CN105295206A - Micropore EPDM foamed material with excellent compression resilience performance and preparation method - Google Patents
Micropore EPDM foamed material with excellent compression resilience performance and preparation method Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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Abstract
The invention discloses a micropore EPDM foamed material with excellent compression resilience performance. The material is prepared from: by mass, 100-200 parts of ethylene-propylene-nonconjugated dialkene copolymer, 0-80 parts of vinylsiloxane rubber, 10-60 parts of inorganic nanoparticles, 0.5-15 parts of low temperature foaming agent and 0.5-10 parts of organic peroxide composition; wherein the nonconjugated dialkene is selected from ethylidene norbornene, hexadiene and isoprene, the mooney viscosity of the copolymer is not less than 20; the degree of polymerization of the vinylsiloxane rubber is not less than 1000 and the vinylsiloxane rubber contains at least two alkenyl groups connected with silicon atom; and organic peroxide composition includes two organic peroxides of which thermal degradation half-life for 1 min less than 155 DEG C and not less than 170 DEG C. The micropore EPDM foamed material with excellent compression resilience performance can be prepared according to the invention, the material has high mechanical strength, good appearance and uniform internal structure.
Description
Technical field
Embodiments of the present invention relate to foam materials field, and more specifically, embodiments of the present invention relate to excellent micropore terpolymer EP rubber foam materials of a kind of compression resilience and preparation method thereof.
Background technology
Winter hardiness, the weathering resistance of terpolymer EP rubber and foam materials thereof are excellent, because proportion is little, be easy to be shaped to different shape, there is the characteristic of good absorption mechanical energy, be widely used as carrier vehicle, navigation naval vessel, various aircraft, high temperature service and instrument, the isolating technique of building doors and windows and sealing material.Owing to having more excellent thermotolerance, compression rebound character, the terpolymer EP rubber foam materials of peroxide cure is little to device dependence, applied range, becomes a study hotspot in recent years.
The present inventor finds when studying and adopting Cellmic C 121 (ADC) to make the terpolymer EP rubber foam materials of whipping agent, adopt ZnO and urea etc. coordinate ADC heat decomposition temperature high (>150 DEG C), peroxide vulcanizing agent coupling bad, be difficult to obtain good cure efficiency, the lax creep of foam materials is large, compression resilience is bad, restorative poor.Even if (8-12%) 2-mercaptobenzimidazole anti-aging agent adopting volume to coordinate coordinates ethylene propylene diene rubber foaming shaping with ADC, organo-peroxide, be also difficult to the EPDM foam materials obtaining good compression rebound resilience, low compression creep.Radiation vulcanizing method is adopted to make sulfuration prepare terpolymer EP rubber foam with foaming proceed step by step, although traditional foaming process sulfuration and vulcanization rate in foaming and expansion rate can be avoided to be difficult to the problem of mating, but the method is very large to the dependency of radiation device, is of limited application.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, micropore terpolymer EP rubber foam materials providing a kind of compression resilience excellent and preparation method thereof, with expect to solve foam materials lax compacted large, compression resilience is bad, restorative poor problem.
According to the research experience in silicon rubber foam material, on the basis of the mechanism of profound understanding organo-peroxide crosslinked polymeric materials and the resolution characteristic of chemical foaming agent, especially be cross-linked for organo-peroxide the fact that lower terpolymer EP rubber macromolecular chain is easy to chain rupture, the present invention researchs and develops excellent terpolymer EP rubber foam materials of the compression resilience being particularly suitable for compression molding of novel peroxide cure and preparation method thereof.The present invention is by the terpolymer EP rubber of Mooney concentration more than 20, and more than 1000 or 1000 organopolysiloxane at least with two basic change alkenyl on the silicon atoms of the polymerization degree, specific surface area (BET method) are 10-400m
2the cooperation of the inorganic nano-particle of/g, production of low-temperature foaming agent, organo-peroxide composition, by low temperature high temperature secondary sulfur foam under the pressure of necessity, obtains the micropore terpolymer EP rubber foam materials that a kind of compression resilience is excellent.Therefore, one embodiment of the present invention are by the following technical solutions:
The micropore terpolymer EP rubber foam materials that compression resilience is excellent, this material is made by comprising the following component of measuring by mass parts:
Non-conjugated diene hydrocarbon in wherein ethylene-propylene-non-conjugated diene hydrocarbon copolymer is selected from ethylidene norbornene, Isosorbide-5-Nitrae-hexadiene and isoprene, and the mooney viscosity of multipolymer is not less than 20; The polymerization degree of vinylsiloxane rubber is not less than 1000 and contains at least 2 alkenyls be connected with Siliciumatom; The organo-peroxide E2 that organo-peroxide composition is not less than 170 DEG C by 1min thermal decomposition half life lower than the organo-peroxide E1 of 155 DEG C and 1min thermal decomposition half life is formed.
Described organo-peroxide E1 is dibenzoyl peroxide, 2, the chloro-dibenzoyl peroxide of 4-bis-, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, 1,1-di-t-butyl peroxy-3,3, at least one in 5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy) cyclohexane, peroxidized t-butyl perbenzoate; Described organo-peroxide E2 is dicumyl peroxide, 1,4-dual-tert-butyl peroxy isopropyl base benzene, 1,3-dual-tert-butyl peroxy isopropyl base benzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexin, 2, at least one in 5-dimethyl-2,5-bis(t-butylperoxy) hexane; The mass ratio that described 1min thermal decomposition half life is greater than the organo-peroxide of 170 DEG C lower than the organo-peroxide of 155 DEG C and described 1min thermal decomposition half life is 0.3-6:10.
The iodine number of described ethylene-propylene-non-conjugated diene hydrocarbon copolymer is (5-30)/100g.
The contents of ethylene of described vinylsiloxane rubber is 0.04-0.5mol%.
Described inorganic nano-particle is the nanoparticle of at least one in silicon-dioxide, calcium carbonate, kaolin, clay, aluminium sesquioxide, titanium dioxide, carbon black, polynite, potter's clay.
The BET method specific surface area of described inorganic nano-particle is 10-400m
2/ g.
Described production of low-temperature foaming agent is dinitrosopentamethlyene tetramine, 4, at least one in 4 '-OBSH, p-toluene sulfonyl hydrazide, Cellmic C 121.
The discharge quantity of described production of low-temperature foaming agent is not less than 100ml/g, and particle diameter is not more than 20 μm, and the temperature of initial decomposition in rubber is not higher than 150 DEG C.
The excellent micropore terpolymer EP rubber foam materials of described compression resilience also comprises cyanacrylate, triallylcyanurate, liquid polybutadiene, Ethylene glycol dimethacrylate, N, N '-isophthalic methylene-bis maleimide, trihemellitic acid allyl ester, trihydroxy methyl propane trimethyl acrylate, dimethacrylate 1, the cure activating ingredient of at least one in 3-butylene terephthalate, magnesinm methacrylate, zinc methacrylate, methacrylic acid, and its consumption is 0.1-10 part.
Present invention also offers the method for the excellent micropore terpolymer EP rubber foam materials of the above-mentioned compression resilience of preparation, comprise the following steps:
A. ethylene-propylene-non-conjugated diene hydrocarbon copolymer, vinylsiloxane rubber are uniformly dispersed in mill or kneader, banburying equipment with inorganic nano-particle respectively, appropriate dispersion agent is added in dispersion process, at high temperature discharge small molecules, obtain two kinds of mixtures, again these two kinds of mixtures are uniformly dispersed by heating is blended under appropriate interfacial agent effect, cool after blanking, obtain EPT rubber composition base-material;
B. in EPT rubber composition base-material, add production of low-temperature foaming agent, cure activating ingredient is uniformly dispersed, under the 10h half life temperature not higher than organo-peroxide E1 and organo-peroxide E2 deducts the temperature condition of 30 DEG C, add these two kinds of organo-peroxides again and be uniformly dispersed, obtaining the sizing material adding production of low-temperature foaming agent;
C. the described sizing material adding production of low-temperature foaming agent is injected die cavity, at temperature 130 DEG C ± 10 DEG C and pressure 0.1MPa-50MPa condition, react 5-20min realizes slight crosslinked, more high temperature vulcanized enough time obtains described micropore terpolymer EP rubber foam materials under temperature 170 DEG C ± 20 DEG C conditions.
Below technical scheme of the present invention is further detailed.
-composition (A)-
Ethylene-propylene-non-conjugated diene the multipolymer of composition (A) is the rubbery copolymer obtained by the copolymerization of ethene, propylene and non-conjugated diene hydrocarbon, and non-conjugated diene hydrocarbon still has a carbon-carbon double bond to retain thus can realize the crosslinked of rubber by vulcanizing agent after copolymerization.Non-conjugated diene is defined as ethylidene norbornene (5-ethylidene-2-norbornene), Isosorbide-5-Nitrae-hexadiene, dicyclopentadiene etc.The concrete example of described ethylene-propylene-non-conjugated diene multipolymer comprises ethylene-propylene-ethyiidenenorbomene copolymer, its derivative comprises the halogenated products of terpolymer EP rubber if chlorination terpolymer EP rubber (chlorinatedEPDMrubber), bromination terpolymer EP rubber (brominatedEPDMrubber), sulfonated EPDM, nitrilation ethylene-propylene rubber(EPR), acroleic acid esterification ethylene-propylene rubber(EPR) and terpolymer EP rubber are from aggressiveness etc., its mooney viscosity
be not less than 20, be advisable between 20-80, preferred 35-55; Wherein the content of Third monomer represents with iodine number, and iodine number is advisable with 5-30, preferred 10-25, more preferably 19-23.
-composition (B)-
The specific features of composition (B) vinylsiloxane rubber is: the polymerization degree be not less than 1000, each molecule is at least containing the organopolysiloxane of 2 alkenyls be directly connected with Siliciumatom.Organopolysiloxane is polymer matrix material, and it on average forms as shown in formula (I).
R
aSiO
(4-a)/2(I)
(in formula, R represents identical or not identical univalence hydrocarbyl, and a is the positive number of 1.95-2.05.)
In average compositional formula (I), R represents identical or not identical univalence hydrocarbyl, is generally 1-6 carbon atom.The univalence hydrocarbyl that R represents can be monosubstituted or polysubstituted, and substituting group can be halogen or cyano group.The example of R comprises the alkyl type of methyl, ethyl, propyl group, butyl, hexyl; The cycloalkyl type of cyclohexyl; The alkenyl type of vinyl, allyl group, butenyl or hexenyl; The aryl type of phenyl, aminomethyl phenyl; The type of unit price substituted hydrocarbon radical comprises chloromethyl, trifluoro propyl or cyano ethyl.
In the univalence hydrocarbyl of organopolysiloxane, preferable methyl, vinyl, phenyl or trifluoro propyl, and the preferred 80-99.99mo1% of the ratio of methyl, more preferably 95-99.99mo1% in R sum.The end group of organopolysiloxane can be the trimethicone of inertia, also can be dimethylvinyl siloxane, dimethyl hydroxyl siloxanes or the trivinyl siloxanes etc. that can participate in crosslinking reaction.
At least containing 2 alkenyls be directly connected with Siliciumatom in the organopolysiloxane of each molecule, as vinyl, allyl group etc.Alkenyl content range is 0.04mol%-0.5mo1%, preferred 0.1mol%-0.3mo1%.
The organopolysiloxane of composition (B) can adopt cyclic low molecular weight organopolysiloxane (trimer of such as organo-siloxane or tetramer ring body) to carry out ring-opening polymerization under alkalescence or an acidic catalyst and hot conditions to prepare organosiloxane polymer, and one or more organohalosilanes also can be selected to be hydrolyzed-condensation polymerization reaction and obtain organosiloxane polymer.
The viscometric degree of polymerization of the organopolysiloxane of composition (B) is more than 1000 and 1000, and preferred 7000-15000, more preferably within the scope of 8000-12000.As long as viscometric degree of polymerization is within the scope of this, composition (A) organopolysiloxane just has suitable mobility, good processibility and suitable physical strength.Viscometric degree of polymerization measures viscosity-average molecular weight by viscosimetry (Ubbelohde viscometer method, HG/T3312-2000), then by the following formulae discovery polymerization degree:
The molecular weight of repeating unit in viscometric degree of polymerization=viscosity-average molecular weight/organopolysiloxane
When composition (B) organopolysiloxane contains several different silicones monomer, the term that adopts in the above formula molecular weight of repeating unit " in the organopolysiloxane " refers to the number-average molecular weight of this several repeating unit.
Composition (B) organopolysiloxane can adopt single molecular chain structure, or has the mixture of differing molecular chain structure or viscometric degree of polymerization two or more organopolysiloxanes not etc.
-composition (C)-
Composition (C) inorganic nano-particle is for ensureing to obtain the terpolymer EP rubber foam materials with suitable mechanical intensity.In order to ensure physical strength, the specific surface area of inorganic nano-particle is at 10-400m
2between/g, preferred 100-300m
2/ g, more preferably 130-240m
2/ g.Described inorganic nano-particle is at least one in silicon-dioxide, calcium carbonate, kaolin, clay, aluminium sesquioxide, titanium dioxide, carbon black, polynite, potter's clay.The example of inorganic nano-particle comprises fumed silica (dry silica, thermal silica) and precipitated silica (wet silicon-dioxide, precipitated silica), calcene, nano kaoline, nano titanium oxide, nano-aluminium oxide, hard (china) clay, soft white clay etc., preferred fumed silica (dry silicon-dioxide), precipitated silica.Inorganic nano-particle can adopt single-material, or the combination of two or more differing materials.The add-on of inorganic nano-particle, coordinate 10-60 mass parts to be advisable with every 100 mass parts compositions (A) with the organic polymer that (B) adds up to, preferred use level is 30-50 mass parts.As long as the amount of inorganic nano-particle is within the scope of this, processibility and physical and mechanical properties just can reach acceptable level.
In order to inorganic nano-particle is dispersed in composition (A, B) in organic polymer, trimethyl silanol can be added, Diphenylsilanediol, hexa methyl silazane, pregnancy basic ring three silazane, dimethyldiethoxysilane, stearic acid, vinylformic acid, methacrylic acid, or end group is hydroxyl, the polydimethylpolysiloxane (hydroxy silicon oil or alkoxyl silicone oil) of alkoxyl group etc. can with the dispersion agent of inorganic nano-particle surface reaction, also alkyl triethoxysilane can be added, alkyl trimethoxysilane etc., alkyl wherein comprises methyl, ethyl, propyl group, butyl, amyl group and hexyl, octyl group, dodecyl, hexadecyl etc.The add-on of dispersion agent coordinates 0.5-30 mass parts to be advisable with every 100 mass parts nanoparticles, preferred 1-20 mass parts.Inorganic nano-particle sub-surface also can carry out hydrophobic treatment with organic acid, Organosilicon Alcohol in Organic, organopolysilazane, hexa methyl silazane, organoalkoxysilane (as dimethyldiethoxysilane), chlorosilane (as dimethyldichlorosilane(DMCS)) etc. in advance.
The mixing of the organic polymer of composition (A), (B) and the inorganic nano-particle of composition (C), can use mill or the machinery such as kneader, Banbury mixer, makes it together with above-mentioned preferred dispersant; In kneader or high temperature drying case, (vacuum) thermal treatment is carried out to gained mixture again, thus obtain the polymer base material containing nanoparticle.(vacuum) heat treated object is volatile component in order to remove in terpolymer EP rubber and vinylsiloxane rubber and the reaction accelerated between nanoparticle powder and dispersant molecule, ensures workability.The thermal treatment of vinylsiloxane rubber, generally by 100-250 DEG C, is heated above mixture 1-6 hour and is carried out at preferred 150-220 DEG C temperature.
-composition (D)-
Composition (D) production of low-temperature foaming agent is dinitrosopentamethlyene tetramine, 4, at least one in 4 '-OBSH, p-toluene sulfonyl hydrazide, Cellmic C 121.
Composition (D) production of low-temperature foaming agent median size is not more than 20.0 μm, the initial pyrolyzation temperature in ethylene-propylene rubber(EPR) composition not higher than 150 DEG C, preferably between 110 DEG C-140 DEG C.The median size of organic chemistry whipping agent, is preferably not more than 10.0 μm, is particularly preferably not more than 5.0 μm.
The production of low-temperature foaming agent of composition (D), for improving expansion ratio, falling low-density chemical substance, by generating chemical abscess, raising terpolymer EP rubber foam materials hole rate in terpolymer EP rubber foam composition.
The production of low-temperature foaming agent example of composition (D) also can be enumerated as whipping agent AK-II (changzhou orchid and chemical company, the mixture of dinitrosopentamethlyene tetramine and Cellmic C 121, auxiliary agent), blowing agent AC P-W (Zhejiang Hangzhou marine rainbow fine chemistry industry Products, the mixture of dinitrosopentamethlyene tetramine and Cellmic C 121, auxiliary agent), whipping agent ND-100 (changzhou Ying Temake chemical company product, the mixture of dinitrosopentamethlyene tetramine and auxiliary agent thereof).The example of composition (D) is also not limited to the combination of above-mentioned whipping agent and composition thereof, also can enumerate if suitable frothing aid is if carboxamide derivatives, organic acid are as phenylformic acid, stearic acid, hydroxy silicon oil, metal oxide if zinc oxide, metal-salt are as the mixture of the materials such as Zinic stearas, as long as make initial decomposition discharge temperature in terpolymer EP rubber foam composition reach not higher than 150 DEG C.Composition (D) can adopt single or two or more combinations of different materials.
In order to ensure that terpolymer EP rubber foam materials has suitable density and cure efficiency, the use level of composition (D) composition coordinates 0.5-15 mass parts to be advisable with the organic polymer that every 100 mass parts compositions (A, B) add up to, preferred 1.0-7.0 mass parts, more preferably 2-5 mass parts.
-composition (E)-
Composition (E) organo-peroxide composition is made up of lower than 155 DEG C and two class superoxide E1, the E2 being not less than 170 DEG C 1min thermal decomposition half life, and its consumption is in 0.5-10 mass parts.Its chemical formula is R
1-OO-R
2, R
1with R
2can be the same or different, can single or multiple peroxy-radical (-OO-) be contained in the molecule.Organo-peroxide is the vulcanizing agent that can be used for crosslinking component (A) ethylene-propylene-non-conjugated diene polymers and composition (B) vinylsiloxane rubber.
The middle 1min thermal decomposition half life of composition (E) is dibenzoyl peroxide (139 DEG C), 2 lower than the organo-peroxide (E1) (being 1min half life temperature in bracket) of 155 DEG C, the chloro-dibenzoyl peroxide of 4-bis-, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, 1,1-di-t-butyl peroxy-3,3, the at least one of 5-trimethyl-cyclohexane (153 DEG C), 1,1-bis(t-butylperoxy) cyclohexane (153 DEG C), peroxidized t-butyl perbenzoate (145 DEG C).1min thermal decomposition half life is not less than the hydrocarbyl superoxide (E2) of 170 DEG C for dicumyl peroxide (171 DEG C), 1,4-dual-tert-butyl peroxy isopropyl base benzene (175 DEG C), 1,3-dual-tert-butyl peroxy isopropyl base benzene (175 DEG C), 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexin, 2,5-dimethyl-2, the at least one of 5-bis(t-butylperoxy) hexane (179 DEG C), cumenyl tert-butyl peroxide (173 DEG C), E1, E2 two the mass ratio of class superoxide between 0.3-6:10.
In E1 and E2 organo-peroxide, all can adopt single organic per-compounds or two kinds, the collocation of even multiple different compound or combination.
(E) consumption of composition becomes the organic polymer of subtotaling to coordinate 0.5-10 mass parts organo-peroxide to be advisable with every 100 mass parts (A), (B), preferred 0.7-7.0 mass parts, more preferably 3-5.0 mass parts.As long as within the scope of this, the ethylene propylene diene rubber foaming composition that solidification effect is good, have high compression rebound resilience, low compression creep properties just can be obtained.The purity of organo-peroxide is advisable to be greater than 90%, as the purity of organo-peroxide lower than 90%, its actual amount can be scaled the quantity of sterling or >=90% even >=95% by its purity.
The present invention is directed to terpolymer EP rubber in the slow and fact having chain rupture to occur of peroxide cure hourly velocity, propose and add many vinyl organic compound and weaken with fast reaction speed the method that its chain rupture affects as cure activating ingredient.Adoptable many vinyl organic compound promoting agent, can be selected from cyanacrylate (TAIC), triallylcyanurate (TAC), liquid polybutadiene (HTPB), Ethylene glycol dimethacrylate (EDMA), N, N '-isophthalic methylene-bis maleimide (HVA-2), trihemellitic acid allyl ester (TATM), trihydroxy methyl propane trimethyl acrylate (TMPTA), dimethacrylate 1, 3-butylene terephthalate, magnesinm methacrylate (NDMA), zinc methacrylate (ZDMA), methacrylic acid.Its consumption becomes the organic polymer of subtotaling to coordinate 0.1-10 mass parts cure activating ingredient to be advisable with every 100 mass parts (A)/(B), preferred 0.5-5.0 mass parts, more preferably 1-3.0 mass parts.
-other compositions-
The present invention also can comprise the thermal conductivity imparting agents such as such as flint, zinc oxide or aluminum oxide; Such as diatomaceous non-reinforcing silica; And the filler of such as calcium carbonate; Such as whiteruss, machinery oil, paraffin oil, cycloalkanes wet goods tenderizer, in order to improve the processibility of terpolymer EP rubber; The such as poly interfacial agent of vinyl-vinyl acetate copolymer, ethylene-methyl acrylate multipolymer, vinyl three second (acyl) TMOS, γ-(methacryloxy) propyl trimethoxy silicane, ethylene-propylene rubber(EPR)-silane grafted copolymers, Silane Grafted; The polymer materialss such as such as polyethylene, polypropylene, polyvinyl acetate, vinyl-vinyl acetate copolymer (EVA resin), to improve its very property and foam mechanical performance, flexible material; Such as other additives of tinting material, heat resistance improver, flame retardant resistance improving agent, thermal conductivity improving agent; Inner pattern releasing agent applicable; Silane coupling agent, titanate coupling agent; And such as organoalkoxysilane, diphenyl silanodiol, carbon functional silane and there is the dispersion agent of the low-molecular-weight siloxane with silanol end-blocking two ends.
-preparation method-
The micropore terpolymer EP rubber foam materials preparation method that described compression resilience is excellent, is characterized in that mainly carrying out according to following steps:
A. the preparation of ethylene propylene diene rubber foaming composition base
The propylene of mooney viscosity more than 20-non-conjugated diene hydrocarbon copolymer or viscometric degree of polymerization are not less than the vinylsiloxane rubber of 1000, specific surface area (BET method) is not less than 10m
2the inorganic nano-particle strengthening agent of/g, necessary dispersion agent and weak reinforced filling are as calcene, diatomite etc., mix by using the methods such as rubber mixing machine, Banbury mixer or kneader, then heat-treat by the mixture of the employing method such as kneader or moisture eliminator to gained, or vacuumize under high temperature in kneader, discharge small molecules, thus obtain organic polymer reinforcement base-material.Heat treated object is to remove volatile component and accelerating the reaction between inorganic nano-particle and dispersion agent, ensures the workability of mixture.Be advisable to be no more than 130 DEG C to the heat treated temperature of terpolymer EP rubber, and heat-up time is not specifically limited, such as thermal treatment at 80 DEG C-120 DEG C, preferably can heat above mixture 10min-6 hour at 100 DEG C of-110 DEG C of temperature.To the heat treated temperature of vinylsiloxane rubber or be not specifically limited heat-up time, such as thermal treatment at 100 DEG C-250 DEG C, preferably can heat above mixture 1-6 hour at 150 DEG C of-220 DEG C of temperature.
When needs add vinylsiloxane rubber, by two kinds of mixtures of inorganic nano-particle and terpolymer EP rubber and vinylsiloxane rubber, heat blended with the interfacial agent of necessity in mill or the traditional method such as kneader, Banbury mixer, and make its dispersed enough time, after blanking, be cooled to normal temperature.
B. ethylene propylene diene rubber foaming composition base and production of low-temperature foaming agent, the mixing of organo-peroxide
In ethylene propylene diene rubber foaming composition base, add production of low-temperature foaming agent, cure activating ingredient etc. and be uniformly dispersed, under the 10h half life temperature not higher than organo-peroxide E1 and E2 subtracts the condition of 30 DEG C, add two class superoxide again and make it be uniformly dispersed, obtaining the sizing material adding production of low-temperature foaming agent.
C. the foaming sulfuration of composition
The sizing material adding production of low-temperature foaming agent is inserted die cavity, under 130 DEG C ± 10 DEG C and 0.1MPa-50MPa condition, react 5-20min realizes slight crosslinked, more high temperature vulcanized enough time obtains the terpolymer EP rubber foam materials of crosslinking curing under 170 DEG C ± 20 DEG C conditions.
To the hybrid mode of each composition, have no particular limits.This mixture is by obtaining with the mentioned component of the mixing pre-determined quantities such as two roll mill, rubber mixing machine, kneader or Banbury mixer, rubber (plastics) Banbury mixer or adding pressure type kneader, screw extrusion press.Concrete restriction is not had to the feed postition of organo-peroxide composition (E), be no matter adopt that two roll rubber mixing mill is mixing, Banbury mixer banburying or pressurization mediate, or adopt paste method, with rubber or rubber unvulcanizate, with the method such as silicone oil mixes, as long as mixed uniformly situation can be reached.
To the temperature condition parked after organo-peroxide composition (E) mixing and mixing, not to be advisable higher than the temperature of (organo-peroxide 10h half life temperature-30 DEG C).During as selected dicumyl peroxide (10h half-life decomposition temperature 117 DEG C), mixing temperature should not higher than 87 DEG C; During to dibenzoyl peroxide (10h half-life decomposition temperature 79 DEG C), mixing temperature should not higher than 49 DEG C; During to 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane (10h half-life decomposition temperature 90 DEG C), mixing temperature should not higher than 60 DEG C.To the situation that two kinds of superoxide add simultaneously, not to be as the criterion higher than the mixing temperature of 10h transformation period lower superoxide, two kinds of superoxide also can be made to add respectively and control its mixing temperature respectively.
High temperature vulcanized blowing temperature condition of the present invention, is preferably the temperature of (E2 organo-peroxide 1 minute half-life decomposition temperature ± 20 DEG C).As long as high temperature vulcanized temperature drops within the scope of this, just good cross-linking effect can be obtained.The temperature that high temperature vulcanized temperature is more preferably (organo-peroxide 1 minute half-life decomposition temperature ± 16 DEG C).As composition (D) select dicumyl peroxide (1 minute half-life decomposition temperature 171 DEG C) time, solidification value is preferably not less than 151 DEG C, is more preferably not less than 160 DEG C.
Crosslinking time when foaming to high temperature does not have concrete restriction, can be cured thin products 5-10min after high-temperature pressurizing, can be cured at 10min-1h general goods, the restriction that the curing time for thick product is not fixed, with goods core crosslinked be entirely suitable.In addition, also in type foam materials can be obtained the goods of required physical dimension and shape by mechanical workout.
Necessary pressure condition, refers to the pressure condition reaching and mould matched moulds, composition mold filling can be made shaping.Pressure condition, is generally 0.1-50MPa, is preferably 1-30MPa.
Crosslinked or the curing mode of the micropore terpolymer EP rubber foam materials that compression resilience of the present invention is excellent does not have special restriction, the modes such as compacting (mold pressing), injection molding or transmission (note pressure), extrusion moulding all can adopt, and preferably adopt compacting, transmission and injection molding etc.
Compared with prior art, one of beneficial effect of the present invention is: can obtain the excellent micropore terpolymer EP rubber foam materials of compression resilience according to the present invention, no matter use compression-moulding methods/extrude or injection moulding method, all can obtain the fine cellular terpolymer EP rubber foam materials that mechanical strength is higher, outward appearance is good, inner homogeneous is consistent.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Below in each embodiment, " part " refers to " mass parts ".
Embodiment 1
By 100 parts of ethylene-propylene-ethyiidenenorbomene copolymer (trade mark MITSUI4045, mooney viscosities
45, iodine number 23), 50 parts of BET specific surface area are 195m
2the dry silica AS-200 of/g (trade(brand)name, Shenyang Chemical Co., Ltd. manufactures), 15 parts of Witco 70s and 3 parts comprise silanol group at two ends and viscosity is 29mm
2the dimethyl polysiloxane of/s (23 DEG C) adds in 5L Banbury mixer, and at 80 DEG C, heat banburying 30min, discharging is cooled to room temperature, namely obtains terpolymer EP rubber reinforcement base-material.
By 100 parts containing dimethyl siloxane units 90.825 % by mole, methyl vinyl siloxane unit 0.15 % by mole, methylphenylsiloxane units 10.0 % by mole, dimethylvinyl siloxane unit 0.025 % by mole, mean polymerisation degree be 8000 organopolysiloxane, 50 parts of BET surface-area 200m
2the fumed silica AS-200 of/g, 5 parts there is silanol group and viscosity is 29mm at two ends
2after the dimethyl polysiloxane of/s (23 DEG C) coordinates with kneading machine, at 180 DEG C thermal treatment 2h, be cooled to room temperature, be namely made vinylsiloxane rubber reinforcement base-material.
By terpolymer EP rubber reinforcement base-material 153 parts and vinylsiloxane rubber reinforcement base-material 15.5 parts, ethylene-acrylate copolymer (du pont company VamacDP) 3 parts blended 20min at 160 DEG C in Banbury mixer, after mixing, discharging cooling obtains EPT rubber composition base-material.
Add in 171.5 parts of EPT rubber composition base-materials prepared like this:
4 parts of ND-100 whipping agents (Changzhou Ying Temake company limited produces, the 1:1 mixture of N, N-dinitrosopentamethlyene tetramine and carboxamide, white particle, median size 6-8 micron, heat decomposition temperature 125-128 DEG C, discharge quantity 160-180ml/g);
The 1:1 mixture (purity 96%) of 4 parts of dibenzoyl peroxide and vinylsiloxane rubber is as component E1;
4 parts of Isosorbide-5-Nitrae-dual-tert-butyl cumene hydroperoxides (purity 96%) are as component E2;
3 parts of zinc oxide (purity 98%, particle diameter is less than 2 microns) are as heat resistance accessory;
0.5 part of anti-aging agent RD (technical grade) protects auxiliary agent as resistance to.
In two roll mill, thoroughly mix all materials except E1 component successively, then mix the sizing material that E1 component obtains containing whipping agent under not higher than the roller temperature of 44 DEG C, and slice prepares compound blank.Then 130 DEG C, mold pressing said composition 7-10min realizes slight crosslinked (i.e. precrosslink) under the condition of 10MPa, then the compound blank that mold pressing is cross-linked in larger die cavity at 165 DEG C obtains the square plate of thickness 7-20mm or difform goods, again goods thick for this 7-20mm are eliminated the micro-molecular gas of its inside by 90-120 DEG C of 8h thermal treatment, eventually pass mechanical workout and obtain difform product or sample.
By terpolymer EP rubber foam materials, according to the hardness of GB/T531-1999 test sample, the rubbery foam sheet of the thickness of 0.5-3mm is obtained by cuing open sheet processing, the rubbery foam sheet cutting 2mm thickness according to the shape cut-off knife of I type sample in GB/T528 obtains tensile property sample, according to method test tensile strength, the tensile yield of GB/T528-1999; By the rubbery foam sheet of 2mm, at 48 DEG C, compress 50%, keep 48h, after unloading test compression tension set during 30min, its physical and mechanical properties data are in table 1.
Embodiment 2
Prepare terpolymer EP rubber reinforcement base-material and vinylsiloxane rubber reinforcement base-material similarly to Example 1; And by the terpolymer EP rubber reinforcement base-material of 51 parts and 108.5 mass parts vinylsiloxane rubber reinforcement base-materials and 3 parts of ethylene-acrylate copolymer (du pont company VamacDP) blended 20min in the Banbury mixer of 150 DEG C, after mixing, obtain EPT rubber composition base-material.
Add in 162.5 parts of EPT rubber composition base-materials prepared like this:
5 parts of ACP-W whipping agent (Hangzhou marine rainbow fine chemistry industry stock company, the mixture of N, N-dinitrosopentamethlyene tetramine and Cellmic C 121 and frothing aid, median size 9-14 micron, discharge quantity 125-135ml/g, initial pyrolyzation temperature 125-133 DEG C);
0.4 part of 1,1-di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane (purity 95%) is as component E1;
3 part of 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (purity 95%) is as component E2;
3 parts of zinc oxide (purity 98%, particle diameter is less than 2 microns) are as heat resistance accessory;
1 part of cyanacrylate is as cure activating ingredient;
0.4 part of antioxidant MB (technical grade) protects auxiliary agent as resistance to.
In twin-roll plastic mixing mill successively thoroughly mixing except E1 component all materials, then adds E1 component under not higher than the roller temperature of 60 DEG C and be mixed to get sizing material containing whipping agent, and slice prepares compound blank.Then at 130 DEG C of mold pressing said composition 7-10min, then obtain the difform goods of thickness 2-20mm 170 DEG C of mold pressing said compositions, then obtain difform product or sample by mechanical workout, its physical and mechanical properties data are in table 1.
Embodiment 3
Except not using component (B), component A is 100 mass parts and component (C) changes 40 parts of carbon blacks 774 into, silicone oil changes 1.0 parts of stearic acid into, 3 parts of zinc oxide, in addition organo-peroxide E1 is adjusted to 1 part 1 by dibenzoyl peroxide, 1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane, 1 of E2,4-dual-tert-butyl cumene hydroperoxide consumption is adjusted to 5 parts and omits beyond blended operation and ethylene acrylate copolymer, prepare terpolymer EP rubber foam materials similarly to Example 1, its physical and mechanical properties data are in table 1.
Embodiment 4
Except component (A), (B) mass parts changes 50 parts into, the component (C) coordinated with component (A) changes 20 parts of carbon blacks 774 into, the component (C) coordinated with component (B) changes 20 parts of dry silica into, silicone oil changes 0.5 part of stearic acid into, 1.5 parts of zinc oxide, in addition by organo-peroxide E1 by 1, 1-di-t-butyl peroxy-3, 3, 5-trimethyl-cyclohexane is adjusted to 4 parts of dibenzoyl peroxide and vinylsiloxane rubber 1:1 mixture, 2 of E2, 5-dimethyl-2, 5-bis(t-butylperoxy) hexane consumption is adjusted to beyond 4 parts, prepare terpolymer EP rubber foam materials similarly to Example 2, its physical and mechanical properties data are in table 1.
Comparative example 1
The method of embodiment 1 is repeated by component concentration each shown in table 1, except without except component (E1), the ND-100 whipping agent of component (D) is adjusted to ACP-W whipping agent, the consumption of component (E2) is adjusted to 3 parts, cryogenic vulcanization temperature is adjusted to 155 DEG C-160 DEG C by 130 DEG C, shaping terpolymer EP rubber foam materials similarly to Example 1, its physical and mechanical properties data are in table 1.
Comparative example 2
The method of embodiment 4 is repeated by each component concentration shown in table 1, except without except component (E2), the ACP-W whipping agent of component (D) is adjusted to ND-100 whipping agent, dibenzoyl peroxide and the vinylsiloxane rubber 1:1 mixture of component (E1) are adjusted to 1,1-di-t-butyl peroxy-3,3,5-trimethyl-cyclohexane 2 parts, cryogenic vulcanization temperature is adjusted to 145 DEG C-150 DEG C by 130 DEG C, shaping terpolymer EP rubber foam materials similarly to Example 1, its physical and mechanical properties data are in table 1.
Table 1 each embodiment physical and mechanical properties data
As can be seen from Table 1, micropore terpolymer EP rubber foam compresses tension set prepared by the present invention is little, and compressive creep is excellent, and therefore the compression resilience of this micropore terpolymer EP rubber foam materials obtains obvious optimization.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.More particularly, in scope disclosed in the present application, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.
Claims (10)
1. the micropore terpolymer EP rubber foam materials that compression resilience is excellent, is characterized in that this material is made by comprising the following component of measuring by mass parts:
Non-conjugated diene hydrocarbon in wherein ethylene-propylene-non-conjugated diene hydrocarbon copolymer is selected from ethylidene norbornene, Isosorbide-5-Nitrae-hexadiene and isoprene, and the mooney viscosity of multipolymer is not less than 20; The polymerization degree of vinylsiloxane rubber is not less than 1000 and contains at least 2 alkenyls be connected with Siliciumatom; The organo-peroxide E2 that organo-peroxide composition is not less than 170 DEG C by 1min thermal decomposition half life lower than the organo-peroxide E1 of 155 DEG C and 1min thermal decomposition half life is formed.
2. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, it is characterized in that described organo-peroxide E1 is dibenzoyl peroxide, 2, the chloro-dibenzoyl peroxide of 4-bis-, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, 1,1-di-t-butyl peroxy-3,3, at least one in 5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy) cyclohexane, peroxidized t-butyl perbenzoate; Described organo-peroxide E2 is dicumyl peroxide, 1,4-dual-tert-butyl peroxy isopropyl base benzene, 1,3-dual-tert-butyl peroxy isopropyl base benzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexin, 2, at least one in 5-dimethyl-2,5-bis(t-butylperoxy) hexane; The mass ratio that described 1min thermal decomposition half life is greater than the organo-peroxide of 170 DEG C lower than the organo-peroxide of 155 DEG C and described 1min thermal decomposition half life is 0.3-6:10.
3. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, is characterized in that the iodine number of described ethylene-propylene-non-conjugated diene hydrocarbon copolymer is for (5-30)/100g.
4. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, is characterized in that the contents of ethylene of described vinylsiloxane rubber is 0.04-0.5mol%.
5. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, is characterized in that described inorganic nano-particle is the nanoparticle of at least one in silicon-dioxide, calcium carbonate, kaolin, clay, aluminium sesquioxide, titanium dioxide, carbon black, polynite, potter's clay.
6. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 5 is excellent, is characterized in that the BET method specific surface area of described inorganic nano-particle is 10-400m
2/ g.
7. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, it is characterized in that described production of low-temperature foaming agent is dinitrosopentamethlyene tetramine, 4, at least one in 4 '-OBSH, p-toluene sulfonyl hydrazide, Cellmic C 121.
8. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 7 is excellent, it is characterized in that the discharge quantity of described production of low-temperature foaming agent is not less than 100ml/g, particle diameter is not more than 20 μm, and the temperature of initial decomposition in rubber is not higher than 150 DEG C.
9. the micropore terpolymer EP rubber foam materials that compression resilience according to claim 1 is excellent, it is characterized in that also comprising cyanacrylate, triallylcyanurate, liquid polybutadiene, Ethylene glycol dimethacrylate, N, N '-isophthalic methylene-bis maleimide, trihemellitic acid allyl ester, trihydroxy methyl propane trimethyl acrylate, dimethacrylate 1, the cure activating ingredient of at least one in 3-butylene terephthalate, magnesinm methacrylate, zinc methacrylate, methacrylic acid, and its consumption is 0.1-10 part.
10. prepare a method for the excellent micropore terpolymer EP rubber foam materials of compression resilience as described in any one of claim 1-9, it is characterized in that comprising the following steps:
A. ethylene-propylene-non-conjugated diene hydrocarbon copolymer, vinylsiloxane rubber are uniformly dispersed in mill or kneader, banburying equipment with inorganic nano-particle respectively, appropriate dispersion agent is added in dispersion process, at high temperature discharge small molecules, obtain two kinds of mixtures, again these two kinds of mixtures are uniformly dispersed by heating is blended under appropriate interfacial agent effect, cool after blanking, obtain EPT rubber composition base-material;
B. in EPT rubber composition base-material, add production of low-temperature foaming agent, cure activating ingredient is uniformly dispersed, under the 10h half life temperature not higher than organo-peroxide E1 and organo-peroxide E2 deducts the temperature condition of 30 DEG C, add these two kinds of organo-peroxides again and be uniformly dispersed, obtaining the sizing material adding production of low-temperature foaming agent;
C. the described sizing material adding production of low-temperature foaming agent is injected die cavity, at temperature 130 DEG C ± 10 DEG C and pressure 0.1MPa-50MPa condition, react 5-20min realizes slight crosslinked, more high temperature vulcanized enough time obtains described micropore terpolymer EP rubber foam materials under temperature 170 DEG C ± 20 DEG C conditions.
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