the XRD figure of chloroprene rubber rubber/montmorillonite nano-composite material.This figure shows that the characteristic peak of 2 θ=4.85 in the figure line that organises disappears, d
001Value is by d
001=2.135nm changes infinity into, illustrates that there is not orderly lattice arrangement in the vermiculite lamella, and lamella is by strip off, and is dispersed in the chloroprene rubber matrix, has obtained chloroprene rubber rubber/montmorillonite nano-composite material.
By XRD and transmission electron microscope the chloroprene rubber/montmorillonite nano-composite material that makes according to the present invention is carried out analysis and characterization.The results are shown in Figure 3, Fig. 4, Fig. 5.
Embodiment
Embodiment 1:
With 40ml toluene the 6g organic montmorillonite is fully soaked into, montmorillonite is dispersed in is A liquid in the solvent.It is B liquid that 100g chloroprene rubber rubber is dissolved in the 150ml toluene solvant.A, B liquid are mixed, stir, heating in water bath to 95 ℃, constant temperature, stirring, back flow reaction 50h, the heating and separating solvent obtains chloroprene rubber rubber/montmorillonite nano-composite material.This matrix material is according to the prescription shown in the table 1, adopt refining glue, vulcanization process and the technology of general chloroprene rubber to be prepared processing (referring to " modern rubber technology ", Sinopec press, the Yang Qingzhi chief editor), obtain chloroprene rubber/montmorillonite nano-composite material.
Its performance is referring to table 2, table 3.
Table 1: sulfurizing formula
Embodiment 2:
With the 50ml tetrahydrofuran (THF) 4g organic montmorillonite is fully soaked into, under magnetic agitation, allow montmorillonite be dispersed in the solvent, as A liquid.100g chloroprene rubber rubber is dissolved in the 200ml toluene solvant, as B liquid.
A, B liquid are mixed, stir, heating in water bath to 55 ℃, constant temperature stirs, back flow reaction 58h, the heating and separating solvent obtains chloroprene rubber rubber/montmorillonite nano-composite material.This matrix material is according to the prescription shown in the table 1, adopt refining glue, vulcanization process and the technology of general chloroprene rubber to be prepared processing (referring to " modern rubber technology ", Sinopec press, the Yang Qingzhi chief editor), obtain chloroprene rubber/montmorillonite nano-composite material.Its performance is referring to table 2, table 3.
Embodiment 3:
With the 40ml tetrahydrofuran (THF) 2～15g organic montmorillonite is fully soaked into, under magnetic agitation, allow montmorillonite be dispersed in the solvent, as A liquid.100g chloroprene rubber rubber is dissolved in the 210ml toluene solvant, as B liquid.
A, B liquid are mixed, stir, heating in water bath to 60 ℃, constant temperature stirs, back flow reaction 50h, the heating and separating solvent obtains chloroprene rubber rubber/montmorillonite nano-composite material.This matrix material is according to the prescription shown in the table 1, adopt refining glue, vulcanization process and the technology of general chloroprene rubber to be prepared processing (referring to " modern rubber technology ", Sinopec press, the Yang Qingzhi chief editor), obtain chloroprene rubber/montmorillonite nano-composite material.Its performance is referring to table 2, table 3.
The test implementation example
The chloroprene rubber/montmorillonite nano-composite material performance
(1) mechanical property
Measure the mechanical property of prepared chloroprene rubber/montmorillonite nano-composite material by the routine measurement method: shore a hardness, tensile strength, 300% stress at definite elongation, 500% stress at definite elongation, setafter break, the results are shown in Table 2.From the data results of table 2 as can be known, described mechanical property is all improved largely, and wherein 300% stress at definite elongation, the more conventional chloroprene rubber material of 500% stress at definite elongation double.
Table 2: chloroprene rubber/montmorillonite nano-composite material mechanical property
By the data of table 2 as can be known, the mechanical property of chloroprene rubber/montmorillonite nano-composite material is improved, all be improved as performances such as shore a hardness, 300%, 500% stress at definite elongation, setafter breaks, its reason may be that the montmorillonite nano fragment is dispersed in the rubber matrix uniformly, twine with rubber macromolecule, be equivalent to increase the cross-linking set between rubber molecule, intermolecular under external force extent of migration reduces, elasticity improves, therefore setafter break reduces, and stress at definite elongation increases; Because the montmorillonite of inorganic phase is to be present in the polymeric matrix with the random form of nanometer lamella, make the hardness of this matrix material also be improved simultaneously.
(2) antistatic property test
Table 3: chloroprene rubber/montmorillonite nano-composite material resistance value
Table 3 is the result show, the resistivity of chloroprene rubber/montmorillonite nano-composite material has decline to a certain degree, the particularly volume specific resistance order of magnitude that descended, and illustrates that the antistatic property of this material is good.
Claims (11)
1. method for preparing exfoliated chloroprene rubber/montmorillonite nano-composite material may further comprise the steps:
A. purifying montmorillonite and carry out sodium;
B. montmorillonite is organised;
C. prepare chloroprene rubber rubber/montmorillonite nano-composite material: soak into and the dispersive montmorillonite that organises mixes with chloroprene rubber rubber in being dissolved in organic solvent with organic solvent, be warming up to 30～90 ℃ and isothermal reaction, obtain chloroprene rubber rubber/montmorillonite nano-composite material after separating solvent, described chloroprene rubber is a W type chloroprene rubber; Described organic solvent is the independent solvent or the mixture of solvent; Under single solvent composition situation, use ethyl acetate, tetrahydrofuran (THF), chloroform, toluene or dimethylbenzene; Under the solvent mixture situation, use the mixture of above-mentioned solvent, perhaps use toluene and vinyl acetate, vinyl acetate and gasoline, toluene and vinyl acetate and gasoline, vinyl acetate and hexanaphthene and gasoline, vinyl acetate and acetone and gasoline;
D. prepare chloroprene rubber/montmorillonite nano-composite material: to chloroprene rubber rubber/montmorillonite nano-composite material plasticate, mixing and the sulfuration, obtain chloroprene rubber/montmorillonite nano-composite material;
In the steps A, the montmorillonite of pulverizing is purified by formulated suspension, with containing sodium solution the montmorillonite after purifying is carried out sodium then.
2. according to the method for claim 1, it is characterized in that, among the step B, na-montmorillonite is organised with montmorillonite properties-correcting agent.
3. according to the method for claim 2, it is characterized in that described montmorillonite properties-correcting agent is quaternary ammonium salt, pyridine derivatives or cationic surfactant.
4. according to the method for claim 3, it is characterized in that described quaternary ammonium salt is an alkylammonium salt.
5. according to the method for claim 3, it is characterized in that described quaternary ammonium salt is dodecyl bromination ammonium, octadecyl ammonium chloride, technical grade dodecyl benzyl dimethyl ammonium chloride, technical grade stearyl dimethyl benzyl ammonium chloride or palmityl trimethyl ammonium chloride.
6. according to the method for claim 1, it is characterized in that 40～90h is carried out in the isothermal reaction among the step C.
7. according to the method for claim 1, it is characterized in that the vulcanizing agent that uses among the step D is metal oxide.
8. according to the method for claim 7, it is characterized in that described metal oxide is zinc oxide, magnesium oxide or silver suboxide.
9. according to the method for claim 1, it is characterized in that, add vulcanization aid when mixing.
10. according to the method for claim 9, it is characterized in that described vulcanization aid is a stearic acid.
11. the exfoliated chloroprene rubber/montmorillonite nano-composite material that makes according to the method for one of claim 1-10.
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