CN1683449A - Process for preparing ethylene-propylene rubber/montmorillonite nano composite material - Google Patents
Process for preparing ethylene-propylene rubber/montmorillonite nano composite material Download PDFInfo
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- CN1683449A CN1683449A CN 200510024420 CN200510024420A CN1683449A CN 1683449 A CN1683449 A CN 1683449A CN 200510024420 CN200510024420 CN 200510024420 CN 200510024420 A CN200510024420 A CN 200510024420A CN 1683449 A CN1683449 A CN 1683449A
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- propylene rubber
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- 229920000181 Ethylene propylene rubber Polymers 0.000 title claims abstract description 107
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 71
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000002114 nanocomposite Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000138 intercalating agent Substances 0.000 claims description 30
- 229920001971 elastomer Polymers 0.000 claims description 24
- 239000005060 rubber Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 238000005341 cation exchange Methods 0.000 claims description 5
- 239000003760 tallow Substances 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- VUIOJLCUVZTATE-UHFFFAOYSA-N [Cl-].C[NH+](C)C.C(CCCCCCCCCCCCCCCCC)[NH3+].[Cl-] Chemical compound [Cl-].C[NH+](C)C.C(CCCCCCCCCCCCCCCCC)[NH3+].[Cl-] VUIOJLCUVZTATE-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005870 Ziram Substances 0.000 claims description 2
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical group [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 2
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- 230000000052 comparative effect Effects 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- -1 alkyl quaternary ammonium salts Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001149 thermolysis Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002449 FKM Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 102100035115 Testin Human genes 0.000 description 1
- 101710070533 Testin Proteins 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 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 1
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- 230000004580 weight loss Effects 0.000 description 1
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Abstract
The present invention provides the preparation process of composite nanometer ethylene-propylene rubber/montmorillonite material. The composite nanometer ethylene-propylene rubber/montmorillonite material consists of ethylene-propylene rubber, montmorillonite, interclation agent, sulfurizing active agent, promoter and sulfurizing agent. The preparation process includes mixing ethylene-propylene rubber, montmorillonite and interclation agent in banburying machine at 30-120 deg.c; shearing and mixing with sulfurizing active agent, promoter and sulfurizing agent in banburying machine at 30-100 deg.c; and finally sulfuring the mixture at 140-200 deg.c to obtain the interclated composite nanometer ethylene-propylene rubber/montmorillonite material. The present invention has simple processing, no need of organically modifying montmorillonite before mixture and greatly raised mechanical performance and heat stability.
Description
Technical field:
The present invention relates to a kind of preparation method's of high molecule nano composite material, particularly a kind of ethylene-propylene rubber/montmorillonite nano composite material preparation method.
Background technology:
Ethylene-propylene rubber(EPR) (EPDM) is a kind of main chain saturated general purpose synthetic rubber fully, because it has excellent ozone resistance, chemical stability and electrical insulation capability and higher thermostability, heat-resisting and Weather performance, so be mainly used in products such as making tire, travelling belt, electric wire, corrosion protective lining, water-proof material, door and window sealing strip and household electrical appliances accessory.
Polynite (MMT) is the very abundant a kind of mineral fillers of China's standing stock, begins both at home and abroad in recent years the polynite reinforced rubber is studied.It has been generally acknowledged that the consistency of nonpolar ethylene-propylene rubber(EPR) and polar polynite is relatively poor, be difficult to prepare the finely disseminated nano composite material of polynite.Polymer, 2002,43:2185-2189 utilizes melt intercalated method to use the polynite and the special vulcanization accelerator of octadecylamine modification to prepare exfoliated ethylene-propylene rubber/montmorillonite nano composite material, compare with the pure glue cross-linked rubber of ethylene-propylene rubber(EPR), the mechanical property of nano composite material significantly improves, and air penetrability descends about 30%.Polymer intemational, 2002,51:319-324 utilizes melt intercalated method to use the polynite of octadecylamine modification and the ethylene-propylene rubber/montmorillonite nano composite material that Liquid Ethylene Propylene Methylene has prepared intercal type.The use of Liquid Ethylene Propylene Methylene has increased the consistency of ethylene-propylene rubber(EPR) and polynite, and the interlamellar spacing of polynite is further increased.The tensile strength of nano composite material, tear strength and tensile yield all significantly improve, and air penetrability obviously reduces simultaneously.We are (the Polymer testin of research group, 2004,23:217-223) adopt the polynite and the promotor PZ of two (2-hydroxyethyl) the cocounut oil alkyl quaternary ammonium salts modifications of methyl to prepare exfoliated ethylene-propylene rubber/montmorillonite nano composite material by melt intercalated method with high tensile, tear strength and tensile yield.Nano composite polymer-montmorillonoid material has multiple preparation method, and wherein the macromole melt intercalated method has simple and easy to doly, need not use solvent, and production cost is lower, more easily realizes advantages such as suitability for industrialized production, thereby more and more causes investigator's concern.In order to improve the consistency of polynite and rubber, make polymkeric substance be easy to the intercalation montmorillonite layer, before preparing nano composite polymer-montmorillonoid material, need carry out in advance organically-modified to polynite with intercalator usually with melt intercalated method.Soon montmorillonite suspension liquid and acidified intercalator aqeous suspension mix 80～90 ℃ of following vigorous stirring, promptly get organo montmorillonite after sieving through filtration, washing, drying and grinding again.For example, United States Patent (USP) 5,840,796 utilize the two quaternary ammonium salt-modified polynites of octadecyl of dimethyl to prepare viton/Nano composite material of montmorillonite by melt intercalated method.
Summary of the invention:
The objective of the invention is to utilize a kind of new method simple and easy to do and with low cost to prepare ethylene-propylene rubber/montmorillonite nano composite material, and significantly improve ethylene-propylene rubber(EPR) mechanical properties of vulcanizate and thermotolerance.This method need not before melt blending is carried out in rubber and polynite polynite to be carried out organically-modified, but obtains ethylene-propylene rubber/montmorillonite nano composite material by direct blended rubber, polynite and intercalator.
The preparation method that the present invention is used for preparing ethylene-propylene rubber/montmorillonite nano composite material is as follows: by weight 100 parts ethylene-propylene rubber(EPR) is joined Banbury mixer, add 1～60 part polynite and 0.5～25 part intercalator then simultaneously, melt blending 5～20min under 30～120 ℃ processing temperatures and 30～150rpm rotor speed obtains intercal type ethylene-propylene rubber/montmorillonite master batch; Then intercal type ethylene-propylene rubber/montmorillonite master batch is added 1～8 part vulcanization leveller, 0.5～5 part of promotor and 0.5～4 part of vulcanizing agent and mixing 5～10min according to prescription under 30～100 ℃ processing temperature and 30～150rpm rotor speed, promptly obtain intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate; At last intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate is vulcanized under 140～200 ℃, curing time 10～30min, sulfide stress 5～10MPa promptly obtains ethylene-propylene rubber/montmorillonite nano composite material after sulfuration.
The ethylene-propylene rubber(EPR) that the present invention uses is that a kind of ethylene content is that 70%, the three monomer is 4.9% for ethylidene norbornene content, and crude rubber Mooney viscosity is
Ethylene propylene copolymer.
The polynite that the present invention uses is the nonmetal stratiform silicate of a class, and its unit cell is made up of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connects by shared Sauerstoffatom between the two, and the montmorillonite layer internal surface has negative charge, interlayer cation such as Na
+, Ca
2+, Mg
2+Be tradable positively charged ion, these positively charged ions can be cemented out by organic ammonium salt positively charged ion etc. by cation exchange reaction.The cation exchange capacity of polynite (CEC) is 50～200meq/100g, is preferably in 70～120meq/100g scope.
The intercalator that the present invention uses is organic uncle's ammonium salt, quaternary ammonium salt (carbon chain lengths is 14～18), as trimethylammonium octadecyl ammonium chloride (1831), two (2-hydroxyethyl) the hydrogenated tallow ammonium chlorides (182H) of methyl, dimethyl stearyl benzyl ammonium chloride (1827), the two hydrogenated-tallow group brometo de amonios (2HT) of dimethyl, trimethylammonium hexadecyl brometo de amonio (1631) and octadecyl ammonium chloride etc.
The vulcanization leveller that the present invention uses is zinc oxide and stearic acid, promotor is ziram (promotor PZ), N-phenylcyclohexane benzothiazolyl sulphenamide (accelerant CZ or CBS), 2-benzothiazolyl mercaptan (captax), dibenzothiazyl disulfide (altax), vulkacit D (vulkacit D PG) or tetramethyl-thiuram disulfide (TM monex TD) etc., vulcanizing agent is a Sulfur, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane or dicumyl peroxide (DCP) etc.
The present invention directly carries out melt blending with polynite and intercalator and ethylene-propylene rubber(EPR), 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 ethylene-propylene rubber(EPR) molecule under the effect in heat and shear field, realize the reaction in intercalation, obtain having the ethylene-propylene rubber/montmorillonite master batch of intercalation configuration.Under lower temperature, in this master batch, add vulcanization leveller, promotor and vulcanizing agent then, behind over cure, obtain having at last the ethylene-propylene rubber/montmorillonite nano composite material of intercalation configuration.
Present method complete processing is simple, saved at polynite and ethylene-propylene rubber(EPR) and carried out pretreated operation being carried out in polynite before mixing, can significantly reduce production costs, and this method can improve the interlamellar spacing and the dispersion of polynite in rubber matrix of polynite effectively.Thereby obtain having the ethylene-propylene rubber/montmorillonite nano composite material of excellent mechanical performances and thermostability.Compare with the ethylene-propylene rubber/montmorillonite matrix material that does not add intercalator with the pure glue cross-linked rubber of ethylene-propylene rubber(EPR), the mechanical property and the thermostability of this nano composite material significantly improve, with the pure glue cross-linked rubber of ethylene-propylene rubber(EPR) mutually the temperature of specific tensile strength, tensile yield, tear strength and thermolysis 50% improve about 350% respectively, 70%, 100% and 20 ℃; With the ethylene-propylene rubber(EPR) cross-linked rubber of filling unmodified polynite mutually the temperature of specific tensile strength, tensile yield, tear strength and thermolysis 50% improve about 100% respectively, 15%, 35% and 15 ℃, and can reach the mechanical property and the thermostability (China Synthetic Rubber Industry of the ethylene-propylene rubber/montmorillonite nano composite material that adopts the organo montmorillonite preparation, 2004,27:157-160; Zheng Hua, Shanghai Communications University's doctorate paper 2004).
Description of drawings:
Fig. 1 is X-ray diffraction (XRD) spectrogram of Comparative Examples 2,3 and embodiment 1～5
Fig. 2 is thermal weight loss (TGA) spectrogram of Comparative Examples 1 and embodiment 1～5
Embodiment:
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
The ethylene-propylene rubber(EPR) that uses in following examples is that a kind of ethylene content is that 70%, the three monomer is 4.9% for ethylidene norbornene content, and crude rubber Mooney viscosity is
Ethylene propylene copolymer.
The polynite of using in following examples is sodium-based montmorillonite, and its cation exchange capacity (CEC) is 90meq/100g, and the original layers spacing of polynite is 1.31nm.
The intercalator that uses in following examples is trimethylammonium octadecyl ammonium chloride (1831), two (2-hydroxyethyl) the hydrogenated tallow ammonium chlorides (182H) of methyl, dimethyl stearyl benzyl ammonium chloride (1827), the two hydrogenated-tallow group brometo de amonios (2HT) of dimethyl, trimethylammonium hexadecyl brometo de amonio (1631).
The vulcanization leveller that uses in following examples is zinc oxide (ZnO) and stearic acid (S.A), and promotor is promotor PZ and captax, and vulcanizing agent is Sulfur (S).
Embodiment 1～5: according to the prescription in the table 1, ethylene-propylene rubber(EPR) is joined in the Banbury mixer, add polynite and corresponding intercalator then simultaneously, melt blending 8min under 70 ℃ processing temperatures and 90rpm rotor speed obtains intercal type ethylene-propylene rubber/montmorillonite master batch; Then above-mentioned sizing material is added zinc oxide under 50 ℃ processing temperature and 60rpm rotor speed, stearic acid, the mixing 6min of promotor and Sulfur promptly obtains intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate; The sulfurizing time (as shown in table 1) that above-mentioned rubber unvulcanizate is recorded according to vulkameter vulcanizes, 175 ℃ of curing temperatures, and pressure 10MPa obtains ethylene-propylene rubber/montmorillonite nano composite material.
The above-mentioned ethylene-propylene rubber/montmorillonite nano composite material that obtains is made the thick dumbbell shape sample of 2mm, according to ASTM D412 standard test mechanical properties of vulcanizate.Fig. 1 utilizes X-ray diffractometer to measure the variation of cheating engaging layer spacing in the ethylene-propylene rubber/montmorillonite matrix material, and the wavelength of X ray is 1.5406Å, tube voltage 40KV tube current 100mA.The scanning angle scope is 1～20 ℃, and sweep velocity is 4 ℃/min.Fig. 2 is a thermal decomposition behavior of investigating the ethylene-propylene rubber(EPR) matrix material of filling polynite with thermogravimetric analyzer; the scanning temperature range is from room temperature to 800 ℃; nitrogen protection, 20 ℃/min of temperature rise rate, the temperature (T of investigation ethylene-propylene rubber/montmorillonite matrix material thermolysis 50%
50) and thermolysis peak temperature (T
p) variation, above result all lists in the table 1.
Table 1 has been investigated different intercalators to composite structure and Effect on Performance.The amount ratio of polynite and intercalator is with Na contained in the polynite interlamination region
+Representing with the mol ratio of intercalator, is 1/0.85 here.As can be seen, when no intercalator exists, the interlamellar spacing of polynite is not compared with the original layers spacing of polynite and is enlarged in the ethylene-propylene rubber/montmorillonite matrix material, and behind the adding intercalator in the ethylene-propylene rubber/montmorillonite matrix material interlamellar spacing of polynite obviously increase, the ethylene-propylene rubber/montmorillonite nano composite material that has formed intercal type is described.Tensile strength, tensile yield and the tear strength of ethylene-propylene rubber/montmorillonite matrix material are apparently higher than ethylene-propylene rubber/montmorillonite matrix material that does not add intercalator and the pure glue cross-linked rubber of ethylene-propylene rubber(EPR) behind the adding intercalator.Also the thermostability of ethylene-propylene rubber/montmorillonite matrix material is compared obvious raising with ethylene-propylene rubber/montmorillonite that does not add intercalator and the pure glue cross-linked rubber of ethylene-propylene rubber(EPR) behind the discovery adding intercalator.
Embodiment 6～9: in order to investigate polynite content to composite structure and Effect on Performance, according to the prescription in the table 2, ethylene-propylene rubber(EPR) is joined in the Banbury mixer, add polynite and intercalator 1827 then simultaneously, melt blending 8min under 70 ℃ processing temperatures and 90rpm rotor speed obtains intercal type ethylene-propylene rubber/montmorillonite master batch.Then above-mentioned sizing material is added zinc oxide under 50 ℃ processing temperature and 60rpm rotor speed, stearic acid, the mixing 6min of promotor and Sulfur promptly obtains intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate.Above-mentioned rubber unvulcanizate is vulcanized according to the sulfurizing time in the table 2,175 ℃ of curing temperatures, pressure 10MPa obtains ethylene-propylene rubber/montmorillonite nano composite material.
The above-mentioned ethylene-propylene rubber/montmorillonite nano composite material that obtains is made the thick dumbbell shape sample of 2mm, and Mechanics Performance Testing, XRD and TGA analyze the same, the results are shown in Table 2.
As can be seen from Table 2, when fixedly the amount ratio of polynite and intercalator 1827 was 1/0.85, along with the increase of polynite consumption, the tensile strength of ethylene-propylene rubber/montmorillonite matrix material and tensile yield increased then earlier and descend.Tear strength then increases along with the increase of polynite consumption.The heat decomposition temperature of ethylene-propylene rubber/montmorillonite matrix material slightly improves along with the increase of polynite consumption.
The above-mentioned ethylene-propylene rubber/montmorillonite nano composite material that obtains is made the thick dumbbell shape sample of 2mm, and Mechanics Performance Testing and TGA analyze the same, the results are shown in Table 3.
As can be seen from Table 3, the interlamellar spacing along with polynite in the increase ethylene-propylene rubber/montmorillonite matrix material of intercalator 1827 consumptions does not have obvious variation.Substantially remain unchanged then along with the tensile strength of the increase ethylene-propylene rubber/montmorillonite matrix material of intercalator 1827 consumptions increases earlier, tensile yield and tear strength then increase along with the increase of intercalator 1827 consumptions earlier, descend then.Along with the heat decomposition temperature of the increase ethylene-propylene rubber/montmorillonite matrix material of intercalator consumption increases.
Prescription, mechanical property and the heat decomposition temperature of table 1 ethylene-propylene rubber/montmorillonite matrix material
| Synergist S-421 95 (weight part) | Comparative Examples | Embodiment | |||||
| ????1 | ????2 | ????1 | ????2 | ????3 | ????4 | ????5 | |
| EPDM Na-MMT 2HT 182H 1,831 1,827 1631 ZnO S.A promoter PZ captax S | ????100 ????0 ????0 ????0 ????0 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????0 ????0 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????9.6 ????0 ????0 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????6.7 ????0 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????0 ????5.7 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????0 ????0 ????5.9 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????0 ????0 ????0 ????4.0 ????5 ????1 ????1.5 ????0.5 ????1.5 |
| Sulfurizing time (min) | ????8.3 | ????13.5 | ????15.7 | ????13.1 | ????15.2 | ????18.5 | ????10.8 |
| The interlamellar spacing d of polynite (001) crystal face 001(nm) * | ????- | ????1.29 | ????4.91 | ????5.73 | ????5.55 | ????5.55 | ????5.23 |
| Mechanical property tensile strength (MPa) tensile yield (%) tear strength (kN/m) | ? ????5.1 ????357 ????22.1 | ? ????11.8 ????530 ????33.7 | ? ????15.9 ????530 ????45.8 | ? ????23.4 ????611 ????45.7 | ? ????25.3 ????569 ????40.0 | ? ????27.8 ????633 ????41.9 | ? ????13.4 ????474 ????30.8 |
| Thermostability T 50(℃) T p(℃) | ? ????512.3 ????518.7 | ? ????527.1 ????528.3 | ? ????535.5 ????541.0 | ? ????541.2 ????541.0 | ? ????518.5 ????520.8 | ? ????534.4 ????535.5 | ? ????521.1 ????525.1 |
*When in the matrix material a plurality of diffraction peak being arranged, refer to the interlamellar spacing of the corresponding polynite of first diffraction peak of appearance in the small angle range.
The prescription and the mechanical property of table 2 ethylene-propylene rubber/montmorillonite matrix material
| Synergist S-421 95 (weight part) | Comparative Examples | Embodiment | ||||||
| ????1 | ????2 | ????3 | ????6 | ????7 | ??4 | ????8 | ??9 | |
| EPDM Na-MMT 1827 ZnO S.A promoter PZ captax S | ????100 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????0 ????5.9 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????5 ????1.5 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????10 ????3.0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ??100 ??20 ??5.9 ??5 ??1 ??1.5 ??0.5 ??1.5 | ????100 ????30 ????8.9 ????5 ????1 ????1.5 ????0.5 ????1.5 | ??100 ??40 ??11.8 ??5 ??1 ??1.5 ??0.5 ??1.5 |
| Sulfurizing time (min) | ????8.3 | ????13.5 | ????18.3 | ????12.1 | ????15.8 | ??18.6 | ????18.0 | ??12.9 |
| The interlamellar spacing d of polynite (001) crystal face 001(nm) * | ????- | ????1.29 | ????- | ????- | ????5.73 | ??5.32 | ????4.33 | ??5.81 |
| Mechanical property tensile strength (MPa) tensile yield (%) tear strength (kN/m) | ? ????5.1 ????357 ????22.1 | ? ????11.8 ????530 ????33.7 | ? ????6.8 ????454 ????24.9 | ? ????13.8 ????478 ????30.5 | ? ????20.6 ????561 ????37.5 | ? ??24.7 ??635 ??46.8 | ? ????23.0 ????629 ????48.1 | ? ??18.9 ??614 ??49.1 |
| Thermostability T 50(℃) ?T p(℃) | ? ????512.3 ????518.7 | ? ????527.1 ????528.3 | ? ????512.5 ????519.8 | ? ????530.8 ????537.4 | ? ????521.9 ????528.8 | ? ??537.1 ??538.0 | ? ????538.2 ????535.2 | ? ??544.3 ??551.1 |
*When in the matrix material a plurality of diffraction peak being arranged, refer to the interlamellar spacing of the corresponding polynite of first diffraction peak of appearance in the small angle range.
Table 3 polynite and intercalator 1827 amount ratios are to the influence of composite materials property and thermal decomposition behavior
| Synergist S-421 95 (weight part) | Comparative Examples | Embodiment | |||||
| ????1 | ????2 | ????10 | ????4 | ????11 | ??12 | ??13 | |
| EPDM Na-MMT 1827 ZnO S.A promoter PZ captax S | ????100 ????0 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????0 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????4.9 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????5.9 ????5 ????1 ????1.5 ????0.5 ????1.5 | ????100 ????20 ????6.9 ????5 ????1 ????1.5 ????0.5 ????1.5 | ??100 ??20 ??8.0 ??5 ??1 ??1.5 ??0.5 ??1.5 | ??100 ??20 ??9.0 ??5 ??1 ??1.5 ??0.5 ??1.5 |
| Sulfurizing time (min) | ????8.3 | ????13.5 | ????21.0 | ????21.0 | ????21.5 | ??21.2 | ??20.1 |
| The interlamellar spacing d of polynite (001) crystal face 001(nm) * | ????- | ????1.29 | ????6.18 | ????6.18 | ????6.18 | ??6.79 | ??6.18 |
| Mechanical property tensile strength (MPa) tensile yield (%) tear strength (kN/m) | ? ????5.1 ????357 ????22.1 | ? ????11.8 ????530 ????33.7 | ? ????18.7 ????581 ????41.6 | ? ????24.7 ????635 ????46.8 | ? ????24.3 ????597 ????42.7 | ? ??23.7 ??566 ??43.4 | ? ??25.0 ??599 ??42.0 |
| Thermostability T 50(℃) ??T p(℃) | ? ????512.3 ????518.7 | ? ????527.1 ????528.3 | ? ????524.1 ????526.5 | ? ????530.4 ????526.6 | ? ????542.7 ????543.0 | ? ??537.2 ??538.7 | ? ??546.0 ??552.6 |
*When in the matrix material a plurality of diffraction peak being arranged, refer to the interlamellar spacing of the corresponding polynite of first diffraction peak of appearance in the small angle range.
Claims (5)
1. the preparation method of ethylene-propylene rubber/montmorillonite nano composite material, it is characterized in that by weight the ethylene-propylene rubber(EPR) with 100 parts joins in the Banbury mixer, add 1～60 part polynite and 0.5～25 part intercalator then simultaneously, melt blending 5～20min under 30～120 ℃ processing temperatures and 30～150rpm rotor speed obtains intercal type ethylene-propylene rubber/montmorillonite master batch; Then intercal type ethylene-propylene rubber/montmorillonite master batch is added 1～8 part vulcanization leveller, 0.5～5 part of promotor and 0.5～4 part of vulcanizing agent and mixing 5～10min according to prescription under 30～100 ℃ processing temperature and 30～150rpm rotor speed, promptly obtain intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate; At last intercal type ethylene-propylene rubber/montmorillonite rubber unvulcanizate is vulcanized under 140～200 ℃, curing time 10～30min, sulfide stress 5～10MPa promptly obtains ethylene-propylene rubber/montmorillonite nano composite material after sulfuration.
2. the preparation method of ethylene-propylene rubber/montmorillonite nano composite material according to claim 1 is characterized in that ethylene-propylene rubber(EPR) is that a kind of ethylene content is that 70%, the three monomer is 4.9% for ethylidene norbornene content, and crude rubber Mooney viscosity is
Ethylene propylene copolymer.
3. the preparation method of ethylene-propylene rubber/montmorillonite nano composite material according to claim 1 is characterized in that polynite is a kind of nonmetal stratiform silicate, and its cation exchange capacity is 70～120meq/100g.
4. the preparation method of ethylene-propylene rubber/montmorillonite nano composite material according to claim 1 is characterized in that intercalator is two (2-hydroxyethyl) the hydrogenated tallow ammonium chlorides of trimethylammonium octadecyl ammonium chloride, methyl, dimethyl stearyl benzyl ammonium chloride, GERBU Adjuvant 100, trimethylammonium hexadecyl brometo de amonio or octadecyl ammonium chloride.
5. the preparation method of ethylene-propylene rubber/montmorillonite nano composite material according to claim 1 is characterized in that vulcanization leveller is zinc oxide and stearic acid; Promotor is ziram, 2-benzothiazolyl mercaptan, N-phenylcyclohexane benzothiazolyl sulphenamide, dibenzothiazyl disulfide, vulkacit D or tetramethyl-thiuram disulfide; Vulcanizing agent is Sulfur, dicumyl peroxide or 2,5-dimethyl-2,5-di-t-butyl peroxide hexane.
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