CN1425712A - Triple ethylene-propylene rubber/montmorillonoid peeling nano composite material and its preparing method - Google Patents
Triple ethylene-propylene rubber/montmorillonoid peeling nano composite material and its preparing method Download PDFInfo
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- CN1425712A CN1425712A CN 03114809 CN03114809A CN1425712A CN 1425712 A CN1425712 A CN 1425712A CN 03114809 CN03114809 CN 03114809 CN 03114809 A CN03114809 A CN 03114809A CN 1425712 A CN1425712 A CN 1425712A
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Abstract
The present invention provides a peeling nano composite ternary ethylene-propylene rubber/montmorillonoid material with compatibilizer and its preparation. The composite material consists of ternary ethylene-propylene rubber, ternary ethylene-propylene rubber-grafting maleic anhydride compatibilizer, organic montmorillonoid, sulfurizing-activating ageing, sulfurizing agent and sulfurizing accelerator. Its preparation includes smelting and blending the compatibilizer, organic montmorillonoid and ternary ethylene-propylene rubber inside an internal mixer and sulfurizing with added sulfurizing-activating ageing, sulfurizing agent and sulfurizing accelerator. The nano compoiste material has the structure with montmorillonoid dispersed in polymer substrate and thus mechanical performance higher than that of pure polymer and inserting nano composite material.
Description
Technical field: the invention belongs to a kind of polymer composites that uses mineral filler, particularly a kind of stripping nano matrix material that adopts the class montmorillonite filled terpolymer EP rubber of expanding material and form and preparation method thereof.
Background technology: polymer nanocomposites becomes more meticulous because of the height of its disperse phase and nanometer size effect has and conventional composite materials (micron order disperse phase) visibly different mechanical property and functional performance.Wherein layered silicate/polymer nanocomposites has more outstanding high rigidity, high strength, high-barrier and high flame retardant etc. with the high shape factor ratio of disperse phase again.Since Fukushima etc. successfully prepares clay/nylon nano matrix material first, many polymkeric substance also prepare successfully in succession as Resins, epoxy (ER), polystyrene (PS), polyester (PET, PBT), polypropylene (PP), paracril (NBR), styrene-butadiene rubber(SBR) nano materials such as (SBR).Terpolymer EP rubber is because the advantage on its structure and the performance and occupy very big proportion on rubber market, thereby relevant its research of nano composite material also receives much attention.But, think that in early days high polar polynite reaches nano level and disperses to be difficult to realize in the terpolymer EP rubber matrix owing to do not include any polar group on its main chain.(US6271297), people adopt coupling agents such as silane, titanic acid ester and aluminic acid ester more for US6462122, US6407155 in a spot of patent report about terpolymer EP rubber and polynite.They are small molecules, oligopolymer or polymkeric substance normally, and their solubility parameters (δ) helps them and matrix enters between clay seam.People such as Yook-Wook Chang adopt liquid epdm rubber further to handle organo montmorillonite, but the bulk stores that occurs in the nano composite material Electronic Speculum figure of made shows that matrix does not make the organo montmorillonite layer peel off.Have only as people such as A.Usuki and adopt ziram, in sulfidation, just prepared exfoliated terpolymer EP rubber/Nano composite material of montmorillonite as the vulcanization crosslinking agent.
Summary of the invention: the present invention adopts the method for the maleic anhydride modified terpolymer EP rubber organic modifiers modified montmorillonoid different with three kinds, resulting grafting maleic anhydride with ethylene propylene terpolymer expanding material and three kinds of organo montmorillonites are dosed in the terpolymer EP rubber and is formed exfoliated nano-composite and preparation method thereof.Nano composite material of the present invention not only has polynite and is dispersed in structure in the polymeric matrix, and its mechanical property has had significantly with respect to straight polymer and intercalation type nano composite material and improves.
The feed composition and the consumption of terpolymer EP rubber of the present invention/polynite stripping nano matrix material are as follows: (weight part)
Terpolymer EP rubber 100
Maleic anhydride 0.5-12
Polynite 0.5-20
Initiator 0.02-1.0
Cation modifier 0.1-15
Vulcanization leveller 1-10
Vulcanizing agent 1-3
Vulcanization accelerator 0.2-2.0
The present invention uses the particle diameter of polynite to be 50-100 μ m, its cation exchange capacity 50-120meq/100g.
It is that a kind of ethylene content is that the 70%, the 3rd monomer is ethylidene norbornene that the present invention uses terpolymer EP rubber, and mooney viscosity is greater than 70 (ML
1+4100 ℃) ethylene propylene copolymer.
It is 2 that the present invention uses initiator, 5-dimethyl-2,5-di-t-butyl peroxide hexane, benzoyl peroxide and dicumyl peroxide.
It is the trimethylammonium octadecyl ammonium chloride that the present invention uses cation modifier, the two octadecyl ammonium chloride of the two methyl of dimethyl benzyl octadecyl ammonium chloride.
It is hydrochloric acid and sulfuric acid that the present invention uses protonating agent.
It is water that the present invention uses dispersion medium.
It is zinc oxide and stearic acid that the present invention uses vulcanization leveller.
It is sulphur that the present invention uses vulcanizing agent.
It is 2-thiol group phenylpropyl alcohol thiazole (M) that the present invention uses vulcanization accelerator, N-cyclohexyl-2-phenylpropyl alcohol thiazolesulfenamide (CZ).
The preparation method of terpolymer EP rubber of the present invention/polynite stripping nano matrix material is undertaken by following step:
(1) with cation exchange capacity be polynite 0.5-20 part of 50-120meq/100g, high-speed stirring in the presence of 100-800 part dispersion medium water forms stable suspension system A.0.1-15 part cation modifier is dissolved in 100-1100 part dispersion medium water, adds 1-20 part protonating agent hydrochloric acid, form solution B.Suspension system A is heated to 70-90 ℃, solution B slowly is added dropwise among the A, after high-speed stirring 3-5 hour, make polynite colloidal sol, use deionized water rinsing, filter, oven dry is ground into the organo montmorillonite powder;
(2) maleic anhydride 0.2-4.0 part is fully milled back stirs into paste with a small amount of paraffin oil, put into premix machine premix with 100 parts of terpolymer EP rubbers then, at last this pre-composition is added in the twin screw extruder, under 150-220 ℃ of processing temperature, react and extrude, the grafting maleic anhydride with ethylene propylene terpolymer expanding material with certain percentage of grafting is dried in granulation;
(3) with above-mentioned grafting maleic anhydride with ethylene propylene terpolymer expanding material, organo montmorillonite and terpolymer EP rubber weight ratio melt blending in Banbury mixer by 1: 2: 20, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time is 10-20min.Behind rubber, organo montmorillonite and expanding material mixing 5-10min, add vulcanization leveller, vulcanization crosslinking agent etc., until mixing end.After this mixture discharging cooling, after thin-pass tens times, press the optimum sulfurating time sulfuration shown in the rotor vulkameter at pony roll in two roller mills, promptly get product.
Embodiment: embodiment 1 (Comparative Examples does not contain organic polynite and expanding material)
57g terpolymer EP rubber and zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g and captax 0.19g and accelerant CZ 0.6g join in the Banbury mixer.90 ℃ of melting temperatures, rotor speed 136rpm, mixing time 10min.After normal temperature thin-pass in two roller mills tens times, press the optimum sulfurating time sulfuration, the cross-linked rubber test piece that promptly gets Comparative Examples after the discharging.Its performance sees Table 1.Embodiment 2 (Comparative Examples contains organic polynite A, does not contain expanding material)
With the cationic exchange total volume is the polynite 10g of 100meq/100g, adds water 500ml, and after waiting to be uniformly dispersed, high-speed stirring 20-30min gets steady suspension A.4.5g the trimethylammonium octadecyl ammonium chloride is dissolved in the 30ml water, adds saturated hydrochloric acid 2.15ml, gets solution B.Suspending liquid A is heated to 80 ℃, under the stirrer effect, drips solution B, be incubated after 3-5 hour, cooling gets white precipitate, with its filtration, repeatedly washes with deionized water, with the AgNO of 0.1N
3Aqueous assay filtrate does not generate to there being the AgCl white precipitate.The polynite colloidal sol of gained after dry 24 hours, is dried in 90 ℃ of vacuum drying ovens, be milled to organo montmorillonite A powder.
Taking by weighing organo montmorillonite A powder 5.7g and terpolymer EP rubber 57g adds in the Banbury mixer.90 ℃ of melting temperatures, rotor speed 136rom, total mixing time 15min.After organo montmorillonite and compounding rubber begin 6-7min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g continue mixing.The discharging cooling of mixing end back after surplus two roller mill normal temperature thin-passes ten times, is pressed the Best Times sulfuration test piece shown in the rotor vulkameter with resulting mixture.Its performance sees Table 1.Embodiment 3 (containing organo montmorillonite A and expanding material)
The process of organising of polynite is seen example 2.
Maleic anhydride 0.2-2.0 part back of fully milling is stirred into paste with a small amount of paraffin oil, put into premix machine premix with 100 parts of terpolymer EP rubber rubbers then, at last this pre-composition is added in the twin screw extruder, under 150-220 ℃ of processing temperature, react and extrude, the grafting maleic anhydride with ethylene propylene terpolymer expanding material with certain percentage of grafting is dried in granulation.
At last, with above-mentioned grafting maleic anhydride with ethylene propylene terpolymer expanding material, organo montmorillonite and terpolymer EP rubber weight ratio melt blending in Banbury mixer by 1: 2: 20, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time is 10-20min.Behind rubber, organo montmorillonite and expanding material mixing 5-10min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g continue mixing, until mixing end.After this mixture discharging cooling, after thin-pass tens times, press the sulfuration of optimum sulfurating time shown in rotor vulkameter test piece at pony roll in two roller mills.Its performance sees Table 1.Embodiment 4 (Comparative Examples contains organic polynite B, does not contain expanding material)
With the cationic exchange total volume is the polynite 20g of 100meq/100g, adds water 500ml, and after waiting to be uniformly dispersed, high-speed stirring 20-30min gets suspending liquid A.7.0g the dimethyl benzyl octadecyl ammonium chloride is dissolved in the 30ml water, adds saturated hydrochloric acid 2.15ml, gets solution B.Suspending liquid A is heated to 80 ℃, under the stirrer effect, drips solution B, be incubated after 3-5 hour, cooling gets white precipitate, with its filtration, repeatedly washes with deionized water, with the AgNO of 0.1N
3Aqueous assay filtrate does not generate to there being the AgCl white precipitate.The polynite colloidal sol of gained after dry 24 hours, is dried in 90 ℃ of vacuum drying ovens, be milled to organo montmorillonite B powder.
Taking by weighing this organo montmorillonite B powder 5.7g and terpolymer EP rubber 57g adds in the Banbury mixer.90 ℃ of melting temperatures, rotor speed 136rom, total mixing time 15min.After organo montmorillonite and compounding rubber begin 6-7min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g.The discharging cooling of mixing end back after surplus two roller mill normal temperature thin-passes ten times, is pressed the Best Times sulfuration test piece shown in the rotor vulkameter with resulting mixture.Its performance sees Table 1.Embodiment 5 (containing organic polynite B and expanding material)
Embodiment 4 is seen in organising of polynite.
Embodiment 3 is seen in the preparation of grafting maleic anhydride with ethylene propylene terpolymer expanding material.
With above-mentioned grafting maleic anhydride with ethylene propylene terpolymer expanding material, organo montmorillonite and terpolymer EP rubber weight ratio melt blending in Banbury mixer according to 1: 2: 20, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time is 10-20min.Behind rubber, organo montmorillonite and expanding material mixing 5-10min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g continue mixing.After the mixing end, after this mixture discharging cooling, after thin-pass tens times, promptly get product at pony roll in two roller mills.Its performance sees Table 1.Embodiment 6 (Comparative Examples contains organic polynite C, does not contain expanding material)
With the cationic exchange total volume is the polynite 20g of 100meq/100g, adds water 500ml, and after waiting to be uniformly dispersed, high-speed stirring 20-30min gets steady suspension A.10.6g the two octadecyl ammonium chloride of two methyl are dissolved in the 80ml water, add saturated hydrochloric acid 2.15ml, get solution B.Suspending liquid A is heated to 80 ℃, under the stirrer effect, slowly drips solution B, be incubated after 3-5 hour, cooling gets white precipitate, with its filtration, repeatedly washes with deionized water, uses 0.1NAgNO
3Solution detects filtrate and does not generate to there being the AgCl white precipitate.The polynite colloidal sol of gained after dry 24 hours, is dried in 90 ℃ of vacuum drying ovens, be milled to organo montmorillonite C powder.
Taking by weighing this organo montmorillonite C powder 5.7g and terpolymer EP rubber 57g adds in the Banbury mixer.90 ℃ of melting temperatures, rotor speed 136rom, total mixing time 15min.After organo montmorillonite and compounding rubber begin 6-7min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g.The discharging cooling of mixing end back after surplus two roller mill normal temperature thin-passes ten times, is pressed the Best Times sulfuration test piece shown in the rotor vulkameter with resulting mixture.Its performance sees Table 1.Embodiment 7 (containing organo montmorillonite C and expanding material)
Embodiment 6 is seen in organising of polynite.
Embodiment 3 is seen in the preparation of grafting maleic anhydride with ethylene propylene terpolymer expanding material.
With above-mentioned grafting maleic anhydride with ethylene propylene terpolymer expanding material, organo montmorillonite and terpolymer EP rubber weight ratio melt blending in Banbury mixer by 1: 2: 20, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time is 10-20min.Behind rubber, organo montmorillonite and expanding material mixing 5-10min, add zinc oxide 1.9g, stearic acid 0.38g, sulphur 0.6g, captax 0.19g and accelerant CZ 0.6g continue mixing.Mixing end after this mixture discharging cooling, after thin-pass tens times, is pressed the Best Times sulfuration test piece shown in the rotor rheometer at pony roll in two roller mills.Its performance sees Table 1.Table 1
Ethylene Propylene Terpolymer
Grafting rubbers d
001The organic illiteracy of embodiment Ethylene Propylene Terpolymer is taken off organic illiteracy and is taken off maleic anhydride and pull apart the elongation tear strength apart from () tensile strength between face
Rubber content soil species class soil content expanding material contains (MPa) rate (%) (kN/m)
(part), (part) amount, (%) 1 100 00 5.75 275 25.4 2 100 A, 10 0 49.6 12.5 424 38.9 3 100 A 10 5-16.8,493 46.3 4 100 B, 10 0 48.5 14.6 389 41.6 5 100 B 10 5-18.2,464 48.5 6 100 C, 10 0 53.2 14.8 442 40.8 7 100 C 10 5-19.9 502 49.4 conditions of vulcanizations: each organic imvite modified dose kind: A of 175 ℃ * 18min: trimethyl octadecyl ammonium chloride
B: dimethyl benzyl octadecyl ammonium chloride
C: the two octadecyl ammonium chloride of two methyl
Claims (8)
1 terpolymer EP rubber/polynite stripping nano matrix material comprises terpolymer EP rubber, maleic anhydride, initiator, organo montmorillonite and vulcanization leveller and vulcanization crosslinking agent, it is characterized in that the feed composition of described matrix material and content are as follows: (weight part)
Terpolymer EP rubber 100
Maleic anhydride 0.5-12
Polynite 0.5-20
Initiator 0.02-1.0
Cation modifier 0.1-15
Vulcanization leveller 1-10
Vulcanizing agent 1-3
Vulcanization accelerator 0.5-2.0
The particle diameter of polynite is 50-100 μ m in the described matrix material, its cation exchange capacity 50-120meq/100g.
2 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described terpolymer EP rubber is that a kind of ethylene content is that the 70%, the 3rd monomer is that ethylidene norbornene, mooney viscosity are greater than 70 (ML
1+4, 100 ℃) ethylene propylene copolymer.
3 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described initiator is 2,5-dimethyl-2,5-di-t-butyl peroxide hexane, benzoyl peroxide and peroxidation two different acenes.
4 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described cation modifier is the trimethylammonium octadecyl ammonium chloride, dimethyl benzyl octadecyl ammonium chloride and the two octadecyl ammonium chloride of two methyl.
5 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described vulcanization leveller is zinc oxide and stearic acid.
6 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described vulcanization crosslinking agent is a sulphur.
7 terpolymer EP rubbers according to claim 1/polynite stripping nano matrix material is characterized in that described vulcanization accelerator is a 2-thiol group phenylpropyl alcohol thiazole, N-cyclohexyl-2-phenylpropyl alcohol thiazolesulfenamide.
The making method of 8 terpolymer EP rubbers/polynite stripping nano matrix material, its feature is carried out as follows:
(1) with cation exchange capacity be polynite 0.5-20 part of 50-120meq/100g, high-speed stirring in the presence of 100-800 part dispersion medium water forms stable suspension system A; 0.1-15 part cation modifier is dissolved in the 100-1100 dispersion medium water, adds 1-20 part protonating agent hydrochloric acid, form solution B.Suspension system A is heated to 70-90 ℃, solution B slowly is added dropwise among the A, after high-speed stirring 3-5 hour, make polynite colloidal sol, use deionized water rinsing, filter, oven dry is ground into the organo montmorillonite powder;
(2) maleic anhydride 0.2-4.0 part is fully milled back stirs into paste with a small amount of paraffin oil, put into premix machine premix with 100 parts of terpolymer EP rubbers then, at last this pre-composition is added in the twin screw extruder, under 150-220 ℃ of processing temperature, react and extrude, the grafting maleic anhydride with ethylene propylene terpolymer expanding material with certain percentage of grafting is dried in granulation;
(3) with above-mentioned grafting maleic anhydride with ethylene propylene terpolymer expanding material, organo montmorillonite and terpolymer EP rubber weight ratio melt blending in Banbury mixer by 1: 2: 20, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time is 10-20min.Behind rubber, organo montmorillonite and expanding material mixing 5-10min, add vulcanization leveller, vulcanizing agent and vulcanization accelerator, until mixing end, after this mixture discharging cooling, at pony roll in two roller mills after thin-pass tens times, press the optimum sulfurating time sulfuration shown in the rotor vulkameter, promptly get product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322053C (en) * | 2004-04-16 | 2007-06-20 | 华南理工大学 | nano composite material of rubber/layer silicate and preparation method |
| CN100386384C (en) * | 2003-09-03 | 2008-05-07 | 中国科学院长春应用化学研究所 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
| CN101381493B (en) * | 2008-10-08 | 2011-08-24 | 中国科学技术大学 | Halogen-free flameproof ternary ethlene propyene rubber compound material and preparation method thereof |
| CN103351539A (en) * | 2013-07-23 | 2013-10-16 | 中国工程物理研究院化工材料研究所 | Ethylene-propylene-diene monomer rubber/montmorillonite nanocomposite and preparation method thereof |
| CN106188880A (en) * | 2016-07-19 | 2016-12-07 | 合肥毅创钣金科技有限公司 | The EPT rubber packing bar that a kind of corona-resistance property strengthens |
| CN110283478A (en) * | 2019-07-11 | 2019-09-27 | 东北大学 | The tertiary-amine modified zeolite of octadecyldimethyl and the compound material and its preparation method of natural rubber |
| CN114801371A (en) * | 2022-05-26 | 2022-07-29 | 浙江柏德密封科技有限公司 | Metal rubber composite board with high compression performance |
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2003
- 2003-01-09 CN CN 03114809 patent/CN1425712A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386384C (en) * | 2003-09-03 | 2008-05-07 | 中国科学院长春应用化学研究所 | Detaching type polymer/montmorillonite composite material and preparing method thereof |
| CN1322053C (en) * | 2004-04-16 | 2007-06-20 | 华南理工大学 | nano composite material of rubber/layer silicate and preparation method |
| CN101381493B (en) * | 2008-10-08 | 2011-08-24 | 中国科学技术大学 | Halogen-free flameproof ternary ethlene propyene rubber compound material and preparation method thereof |
| CN103351539A (en) * | 2013-07-23 | 2013-10-16 | 中国工程物理研究院化工材料研究所 | Ethylene-propylene-diene monomer rubber/montmorillonite nanocomposite and preparation method thereof |
| CN106188880A (en) * | 2016-07-19 | 2016-12-07 | 合肥毅创钣金科技有限公司 | The EPT rubber packing bar that a kind of corona-resistance property strengthens |
| CN110283478A (en) * | 2019-07-11 | 2019-09-27 | 东北大学 | The tertiary-amine modified zeolite of octadecyldimethyl and the compound material and its preparation method of natural rubber |
| WO2021003760A1 (en) * | 2019-07-11 | 2021-01-14 | 东北大学 | Composite material of octadecyldimethyl-tertiary-amine-modified zeolite and natural rubber and preparation method therefor |
| CN114801371A (en) * | 2022-05-26 | 2022-07-29 | 浙江柏德密封科技有限公司 | Metal rubber composite board with high compression performance |
| CN114801371B (en) * | 2022-05-26 | 2023-07-14 | 浙江柏德密封科技有限公司 | Metal rubber composite board with high compression performance |
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