CN100545199C - A kind of preparation method of brominated butyl rubber/Nano composite material of montmorillonite - Google Patents
A kind of preparation method of brominated butyl rubber/Nano composite material of montmorillonite Download PDFInfo
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- CN100545199C CN100545199C CNB2007100380693A CN200710038069A CN100545199C CN 100545199 C CN100545199 C CN 100545199C CN B2007100380693 A CNB2007100380693 A CN B2007100380693A CN 200710038069 A CN200710038069 A CN 200710038069A CN 100545199 C CN100545199 C CN 100545199C
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Abstract
The invention discloses a kind of preparation method of brominated butyl rubber/Nano composite material of montmorillonite.At first, mixing with carrying out in brominated butyl rubber, polynite, intercalator and the coupling agent adding Banbury mixer under 10-80 ℃ processing temperature, obtain intercal type brominated butyl rubber/polynite master batch; Add vulcanization leveller, promotor and vulcanizing agent then.In this process, intercalator and butyl rubber bromide xanthan molecule will take place in-situ inserted, make the interlamellar spacing of polynite that tangible expansion be arranged, and obtain intercal type brominated butyl rubber/polynite rubber unvulcanizate.At last rubber unvulcanizate is vulcanized under 150-190 ℃, the interlamellar spacing of the polynite behind over cure further enlarges, thereby obtains a kind of brominated butyl rubber/Nano composite material of montmorillonite of intercal type.Preparation method provided by the invention and complete processing are simple, and preparation cost is low, need not before mixing polynite to be carried out organically-modified, and can improve the mechanical property and the chemical resistance of brominated butyl rubber.
Description
Technical field:
The present invention relates to a kind of preparation method's of high molecule nano composite material, particularly a kind of brominated butyl rubber/Nano composite material of montmorillonite preparation method.
Background technology:
Isoprene-isobutylene rubber is the multipolymer (being called for short IIR) of iso-butylene and isoprene.Be to introduce unsaturated link(age) with the purpose of isoprene copolymer to polymkeric substance, so that available sulfur vulcanization, thereby the versatility of raising isoprene-isobutylene rubber.Isoprene-isobutylene rubber is widely used as the inner tube of a tyre, air cushion, wear ring.
Brominated butyl rubber (BIIR) is that isoprene-isobutylene rubber and bromo element react and make, and brominated butyl rubber is a kind of active elastomerics that has.Under situation without any promotor or promoting agent, available Sulfur individual curing, also available aminated compounds sulfuration.The C=C key helps the vulcanization crosslinking of rubber, and in addition, the activity of C-Br key is also very big, because the electronegativity of Br in the side chain is disperseed the electronics of C=C key, has improved vulcanization rate and efficient.Brominated butyl rubber has been except having kept the original low gas permeability of isoprene-isobutylene rubber, high decay property, and ageing resistance, gasproof marquis property, outside the characteristics such as ozone resistance and chemical proofing, also increased the not available following characteristic of conventional butyl rubbers: vulcanization rate is fast; With natural picture glue, the compatibility performance of styrene-butadiene rubber(SBR) is good; With natural rubber, the adhesiveproperties of styrene-butadiene rubber(SBR) improves; Can be separately with zinc oxide sulfuration, vulcanization variation; Better heat-resisting is arranged.Just because of the bromination butyl has so many advantage, so it substitutes conventional butyl rubbers just step by step in multiple Application Areas, as tire, the heat-resisting inner tube of a tyre, pressure vessels for the chemical industry lining, Industrial products such as medicine bottle block.
Polynite (MMT) is a kind of particulate clay mineral of lamellar aluminosilicate.At present, the preparation matrix material is one of key areas of investigation of materials.Domestic and international research Showed Very Brisk: for example to polynite/polymer composites, world rubber industry, 2006, utilize melting intercalation method prepare nano imvite/SBR matrix material at 33 (4): 13, the modern plastics processed and applied, adopt expressing technique, melting intercalation method prepared high-impact polystyrene/organo montmorillonite (HIPS/OMMT) matrix material, and preferably flame retardant properties arranged at 2006,18 (1): 15; Polymer, 2005, the 46:12430-12439 utilization melt extrudes polymerization and has prepared poly-succinic/adipate diol ester (PBSA)/Nano composite material of montmorillonite, and studied its structure, visco-elasticity and correlated performance, show to add that the mechanical property of PBSA is significantly improved after the polynite, tensile strength and elongation at break etc. has remarkable increase.
At present, the high polymer nano matrix material of having prepared, its preparation method mainly contains intercalation compounding, sol-gel method, blending method etc.Intercalation compounding is the novel method of preparation high-performance polymer/Nano composite material of montmorillonite, also is the focus of present material scientific domain research.Wherein melting intercalation method is the polynite after organically-modified and rubber to be carried out mechanical blending prepare nano composite material under higher temperature, and its technical matters is simple, and is easy to control, is easy to realize suitability for industrialized production.In order to improve the consistency of polynite and rubber, make polymkeric substance be easy to intercalation in montmorillonite layer, before preparing nano composite polymer-montmorillonoid material, melt intercalated method with intercalator organically-modified pre-treatment is carried out in polynite usually.
Summary of the invention:
The objective of the invention is to utilize a kind of new simple and easy to do and method that cost is low to prepare brominated butyl rubber/Nano composite material of montmorillonite, thereby improve brominated butyl rubber mechanical properties of vulcanizate and chemical resistance.This method need not before melt blending is carried out in rubber and polynite polynite to be carried out organically-modified, but obtains brominated butyl rubber/Nano composite material of montmorillonite by direct blended rubber, polynite and intercalator.
The preparation method of a kind of brominated butyl rubber/Nano composite material of montmorillonite of the present invention is as follows, below all represents with mass parts:
100 parts brominated butyl rubbers are joined in the Banbury mixer, under 10-80 ℃ processing temperature and 30-60rpm rotor speed, after mixing 5-15 minute, under identical processing temperature and rotor speed condition, add 1-3 part two-[γ-(triethoxysilicane) propyl group] tetrasulfide, the intercalator of the polynite of 5-50 part and 10-30 part blend 10-30 minute, obtains intercal type brominated butyl rubber/polynite master batch; Then with intercal type brominated butyl rubber/polynite master batch in Banbury mixer, add vulcanization leveller, 0.3-5 part promotor and 0.3-4 part Sulfur of 1-10 part and mixing 5-10 minute under 10-80 ℃ processing temperature and the 30-60rpm rotor speed, promptly obtain intercal type brominated butyl rubber/polynite rubber unvulcanizate; At last intercal type brominated butyl rubber/polynite rubber unvulcanizate is vulcanized under 150-190 ℃, sulfurizing time is 6-20 minute, and sulfide stress is 5-20MPa, obtains a kind of brominated butyl rubber/Nano composite material of montmorillonite.
The crude rubber Mooney viscosity of the brominated butyl rubber that the present invention uses is ML
1+4 125 ℃=27-36.
The polynite that the present invention uses is a kind of lamellated silico-aluminate, and its cation exchange capacity is 50-200meq/100g.
The intercalator that the present invention uses is octadecyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride or octadecyl double hydroxyethyl ammonio methacrylate.
The vulcanization leveller that the present invention uses is zinc oxide, magnesium oxide and stearic acid, and its mol ratio is 1: 1: 1 to 6: 5: 3; Promotor is 2-benzothiazolyl mercaptan and ziram, and its mol ratio is 1: 1 to 3: 1.
The present invention directly carries out melt blending with polynite and intercalator and brominated butyl rubber, utilization intercalator under solid-state and liquid state all can carry out the principle of intercalation by cation exchange reaction to polynite, make intercalator and butyl rubber bromide xanthan molecule under the effect in heat and shear field, realize intercalation, obtain having the brominated butyl rubber/polynite master batch of intercalation configuration.Add vulcanization leveller, promotor and vulcanizing agent to this master batch at low temperatures again, behind over cure, obtain having at last the brominated butyl rubber/Nano composite material of montmorillonite of intercalation effect.
Present method complete processing is simple, not be used in polynite and brominated butyl rubber and carries out earlier organosilicon prepolymer being carried out in polynite before mixing and handle, and reduce production costs, and this method can effectively improve the interlamellar spacing and the dispersion of polynite in rubber of polynite.By the blending ratio of polynite and intercalator and the consumption of polynite, can optimize the mechanical property of matrix material, tensile strength improves 50%-65% than the pure glue cross-linked rubber of brominated butyl rubber, tear strength improves 1-2 doubly, thereby obtains the brominated butyl rubber/Nano composite material of montmorillonite of excellent mechanical performances and better chemical resistance.With pure brominated butyl rubber and compound the comparing of brominated butyl rubber/montmorillonite-based nano that do not add intercalator, the mechanical property and the chemical resistance of this nano composite material improve a lot.
Description of drawings:
Fig. 1 is X-ray diffraction (XRD) spectrogram of embodiment 3-6 and Comparative Examples 2.
Embodiment:
Following examples are to further specify of the present invention, but not limit the scope of the invention.
The brominated butyl rubber trade mark that uses in following examples is Polysar 2030, German Bayer AG, ML
1+4 125 ℃=27-36
The polynite of using in following examples, its cation exchange capacity (CEC) is 90meq/100g, the original layers spacing of polynite is 1.51nm.
The intercalator that uses in following examples is octadecyl trimethyl ammonium chloride (OTAC), stearyl dimethyl benzyl ammonium chloride (ODBAC) or octadecyl double hydroxyethyl ammonio methacrylate (ODHAC).
The vulcanization leveller that uses in following examples is zinc oxide, magnesium oxide and stearic acid, and promotor is captax and promotor PZ, and vulcanizing agent is a Sulfur, and coupling agent is two-[γ-(triethoxysilicane) propyl group] tetrasulfide.
Embodiment 1-6: press the prescription in the table 1, brominated butyl rubber is joined in the Banbury mixer, under room temperature and 32rpm rotor speed, after mixing 10 minutes, under identical processing temperature and rotor speed condition, add two-[γ-(triethoxysilicane) propyl group] tetrasulfide, polynite and intercalator, blend 20 minutes obtains intercal type brominated butyl rubber/polynite master batch; Then above-mentioned master batch is added zinc oxide, magnesium oxide, stearic acid according to prescription under room temperature and 32rpm rotor speed, 2-benzothiazolyl mercaptan (captax), ziram (promotor PZ), mixing 5 minutes of Sulfur promptly obtains intercal type brominated butyl rubber/polynite rubber unvulcanizate; With the sulfurizing time (as shown in table 1) that the intercal type brominated butyl rubber/the polynite rubber unvulcanizate records according to vulkameter, vulcanize under 170 ℃ of curing temperatures at last, sulfide stress is 10MPa, obtains brominated butyl rubber/Nano composite material of montmorillonite.
Above-mentioned brominated butyl rubber/the Nano composite material of montmorillonite that obtains is made the thick dumbbell shape sample of 2mm, according to GB528-92 standard test mechanical properties of vulcanizate.Fig. 1 measures the variation of cheating engaging layer spacing in brominated butyl rubber/Nano composite material of montmorillonite for utilizing X-ray diffractometer (XRD), and the wavelength of X ray is 0.1542nm, tube voltage 40KV, tube current 20mA.The scanning angle scope is 1-10 °, and sweep velocity is 1 °/min.Square test piece with the above-mentioned brominated butyl rubber/Nano composite material of montmorillonite that obtains is made 25 * 25mm is soaked in 25%NaOH solution, 25%HCl solution and 25%H respectively
2SO
4Solution takes out behind the certain hour, blots surface solvent, weighs, and measures the chemical resistance of matrix material, with the weight rate SR=(W of sample
2-W
1)/W1 * 100% (wherein, W
1And W
2Be respectively the weight of sample immersion front and back) expression.Above result all lists in the table 1.
Comparative Examples 1-2: according to the prescription in the table 1, its complete processing is identical with embodiment 1-6 with test condition with method, and the results are shown in Table 1.
The prescription of table 1 brominated butyl rubber/montmorillonite composite material, mechanical property and solvent absorbing rate
Table 1 has been investigated intercalator OTAC consumption to composite structure and Effect on Performance.Fig. 1 as can be seen, when no intercalator OTAC exists, the interlamellar spacing of polynite is compared with polynite original layers spacing and is not enlarged in brominated butyl rubber/montmorillonite composite material, after adding intercalator OTAC, the interlamellar spacing of polynite has tangible increase in brominated butyl rubber/montmorillonite composite material, has promptly formed the brominated butyl rubber/Nano composite material of montmorillonite of intercal type.
In table 1, can find out, the tensile strength of brominated butyl rubber/montmorillonite composite material behind the adding intercalator OTAC, hardness and tear strength are all apparently higher than brominated butyl rubber/montmorillonite composite material that does not add intercalator OTAC and the pure glue cross-linked rubber of brominated butyl rubber, and elongation at break then is lower than brominated butyl rubber/montmorillonite composite material and the pure glue cross-linked rubber of brominated butyl rubber that does not add intercalator OTAC.When polynite and intercalator OTAC consumption mol ratio are 1.5/1 left and right sides, comprehensive mechanical property the best.
Embodiment 7-10: press prescription in the table 2, brominated butyl rubber is joined in the Banbury mixer, under room temperature and 32rpm rotor speed, after mixing 10 minutes, under identical processing temperature and rotor speed condition, add two-[γ-(triethoxysilicane) propyl group] tetrasulfide, polynite, intercalator OTAC blend 20 minutes obtain intercal type brominated butyl rubber/polynite master batch; Then above-mentioned master batch is added zinc oxide according to prescription under room temperature and 32rpm rotor speed, magnesium oxide, stearic acid, captax, promotor PZ, mixing 5 minutes of Sulfur promptly obtains intercal type brominated butyl rubber/polynite rubber unvulcanizate; With the sulfurizing time (as shown in table 2) that the intercal type brominated butyl rubber/the polynite rubber unvulcanizate records according to vulkameter, vulcanize under 170 ℃ of curing temperatures at last, sulfide stress is 10MPa, obtains brominated butyl rubber/Nano composite material of montmorillonite.
Above-mentioned brominated butyl rubber/the Nano composite material of montmorillonite that obtains is made the thick dumbbell shape sample of 2mm, and Mechanics Performance Testing and XRD data analysis and chemical-resistant resistance are analyzed the same, the results are shown in Table 2.
As seen from Table 2, fixedly during mole dosage such as polynite and intercalator OTAC, increase along with the polynite consumption, when the tensile strength of brominated butyl rubber/montmorillonite composite material is the 20phr left and right sides at the polynite consumption, reach a maximum value, tear strength is overall increase trend along with the increase of polynite consumption.
The prescription of table 2 brominated butyl rubber/montmorillonite composite material, mechanical property and solvent absorbing rate
Embodiment 11-12: the consumption of polynite and intercalator was fixed as mol ratio 1: 1, and more different then intercalators are to brominated butyl rubber/montmorillonite composite material structure and Effect on Performance.According to the prescription in the table 3, brominated butyl rubber is joined in the Banbury mixer, under room temperature and 120rpm rotor speed, after mixing 10 minutes, under identical processing temperature and rotor speed condition, add Si-69, polynite and intercalator, blend 20 minutes obtains intercal type brominated butyl rubber/polynite master batch; Then above-mentioned master batch is added zinc oxide according to prescription under room temperature and 120rpm rotor speed, magnesium oxide, stearic acid, captax, promotor PZ, mixing 5 minutes of Sulfur promptly obtains intercal type brominated butyl rubber/polynite rubber unvulcanizate; With the sulfurizing time (as shown in table 3) that the intercal type brominated butyl rubber/the polynite rubber unvulcanizate records according to vulkameter, vulcanize under 170 ℃ of curing temperatures at last, sulfide stress is 10MPa, obtains brominated butyl rubber/Nano composite material of montmorillonite.
Above-mentioned brominated butyl rubber/the Nano composite material of montmorillonite that obtains is made the thick dumbbell shape sample of 2mm, and Mechanics Performance Testing and XRD data analysis are the same, the results are shown in Table 3.
The different intercalators of table 3 are to the influence of the mechanical property and the solvent absorbing rate of brominated butyl rubber/montmorillonite composite material
Draw from table 3, the adding of different intercalators can have raising in various degree to the mechanical energy of brominated butyl rubber/montmorillonite composite material, and wherein the reinforcement over-all properties of OTAC is better.And the big I by the cheating engaging layer spacing finds out that the intercalation effect of intercalator OTAC is best, enlarge when making the interlamellar spacing of polynite more originally without intercalator a lot, thereby further mention its mechanical property and chemical resistance.
Claims (1)
1. the preparation method of a brominated butyl rubber/Nano composite material of montmorillonite is characterized in that the preparation method is as follows, below all represents with mass parts:
100 parts brominated butyl rubbers are joined in the Banbury mixer, under room temperature and 32rpm rotor speed, after mixing 10 minutes, under identical processing temperature and rotor speed condition, add 20 parts polynite, 1.4,2.8,4.3,5.7,7.1 or 8.6 parts octadecyl trimethyl ammonium chloride and 3 parts two-[γ-(triethoxysilicane) propyl group] tetrasulfide blend 20 minutes, obtain intercal type brominated butyl rubber/polynite master batch; Then intercal type brominated butyl rubber/polynite master batch is added 5 parts of zinc oxide according to prescription under room temperature and 32rpm rotor speed, 4 parts of magnesium oxide and 2 parts of stearic acid, 0.6 part 2-benzothiazolyl mercaptan and 1.5 parts of zirams and 1.5 parts of sulphur, mixing 5 minutes, promptly obtain intercal type brominated butyl rubber/polynite rubber unvulcanizate; At last intercal type brominated butyl rubber/polynite rubber unvulcanizate is vulcanized, curing temperature is 170 ℃, and sulfide stress is 10MPa, at the octadecyl trimethyl ammonium chloride consumption is 1.4,2.8,4.3,5.7 in the time of 7.1 or 8.6 parts, corresponding with it sulfurizing time is respectively 15.8,15.4,14,12.1,11.2 or 9.4 minutes, behind over cure, obtain brominated butyl rubber/Nano composite material of montmorillonite, wherein: the trade mark of brominated butyl rubber is Polysar 2030, Germany Bayer AG produces, ML
1+4 125 ℃=27-36; The cation exchange capacity of polynite is 90meq/100g, and the original layers spacing is 1.51nm.
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| CN103159990B (en) * | 2011-12-08 | 2014-12-31 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN103159994B (en) * | 2011-12-08 | 2015-02-11 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN106061890A (en) * | 2014-02-28 | 2016-10-26 | 埃克森美孚化学专利公司 | Nanocomposite mooney viscosity stability |
| CN104788053B (en) * | 2015-03-27 | 2017-06-23 | 山东科技大学 | A kind of experimental technique for preparing rubber grain concrete |
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Non-Patent Citations (4)
| Title |
|---|
| New Method for Preparing PolybutadieneRubber/ClayComposites. Shaohui Wang, Yong Zhang, Zonglin Peng, Yinxi Zhang.Journal of Applied Polymer Science,Vol.Vol.98 . 2005 |
| New Method for Preparing PolybutadieneRubber/ClayComposites. Shaohui Wang, Yong Zhang, Zonglin Peng, Yinxi Zhang.Journal of Applied Polymer Science,Vol.Vol.98 . 2005 * |
| OMMT/IIR纳米复合材料结构与性能的研究. 梁玉蓉，姜海鹏，王益庆，李昭，张立群.橡胶工业，第52卷第5期. 2005 |
| OMMT/IIR纳米复合材料结构与性能的研究. 梁玉蓉，姜海鹏，王益庆，李昭，张立群.橡胶工业，第52卷第5期. 2005 * |
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