CN105602052A - Anti-aging rubber fender for vessel - Google Patents
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- CN105602052A CN105602052A CN201610000170.9A CN201610000170A CN105602052A CN 105602052 A CN105602052 A CN 105602052A CN 201610000170 A CN201610000170 A CN 201610000170A CN 105602052 A CN105602052 A CN 105602052A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses an anti-aging rubber fender for a vessel. The anti-aging rubber fender is prepared from, by weight, 15-32 parts of natural rubber, 10-25 parts of chloroprene rubber, 5-24 parts of epichlorohydrin rubber, 15-24 parts of ABS resin, 0.5-1.5 parts of dicumyl peroxide, 0.8-1.4 parts of isocyanuric acid triallyl ester, 0.5-1.5 parts of magnesium oxide, 30-55 parts of modified halloysite nanotubes, 8-14 parts of hard clay, 10-18 parts of mica powder, 8-14 parts of nano-silica, 5-12 parts of carbon black N330, 1-2.5 parts of coumarone, 1-2.5 parts of paraffin, 1-2.5 parts of dioctyl phthalate, 0.5-1.5 parts of an antioxidant MD-1024 and 0.5-1.5 parts of an antioxidant BHT. The anti-aging rubber fender is resistant to abrasion and aging and excellent in elasticity.
Description
Technical field
The present invention relates to rubber technology field, relate in particular to a kind of ageing-resistant boats and ships rubber fender.
Background technology
The elastomeric material that boats and ships use normally plays vital effect, elastomeric material aspect operation maintaining boats and shipsMust be able to resist Exposure to Sunlight, aging and soda acid erosion, and can bear the weather conditions that high temperature, severe cold etc. are harsh, simultaneously in unexpected calamityIn evil situation, still can temporarily ensure that it normally moves. The working environment very severe of rubber fender in boats and ships, should ensure resistance toMill, ageing-resistant, and require again to have excellent elasticity, a lot of shipowners, from for the purpose of the safe operation of boats and ships, prevent boats and ships fender instituteThe damage of the elastomeric material using, often changes fender, has not only increased operation costs, while also having restricted the continuous length of some needsBetween the safe operation of the boats and ships of executing the task.
Summary of the invention
The present invention proposes a kind of ageing-resistant boats and ships rubber fender, wear-resisting, ageing-resistant, good springiness.
The ageing-resistant boats and ships rubber fender of one that the present invention proposes, its raw material comprises by weight: natural rubber 15～32 parts, 10～25 parts of neoprenes, 5～24 parts of chlorohydrin rubbers, 15～24 parts of ABS resins, cumyl peroxide 0.5～1.5Part, 0.8～1.4 part of triallyl isocyanurate, 0.5～1.5 part, magnesia, 30～55 parts of modification halloysite nanotubes, hard8～14 parts, potter's clay, 10～18 parts of mica powders, 8～14 parts of nano silicons, carbon black N3305～12 part, coumarone 1～2.5Part, 1～2.5 part, paraffin, 1～2.5 part of dioctyl phthalate, antioxidant MD-10240.5～1.5 part, antioxidant BHT0.5～1.5 part.
Preferably, modification halloysite nanotubes adopts following technique preparation: o-chloraniline, p-methyl benzenesulfonic acid, chlorobenzene are mixedClose evenly, rising temperature to 115～129 DEG C, add crotonaldehyde to reflux, and solvent is removed in decompression distillation, collect 145～150 DEG C/246Pa cut, adds ortho-aminobenzoic acid, KI, mixed in hydrochloric acid even, is heated to 90～98 DEG C, adds crotonaldehyde to reflux,Add again halloysite nanotubes, white carbon, acetone, maleic anhydride, γ-glycidyl ether oxygen propyl trimethoxy silicane to stirMix, then add antioxidant H, antioxidant 4010, antioxidant A, under nitrogen protection, stir, filter, washing, vacuum drying obtainsTo modification halloysite nanotubes.
Preferably, in the preparation technology of modification halloysite nanotubes, the weight ratio of o-chloraniline, p-methyl benzenesulfonic acid, chlorobenzeneBe 8～22:0.2～0.8:80～120.
Preferably, in the preparation technology of modification halloysite nanotubes, ortho-aminobenzoic acid, KI, halloysite nanotubes,The weight ratio of white carbon, maleic anhydride, γ-glycidyl ether oxygen propyl trimethoxy silicane be 10～18:0.2～0.8:17～24：2～3.5：0.5～3.5：1.2～1.8。
Preferably, in the preparation technology of modification halloysite nanotubes, the weight of antioxidant H, antioxidant 4010, antioxidant AThan being 0.2～1.5:0.2～1.5:0.2～1.5.
Preferably, modification halloysite nanotubes adopts following technique preparation: by weight by 8～22 parts of o-chloranilines, 0.2～0.8 part of p-methyl benzenesulfonic acid, 80～120 parts of chlorobenzenes mix, and rising temperature to 115～129 DEG C add 5～12 parts of crotonsAldehyde backflow 30～60min, solvent is removed in decompression distillation, collects 145～150 DEG C/246Pa cut, adds 10～18 parts of adjacent aminoThe mixed in hydrochloric acid that benzoic acid, 0.2～0.8 part of KI, 60～90 parts of concentration are 1.5～2.5mol/L is even, be heated to 90～98 DEG C, add 15～25 parts of crotonaldehydes backflow 0.5～1.5h, then add 17～24 parts of halloysite nanotubes, 2～3.5 parts of hard charcoalsBlack, 50～90 parts of acetone, 0.5～3.5 part of maleic anhydride, 1.2～1.8 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanesStir, whipping temp is 55～75 DEG C, and mixing time is 5～12h, then add 0.2～1.5 part of antioxidant H, 0.2～1.5 parts of antioxidant 4010s, 0.2～1.5 part of antioxidant A, continue to stir 12～18h under nitrogen protection, filter, and washing, vacuum is dryThe dry modification halloysite nanotubes that obtains.
Preferably, the weight ratio of modification halloysite nanotubes, natural rubber, neoprene, chlorohydrin rubber, ABS resin is40～46：26～28：22～24：15～20：21～23。
Preferably, the weight of modification halloysite nanotubes, hard (china) clay, mica powder, nano silicon, carbon black N330Than being 40～46:9～11:12～15:9～12:6～8.
Preferably, the weight ratio of modification halloysite nanotubes, antioxidant MD-1024, antioxidant BHT is 40～46:0.6～1：0.6～1。
Preferably, described ageing-resistant boats and ships rubber fender, its raw material comprises by weight: natural rubber 26～28Part, 22～24 parts of neoprenes, 15～20 parts of chlorohydrin rubbers, 21～23 parts of ABS resins, 1～1.2 part of cumyl peroxide,0.9～1.1 part of triallyl isocyanurate, 0.6～0.8 part, magnesia, 40～46 parts of modification halloysite nanotubes, hard pottery9～11 parts, soil, 12～15 parts of mica powders, 9～12 parts of nano silicons, carbon black N3306～8 part, 1.6～2 parts of coumarones,2.2～2.4 parts, paraffin, 1.8～2 parts of dioctyl phthalates, antioxidant MD-10240.6～1 part, antioxidant BHT0.6～1 part.
Wherein, ageing-resistant boats and ships of the present invention adopt preparation technology's preparation of general General Purpose Rubber with rubber fender.
The present invention is taking natural rubber, neoprene, chlorohydrin rubber, ABS resin as major ingredient, adopt cumyl peroxide,Triallyl isocyanurate, magnesia vulcanize, and make the present invention ageing-resistant better with wearability; And modification galapectite nanometerPipe, hard (china) clay, mica powder, nano silicon, carbon black N330, significantly can improve anti-wear performance of the present invention, then with ancient horseGrand, paraffin, dioctyl phthalate act synergistically, and are strengthening under the prerequisite of hardness of the present invention, make elasticity of the present invention suitableIn.
In the preparation technology of modification halloysite nanotubes, in o-chloraniline, amino ortho position chlorine atom is due to sterically hindered effectShould, on chlorine atom outermost layer P electronics and aromatic ring, large π key forms conjugation, causes cloud density increase, and alkalescence is stronger, and to firstAfter benzene sulfonic acid, crotonaldehyde organically combine, then with ortho-aminobenzoic acid, KI, halloysite nanotubes, maleic anhydride, γ-Glycidyl ether oxygen propyl trimethoxy silicane, antioxidant H, antioxidant 4010, antioxidant A organically combine, KI whereinCan destroy carboxyl and amino combination in ortho-aminobenzoic acid, the carboxyl in amino benzoic Acid with amino can with maleic anhydride in the utmost pointIn the silicon hydroxyl of property group, white carbon and antioxidant H, antioxidant 4010, antioxidant A, group mutually combines, the not only active force utmost pointBy force, make ageing-resistant performance of the present invention very excellent, and antioxidant H, antioxidant 4010, antioxidant A dispersed utmost point in major ingredientGood, under the effect of maleic anhydride, γ-glycidyl ether oxygen propyl trimethoxy silicane, fabulous with the compatibility of major ingredient, interfaceAdhesion is strong, is difficult for occurring migration and causes losing anti-aging effect. Halloysite nanotubes is curling tubular structure simultaneously, its hardnessLow, absorption property is fabulous, under the synergy of maleic anhydride, γ-glycidyl ether oxygen propyl trimethoxy silicane, and galapectiteNanotube and hard (china) clay, mica powder, nano silicon, carbon black N330 organically combine, and make hardness of the present invention and elasticityReach balanced, tear-resistant performance is very excellent.
And modification halloysite nanotubes and antioxidant MD-1024, antioxidant BHT effect can further strengthen the present inventionAgeing-resistant performance, extends service life of the present invention; Simultaneously modification halloysite nanotubes can prevent mica powder, nano silicon,Carbon black N330 reunites, and also can effectively strengthen between hard (china) clay, mica powder, nano silicon, carbon black N330 and major ingredientInteraction, not only improved the dispersiveness of above-mentioned material in major ingredient, and can form physics crosspoint, make rubber moleculeChain tangles mutually around modification halloysite nanotubes, hard (china) clay, mica powder, nano silicon, carbon black N330, when stretchingBe difficult for sliding, make the tear-resistant intensity of the present invention fabulous, the utmost point is applicable to boats and ships fender.
Detailed description of the invention
Embodiment 1
A kind of ageing-resistant boats and ships rubber fender, its raw material comprises by weight: 15 parts of natural rubbers, 25 parts of neoprenes, chlorine5 parts of hydrin rubbers, 24 parts of ABS resins, 0.5 part of cumyl peroxide, 1.4 parts of triallyl isocyanurates, 0.5 part, magnesia,55 parts of modification halloysite nanotubes, 8 parts of hard (china) claies, 18 parts of mica powders, 8 parts of nano silicons, carbon black N33012 part, GuGrand 1 part of horse, 2.5 parts, paraffin, 1 part of dioctyl phthalate, antioxidant MD-10241.5 part, 0.5 part of antioxidant BHT.
Embodiment 2
A kind of ageing-resistant boats and ships rubber fender, its raw material comprises by weight: 32 parts of natural rubbers, 10 parts of neoprenes, chlorine24 parts of hydrin rubbers, 15 parts of ABS resins, 1.5 parts of cumyl peroxides, 0.8 part of triallyl isocyanurate, magnesia 1.5Part, 30 parts of modification halloysite nanotubes, 14 parts of hard (china) claies, 10 parts of mica powders, 14 parts of nano silicons, carbon black N3305Part, 2.5 parts of coumarones, 1 part, paraffin, 2.5 parts of dioctyl phthalates, antioxidant MD-10240.5 part, antioxidant BHT1.5 part.
Embodiment 3
A kind of ageing-resistant boats and ships rubber fender, its raw material comprises by weight: 26 parts of natural rubbers, 24 parts of neoprenes, chlorine15 parts of hydrin rubbers, 23 parts of ABS resins, 1 part of cumyl peroxide, 1.1 parts of triallyl isocyanurates, 0.6 part, magnesia,46 parts of modification halloysite nanotubes, 9 parts of hard (china) claies, 15 parts of mica powders, 9 parts of nano silicons, carbon black N3308 part, ancient horseGrand 1.6 parts, 2.4 parts, paraffin, 1.8 parts of dioctyl phthalates, antioxidant MD-10241 part, 0.6 part of antioxidant BHT.
Modification halloysite nanotubes adopts the preparation of following technique: by weight by 22 parts of o-chloranilines, 0.2 part to toluene sulphurAcid, 120 parts of chlorobenzenes mix, and rising temperature to 115 DEG C, adds 12 parts of crotonaldehyde backflow 30min, and decompression distillation is removed moltenAgent, collects 145～150 DEG C/246Pa cut, adds 18 parts of ortho-aminobenzoic acids, 0.2 part of KI, 90 parts of concentration to beThe mixed in hydrochloric acid of 1.5mol/L is even, is heated to 98 DEG C, adds 15 parts of crotonaldehyde backflow 1.5h, then adds 17 parts of galapectite nanometersPipe, 3.5 parts of white carbons, 50 parts of acetone, 3.5 parts of maleic anhydrides, 1.2 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes enterRow stirs, and whipping temp is 75 DEG C, and mixing time is 5h, then adds 1.5 parts of antioxidant H, 0.2 part of antioxidant 4010,1.5 partsAntioxidant A, continues to stir 12h under nitrogen protection, filters, and washing, vacuum drying obtains modification halloysite nanotubes.
Embodiment 4
A kind of ageing-resistant boats and ships rubber fender, its raw material comprises by weight: 28 parts of natural rubbers, 22 parts of neoprenes, chlorine20 parts of hydrin rubbers, 21 parts of ABS resins, 1.2 parts of cumyl peroxides, 0.9 part of triallyl isocyanurate, magnesia 0.8Part, 40 parts of modification halloysite nanotubes, 11 parts of hard (china) claies, 12 parts of mica powders, 12 parts of nano silicons, carbon black N3306Part, 2 parts of coumarones, 2.2 parts, paraffin, 2 parts of dioctyl phthalates, antioxidant MD-10240.6 part, antioxidant BHT 1Part.
Modification halloysite nanotubes adopts the preparation of following technique: by weight by 8 parts of o-chloranilines, 0.8 part to toluene sulphurAcid, 80 parts of chlorobenzenes mix, and rising temperature to 129 DEG C, adds 5 parts of crotonaldehyde backflow 60min, and solvent is removed in decompression distillation,Collect 145～150 DEG C/246Pa cut, adding 10 parts of ortho-aminobenzoic acids, 0.8 part of KI, 60 parts of concentration is 2.5mol/LMixed in hydrochloric acid even, be heated to 90 DEG C, add 25 parts of crotonaldehyde backflow 0.5h, then add 24 parts of halloysite nanotubes, 2 parts whiteCarbon black, 90 parts of acetone, 0.5 part of maleic anhydride, 1.8 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes stir, and stirTemperature is 55 DEG C, and mixing time is 12h, then adds 0.2 part of antioxidant H, 1.5 parts of antioxidant 4010s, 0.2 part of antioxidant A, nitrogenThe lower stirring 18h that continues of gas protection, filters, washing, and vacuum drying obtains modification halloysite nanotubes.
Embodiment 5
A kind of ageing-resistant boats and ships rubber fender, its raw material comprises by weight: 27 parts of natural rubbers, 23 parts of neoprenes, chlorine18 parts of hydrin rubbers, 22 parts of ABS resins, 1.1 parts of cumyl peroxides, 1 part of triallyl isocyanurate, 0.7 part, magnesia,44 parts of modification halloysite nanotubes, 10 parts of hard (china) claies, 14 parts of mica powders, 11 parts of nano silicons, carbon black N3307 part, GuGrand 1.8 parts of horse, 2.3 parts, paraffin, 1.9 parts of dioctyl phthalates, antioxidant MD-10240.8 part, antioxidant BHT 0.8Part.
Modification halloysite nanotubes adopts the preparation of following technique: by weight by 16 parts of o-chloranilines, 0.6 part to toluene sulphurAcid, 110 parts of chlorobenzenes mix, and rising temperature to 119 DEG C, adds 8 parts of crotonaldehyde backflow 40min, and solvent is removed in decompression distillation,Collect 145～150 DEG C/246Pa cut, adding 14 parts of ortho-aminobenzoic acids, 0.6 part of KI, 82 parts of concentration is 1.9mol/LMixed in hydrochloric acid even, be heated to 94 DEG C, add 19 parts of crotonaldehyde backflow 1h, then add 19 parts of halloysite nanotubes, 3.2 parts whiteCarbon black, 70 parts of acetone, 1.5 parts of maleic anhydrides, 1.6 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes stir, and stirTemperature is 59 DEG C, and mixing time is 8h, then adds 0.9 part of antioxidant H, 0.7 part of antioxidant 4010,0.8 part of antioxidant A, nitrogenThe lower stirring 16h that continues of gas protection, filters, washing, and vacuum drying obtains modification halloysite nanotubes.
The above, be only preferably detailed description of the invention of the present invention, but protection scope of the present invention is not limited to this,Anyly be familiar with in technical scope that those skilled in the art disclose in the present invention, according to technical scheme of the present invention andInventive concept is equal to replaces or changes, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. an ageing-resistant boats and ships rubber fender, is characterized in that, its raw material comprises by weight: natural rubber 15～32Part, 10～25 parts of neoprenes, 5～24 parts of chlorohydrin rubbers, 15～24 parts of ABS resins, 0.5～1.5 part of cumyl peroxide,0.8～1.4 part of triallyl isocyanurate, 0.5～1.5 part, magnesia, 30～55 parts of modification halloysite nanotubes, hard pottery8～14 parts, soil, 10～18 parts of mica powders, 8～14 parts of nano silicons, carbon black N3305～12 part, 1～2.5 part of coumarone,1～2.5 part, paraffin, 1～2.5 part of dioctyl phthalate, antioxidant MD-10240.5～1.5 part, antioxidant BHT0.5～1.5 part.
2. ageing-resistant boats and ships rubber fender according to claim 1, is characterized in that, modification halloysite nanotubes adoptsFollowing technique preparation: o-chloraniline, p-methyl benzenesulfonic acid, chlorobenzene are mixed, and rising temperature to 115～129 DEG C, add crotonsAldehyde refluxes, and solvent is removed in decompression distillation, collects 145～150 DEG C/246Pa cut, adds ortho-aminobenzoic acid, KI, hydrochloric acidMix, be heated to 90～98 DEG C, add crotonaldehyde to reflux, then add halloysite nanotubes, white carbon, acetone, maleic acidAcid anhydride, γ-glycidyl ether oxygen propyl trimethoxy silicane stir, and then add antioxidant H, antioxidant 4010, age resistorA, stirs under nitrogen protection, filters, and washing, vacuum drying obtains modification halloysite nanotubes.
3. ageing-resistant boats and ships rubber fender according to claim 2, is characterized in that the system of modification halloysite nanotubesIn standby technique, the weight ratio of o-chloraniline, p-methyl benzenesulfonic acid, chlorobenzene is 8～22:0.2～0.8:80～120.
4. ageing-resistant boats and ships rubber fender according to claim 2, is characterized in that the system of modification halloysite nanotubesIn standby technique, ortho-aminobenzoic acid, KI, halloysite nanotubes, white carbon, maleic anhydride, γ-glycidyl ether oxygen propylThe weight ratio of trimethoxy silane is 10～18:0.2～0.8:17～24:2～3.5:0.5～3.5:1.2～1.8.
5. ageing-resistant boats and ships rubber fender according to claim 2, is characterized in that the system of modification halloysite nanotubesIn standby technique, the weight ratio of antioxidant H, antioxidant 4010, antioxidant A is 0.2～1.5:0.2～1.5:0.2～1.5.
6. according to the ageing-resistant boats and ships rubber fender described in claim 1-5 any one, it is characterized in that, modification galapectite is receivedMitron adopts the preparation of following technique: by weight by 8～22 parts of o-chloranilines, 0.2～0.8 part of p-methyl benzenesulfonic acid, 80～120 partsChlorobenzene mixes, and rising temperature to 115～129 DEG C add 5～12 parts of crotonaldehydes backflow 30～60min, and decompression distillation is removedSolvent, collects 145～150 DEG C/246Pa cut, add 10～18 parts of ortho-aminobenzoic acids, 0.2～0.8 part of KI, 60～The mixed in hydrochloric acid that 90 parts of concentration is 1.5～2.5mol/L is even, is heated to 90～98 DEG C, adds 15～25 parts of crotonaldehydes to reflux0.5～1.5h, then add 17～24 parts of halloysite nanotubes, 2～3.5 parts of white carbons, 50～90 parts of acetone, 0.5～3.5 portion of horseCarry out acid anhydrides, 1.2～1.8 parts of γ-glycidyl ether oxygen propyl trimethoxy silicanes stir, whipping temp is 55～75 DEG C,Mixing time is 5～12h, then adds 0.2～1.5 part of antioxidant H, 0.2～1.5 part of antioxidant 4010,0.2～1.5 part anti-Old agent A, continues to stir 12～18h under nitrogen protection, filters, and washing, vacuum drying obtains modification halloysite nanotubes.
7. according to the ageing-resistant boats and ships rubber fender described in claim 1-6 any one, it is characterized in that, modification galapectite is receivedThe weight ratio of mitron, natural rubber, neoprene, chlorohydrin rubber, ABS resin is 40～46:26～28:22～24:15～20:21～23。
8. according to the ageing-resistant boats and ships rubber fender described in claim 1-7 any one, it is characterized in that, modification galapectite is receivedThe weight ratio of mitron, hard (china) clay, mica powder, nano silicon, carbon black N330 be 40～46:9～11:12～15:9～12：6～8。
9. according to the ageing-resistant boats and ships rubber fender described in claim 1-8 any one, it is characterized in that, modification galapectite is receivedThe weight ratio of mitron, antioxidant MD-1024, antioxidant BHT is 40～46:0.6～1:0.6～1.
10. according to the ageing-resistant boats and ships rubber fender described in claim 1-9 any one, it is characterized in that, its raw material is by heavyAmount part comprises: 26～28 parts of natural rubbers, and 22～24 parts of neoprenes, 15～20 parts of chlorohydrin rubbers, 21～23 parts of ABS resins,1～1.2 part of cumyl peroxide, 0.9～1.1 part of triallyl isocyanurate, 0.6～0.8 part, magnesia, modification dust Lip river40～46 parts of stone nanotubes, 9～11 parts of hard (china) claies, 12～15 parts of mica powders, 9～12 parts of nano silicons, carbon black N3306～8 parts, 1.6～2 parts of coumarones, 2.2～2.4 parts, paraffin, 1.8～2 parts of dioctyl phthalates, antioxidant MD-10240.6～1 part, 0.6～1 part of antioxidant BHT.
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| CN106496669A (en) * | 2016-11-25 | 2017-03-15 | 安徽美翔塑业有限公司 | A kind of rubber tube material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496669A (en) * | 2016-11-25 | 2017-03-15 | 安徽美翔塑业有限公司 | A kind of rubber tube material and preparation method thereof |
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