CN106009603A - Preparation method of tear-resistant modified composite environment-friendly rubber base material - Google Patents
Preparation method of tear-resistant modified composite environment-friendly rubber base material Download PDFInfo
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- CN106009603A CN106009603A CN201610617284.8A CN201610617284A CN106009603A CN 106009603 A CN106009603 A CN 106009603A CN 201610617284 A CN201610617284 A CN 201610617284A CN 106009603 A CN106009603 A CN 106009603A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 47
- 239000010439 graphite Substances 0.000 claims description 47
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 17
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 239000004014 plasticizer Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- OFGVPLJWXLEAEN-UHFFFAOYSA-N 2,2-dimethylpropoxy-diethoxy-pentylsilane Chemical compound CC(CO[Si](OCC)(OCC)CCCCC)(C)C OFGVPLJWXLEAEN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 5
- 238000004220 aggregation Methods 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004677 Nylon Substances 0.000 abstract description 17
- 229920001778 nylon Polymers 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 abstract description 2
- 229960001545 hydrotalcite Drugs 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract 4
- 229920000049 Carbon (fiber) Polymers 0.000 abstract 1
- 239000010426 asphalt Substances 0.000 abstract 1
- 239000004917 carbon fiber Substances 0.000 abstract 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
- C08L71/03—Polyepihalohydrins
-
- 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
- C08K2201/001—Conductive additives
-
- 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
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses a preparation method of a tear-resistant modified composite environment-friendly rubber base material. The method comprises the following steps: preparing graphene oxide with high oxidation degree; and modifying the graphene oxide to prepare the tear-resistant modified composite environment-friendly rubber base material. In the invention, by adopting asphalt-based carbon fiber, the mechanical property of the material is enhanced, the harmful gases and dust matters in tail gas can be greatly adsorbed and eliminated, and the obtained MC nylon has good overall performance. By cooperatively adopting the main materials including epichlorohydrin rubber, nitrile butadiene rubber, acrylonitrile-butadiene copolymer rubber, diene rubber, styrene butadiene rubber and regenerated rubber, the toughness of the material is greatly improved, and the condition that a conveyer belt is easily broken is effectively solved; meanwhile, gases harmful to a human body are not generated at relatively high temperature; and through perfect fusion of the high-temperature resistance, tear resistance and the like, the tear-resistant modified composite environment-friendly rubber base material provided by the invention can be applied to various severe conditions. The added components not only effectively ensure that the protected material is not burnt easily, and but also avoid the generation of gases harmful to the human body when being burnt at extremely high temperature; and compared with the hydrotalcite currently applied on the market, the tear-resistant modified composite environment-friendly rubber base material has obvious advantages of high-temperature resistance, fireproof property and flame retardance.
Description
Technical field
The present invention relates to the preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate, particularly to a kind of MC Buddhist nun
The preparation method of dragon/modified graphene oxide nano composite material.
Background technology
Monomer cast nylon (MC nylon) is one of current most widely used engineering plastics, and it has low cost, high yield, height
The advantages such as reaction rate and good mechanical performance, are widely used in preparing bearing, gear, pulley etc., especially prepare
The large-scale device can not prepared by compression moulding or extrusion molding, MC nylon progressively replaces some metal materials in a lot of fields,
Such as copper, aluminum, steel and ferrum etc..But, compared with metal material, it is high that MC nylon there are still elastic modelling quantity, and low-temperature flexibility is poor,
The shortcomings such as impact strength is on the low side, and dimensional stability is bad, make the application of MC nylon be somewhat limited, domestic for this
External enhancing, the aspect such as toughness reinforcing conduct extensive research.
Implant is mainly incorporated into polymerization forming in caprolactam monomer by the activeness and quietness modification of MC nylon, main
Implant has inorganic filler, fibrous material, elastomeric material and nano material.Traditional modifying agent and method mostly can only be improved
MC nylon performance in a certain respect, and to a certain extent to weaken other performance as cost.Such as add mineral powder, toughness reinforcing
While often make intensity reduce；Toughness is the most generally made to reduce during fiberglass reinforced；And often add graft copolymerization elastic body toughening
It is with the valuable rigidity of expendable material, dimensional stability, thermostability as cost, carries it is therefore necessary to find a kind of modifying agent
The combination property of high MC nylon.
Summary of the invention
The present invention solves that above-mentioned technical problem provides the preparation side of a kind of tear-resistant modified composite environmental-friendly rubber substrate
Method, the method preparation simplicity, technique is simple, and the tear-resistant modified composite environmental-friendly rubber substrate combination property of one obtained is good,
On the premise of keeping MC nylon hot strength and hardness, significantly improve the impact strength of MC nylon.
The technical scheme is that the preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate, including following
Step:
A. the graphite oxide of high oxidation degree is prepared；
B. the graphite oxide using cetyl trimethylammonium bromide to obtain step a is modified processing, and to changing of obtaining
Property graphite oxide use and ultrasonic obtain graphene oxide；
C. situ aggregation method is used to prepare MC nylon/modified graphene oxide nano composite material；
D. nitrile rubber modified phenolic resin, hexamethylenamine, decompression residuum, non-halogenated organophosphinate, six methines are added
Tetramine, tri-methyl-amyl triethoxysilane, conductive mica powder, conductive nano graphite powder, the trimer of polyisocyanates, poly-four
Fluorothene fiber, nanoparticle active agent, plasticizer, age resistor, nano-cerium oxide, accelerator；
E. after remaining component being pulverized and mixed, standby after crossing 100-200 mesh screen；Stir prepared high temperature 90-100 DEG C
Base material；
F. by compound, base material being extruded into adobe by vacuum extruder, the vacuum of vacuum extruder is 1.0-1.8Mpa,
Extrusion pressure is 15-20Mpa；
Each component proportion described is: chlorohydrin rubber 90-100 part, nitrile rubber 20-30 part, acrylonitrile-butadiene copolymer rubber
Glue 30-60 part, diene rubber 30-55 part, butadiene-styrene rubber 10-20 part, reclaimed rubber 20-30 part, graphene oxide 5-10 weight
Part, non-halogenated organophosphinate 5-7 part, hexamethylenetetramine 8-10 part, tri-methyl-amyl triethoxysilane 2-4 part, lead
Electricity mica powder 0.3-0.5 weight portion, conductive nano graphite powder 0.2-0.4 weight portion, the trimer 0.8-1 weight of polyisocyanates
Part, polytetrafluoroethylene fibre 1-2 weight portion, nanoparticle active agent 20-30 weight portion, plasticizer 2-8 weight portion, age resistor 1-5 weight
Amount part, nano-cerium oxide 6-14 weight portion, accelerator 2-6 weight portion；
G. by after the adobe of step (f) under field conditions (factors) dry in the sun 15 days at a temperature of 700 DEG C sinter molding；Base material is put into
In Mechanical processing of casting machine, first adding pressurizing melting on vulcanizing press at foundry goods, melt temperature is 160-190 DEG C, after constant temperature 3-5h certainly
So cooling.
Step a is prepared high oxidation degree graphite oxide include: added by concentrated sulphuric acid in graphite, through-20 DEG C ~-10 DEG C
Low temperature stirs 5-12 hour, then after 0 DEG C ~ 5 DEG C stirrings 5-12 hour, addition potassium permanganate carries out oxidation reaction and aoxidized
Graphite solution.
Step b use cetyl trimethylammonium bromide (CTAB) graphene oxide modification is included: in step a
In obtain graphite oxide solution is directly added into CTAB, CTAB and graphite oxide flocculated and modified-reaction obtains modified oxidized
Graphite solution.
Graphite with the mass ratio of CTAB is: 10:1 ~ 20:1, and graphite with the mass ratio of potassium permanganate is: 1:1 ~ 1:5.
In step c, use situ aggregation method to prepare MC nylon/modified graphene oxide nano composite material and include: incite somebody to action oneself
Lactams is heated to 70 DEG C-100 DEG C and extremely melts, and the modified graphene oxide solution that mass fraction is 0.05% ~ 5% joins oneself
Adding a certain amount of catalyst in lactams fused solution, decompression distillation removes by-product in 30-60 minute, is eventually adding a certain amount of
Activator (TDI), pours in preheated mould after stirring rapidly, react 1-4 hour at 80-150 DEG C.
Described catalyst is sodium hydroxide, and described activator is 2,4 toluene diisocyanate.
In the present invention, with chlorohydrin rubber, nitrile rubber, acrylonitrile-butadiene copolymer rubber, diene rubber, butylbenzene rubber
Glue, reclaimed rubber are major ingredient with the use of substantially increasing the toughness of material, effectively solve the feelings that conveyer belt is easily broken off
The performances such as condition, also will not produce harmful gas high temperature resistant simultaneously under higher temperature, tear-resistant perfectly merge so that
The present invention can apply to work under various mal-condition.Use two benches low temperature process to prepare graphite oxide, concentrated sulphuric acid is added
In graphite, first pass around-20 DEG C ~-10 DEG C low temperature and stir 5-12 hour, then after 0 DEG C ~ 5 DEG C stirrings 5-12 hour, add height
Violent acid potassium solution prepares graphite oxide, uses two benches low temperature process, and concentrated sulphuric acid carries out pre-oxidation to graphite, adds permanganic acid
Graphite is carried out, in profound oxidizing process, to significantly improve the degree of oxidation of graphite oxide by potassium, resistance in follow-up preparation one
In the modified composite environmental-friendly rubber substrate of tear, improve graphene oxide dispersibility in MC nylon.
Using CTAB to be modified graphite oxide processing, modified graphite oxide specific surface area is big, with matrix Buddhist nun simultaneously
Dragon has and contacts more fully；The most modified graphite oxide and TDI are easy to react, and result is divided at modified graphite oxide
Son introduces NCO.These characteristics strengthen the strong interaction between modified graphene oxide and nylon molecules, carry
Both interface adhesions high.
Modified graphene oxide is used to be modified MC nylon processing, the tear-resistant modified complex loop of one prepared
Protect rubber substrate and possess excellent combination property, on the basis of keeping the original hot strength of MC nylon and hardness, use Colophonium
Base carbon fibre enhances the mechanical property of material and can adsorb greatly and the harmful gas of removing in tail gas and dust material,
With the use of plasticizer, age resistor, self-control modified hydrotalcite, attapulgite clay, nano titanium oxide, nano-cerium oxide, rush
Entering agent etc. for adjuvant, component raw material prepares reasonable science, and the composition of interpolation not only can have and effective ensures material of its protection not
Easy firing, and the too high burning of temperature also will not produce harmful gas；Wherein, self-control modified hydrotalcite is by necessarily
The magnesium aluminum-hydrotalcite of amount is scattered in after making serosity in the deionized water of de-CO2 and the NaH2PO4 2H2O of excess is dissolved in water institute
Wiring solution-forming is poured slowly in serosity, and heated and stirred also regulates PH to about 3.7 with acetic acid, reacts 3 hours under reflux temperature,
After natural cooling, with deionized water wash product the filtration of de-CO2 until filtrate PH=7, then it is dried and prepares, with mesh
The brucite used on front market, has the most high temperature resistant, fire prevention, fire-retardant advantage.
Detailed description of the invention
For being fully understood by the purpose of the present invention, feature and effect, by following specific embodiment, the present invention is done in detail
Describe in detail bright.
Embodiment one:
Under cryosel is bathed, adding 30ml concentrated sulphuric acid in the there-necked flask equipped with 1g graphite (325 mesh), mixture stirs at-15 DEG C
After mixing 12 hours certain times of reaction, then 0 DEG C of stirring reaction 5 hours, it is then slowly added into 2g potassium permanganate, is warming up to 35
DEG C, after reaction certain time, add deionized water, then be warming up to 90 DEG C, be eventually adding H2O2Become golden yellow to product, obtain
Graphite oxide solution, adds 0.2gCTAB in product, and graphite oxide settles the most rapidly, filters, washs, 50
DEG C vacuum drying 24 hours, i.e. obtains the modified graphene oxide modified with CTAB.
Embodiment 2
Under cryosel is bathed, adding 30ml concentrated sulphuric acid in the there-necked flask equipped with 1g graphite (325 mesh), mixture stirs at-10 DEG C
After mixing 10 hours certain times of reaction, then 0 DEG C of stirring reaction 3 hours, it is then slowly added into 2.3g potassium permanganate, is warming up to
35 DEG C, after reaction certain time, add deionized water, then be warming up to 90 DEG C, be eventually adding H2O2Become golden yellow to product,
To graphite oxide solution, adding 0.3gCTAB in product, graphite oxide settles the most rapidly, filters, washs,
50 DEG C are vacuum dried 24 hours, i.e. obtain the modified graphene oxide modified with CTAB.
Embodiment 3
Under cryosel is bathed, adding 30ml concentrated sulphuric acid in the there-necked flask equipped with 1g graphite (325 mesh), mixture stirs at-20 DEG C
After mixing 12 hours certain times of reaction, then 0 DEG C of stirring reaction 6 hours, it is then slowly added into 3g potassium permanganate, is warming up to 35
DEG C, after reaction certain time, add deionized water, then be warming up to 90 DEG C, be eventually adding H2O2Become golden yellow to product, obtain
Graphite oxide solution, adds 0.1gCTAB in product, and graphite oxide settles the most rapidly, filters, washs, 50
DEG C vacuum drying 24 hours, i.e. obtains the modified graphene oxide modified with CTAB.
B. the graphite oxide of high oxidation degree is prepared；
B. the graphite oxide using cetyl trimethylammonium bromide to obtain step a is modified processing, and to changing of obtaining
Property graphite oxide use and ultrasonic obtain graphene oxide；
C. situ aggregation method is used to prepare MC nylon/modified graphene oxide nano composite material；
D. chlorohydrin rubber, nitrile rubber, acrylonitrile-butadiene copolymer rubber, diene rubber, butadiene-styrene rubber, regeneration rubber are added
Glue, non-halogenated organophosphinate, hexamethylenetetramine, tri-methyl-amyl triethoxysilane, conductive mica powder, conductive nano
Graphite powder, the trimer of polyisocyanates, polytetrafluoroethylene fibre, nanoparticle active agent, plasticizer, age resistor, nano-cerium oxide,
Accelerator；
E. after remaining component being pulverized and mixed, standby after crossing 100-200 mesh screen；Stir prepared high temperature 90-100 DEG C
Base material；
F. by compound, base material being extruded into adobe by vacuum extruder, the vacuum of vacuum extruder is 1.0-1.8Mpa,
Extrusion pressure is 15-20Mpa；
Each component proportion described is: chlorohydrin rubber 90-100 part, nitrile rubber 20-30 part, acrylonitrile-butadiene copolymer rubber
Glue 30-60 part, diene rubber 30-55 part, butadiene-styrene rubber 10-20 part, reclaimed rubber 20-30 part, graphene oxide 5-10 weight
Part, non-halogenated organophosphinate 5-7 part, hexamethylenetetramine 8-10 part, tri-methyl-amyl triethoxysilane 2-4 part, lead
Electricity mica powder 0.3-0.5 weight portion, conductive nano graphite powder 0.2-0.4 weight portion, the trimer 0.8-1 weight of polyisocyanates
Part, polytetrafluoroethylene fibre 1-2 weight portion, nanoparticle active agent 20-30 weight portion, plasticizer 2-8 weight portion, age resistor 1-5 weight
Amount part, nano-cerium oxide 6-14 weight portion, accelerator 2-6 weight portion；
G. by after the adobe of step (f) under field conditions (factors) dry in the sun 15 days at a temperature of 700 DEG C sinter molding；Base material is put into
In Mechanical processing of casting machine, first adding pressurizing melting on vulcanizing press at foundry goods, melt temperature is 160-190 DEG C, after constant temperature 3-5h certainly
So cooling.
In the present invention, the nitrile rubber modified phenolic resin of interpolation mixes with raw material, solidifies, at hexamethylenamine during heating
Under the effect of the methylene decomposited, the three-dimensional-structure that melted resin cannot not rapidly transformed into meltedly by linear structure;Improvement machine
Tool performance so that it is there is high temperature resistant, the performance of low bulk.The graphite oxide of high oxidation degree is prepared by low temperature two-phase method,
And use CTAB to be modified processing to it, on the one hand improve graphene oxide dispersibility in MC nylon matrix, the opposing party
Face, it is long to there is finishing time in graphene oxide in last handling process, the problem that technique is loaded down with trivial details, and this also constrains graphite oxide
Alkene realizes application, uses CTAB to be added directly in graphite oxide solution, and while modification, CTAB is to graphite oxide
Solution has carried out flocculation treatment, is substantially shorter the last handling process of graphite oxide, improves graphite oxide preparation efficiency, therefore,
Use CTAB that graphite oxide is carried out post processing, while modification, shorten graphite oxide aftertreatment technology.Use modified
MC nylon is modified by graphene oxide, and in the case of modified graphene oxide content is little, a kind of tear-resistant modification is multiple
Rubber substrate is protected in cyclization just can reach good mechanical property.
Above example is the preferred embodiments of the present invention, and those skilled in the art draw according to technical scheme
Rational technique scheme is also within scope.
Claims (6)
1. the preparation method of a tear-resistant modified composite environmental-friendly rubber substrate, it is characterised in that comprise the following steps:
The graphite oxide of preparation high oxidation degree；
B. the graphite oxide using cetyl trimethylammonium bromide to obtain step a is modified processing, and to changing of obtaining
Property graphite oxide use and ultrasonic obtain graphene oxide；
C. situ aggregation method is used to prepare MC nylon/modified graphene oxide nano composite material；
D. chlorohydrin rubber, nitrile rubber, acrylonitrile-butadiene copolymer rubber, diene rubber, butadiene-styrene rubber, regeneration rubber are added
Glue, non-halogenated organophosphinate, hexamethylenetetramine, tri-methyl-amyl triethoxysilane, conductive mica powder, conductive nano
Graphite powder, the trimer of polyisocyanates, polytetrafluoroethylene fibre, nanoparticle active agent, plasticizer, age resistor, nano-cerium oxide,
Accelerator；
E. after remaining component being pulverized and mixed, standby after crossing 100-200 mesh screen；Stir prepared high temperature 90-100 DEG C
Base material；
F. by compound, base material being extruded into adobe by vacuum extruder, the vacuum of vacuum extruder is 1.0-1.8Mpa,
Extrusion pressure is 15-20Mpa；
Each component proportion described is: chlorohydrin rubber 90-100 part, nitrile rubber 20-30 part, acrylonitrile-butadiene copolymer rubber
Glue 30-60 part, diene rubber 30-55 part, butadiene-styrene rubber 10-20 part, reclaimed rubber 20-30 part, graphene oxide 5-10 weight
Part, non-halogenated organophosphinate 5-7 part, hexamethylenetetramine 8-10 part, tri-methyl-amyl triethoxysilane 2-4 part, lead
Electricity mica powder 0.3-0.5 weight portion, conductive nano graphite powder 0.2-0.4 weight portion, the trimer 0.8-1 weight of polyisocyanates
Part, polytetrafluoroethylene fibre 1-2 weight portion, nanoparticle active agent 20-30 weight portion, plasticizer 2-8 weight portion, age resistor 1-5 weight
Amount part, nano-cerium oxide 6-14 weight portion, accelerator 2-6 weight portion；
G. by after the adobe of step (f) under field conditions (factors) dry in the sun 15 days at a temperature of 700 DEG C sinter molding；Base material is put into
In Mechanical processing of casting machine, first adding pressurizing melting on vulcanizing press at foundry goods, melt temperature is 160-190 DEG C, after constant temperature 3-5h certainly
So cooling.
The preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate the most as claimed in claim 1, it is characterised in that:
Step a is prepared high oxidation degree graphite oxide include: added by concentrated sulphuric acid in graphite, through-20 DEG C ~-10 DEG C low temperature stirrings
5-12 hour, then after 0 DEG C ~ 5 DEG C stirrings 5-12 hour, add potassium permanganate and carry out oxidation reaction to obtain graphite oxide molten
Liquid.
The preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate the most as claimed in claim 1, it is characterised in that:
Step b use cetyl trimethylammonium bromide (CTAB) graphene oxide modification is included: to obtain oxygen in step a
Graphite solution is directly added into CTAB, CTAB graphite oxide is flocculated and modified-reaction to obtain modified graphite oxide molten
Liquid.
4. the preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate as described in claim 2-3, its feature exists
In, graphite with the mass ratio of CTAB is: 10:1 ~ 20:1, and graphite with the mass ratio of potassium permanganate is: 1:1 ~ 1:5.
The preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate the most as claimed in claim 1, it is characterised in that:
In step c, use situ aggregation method to prepare MC nylon/modified graphene oxide nano composite material and include: caprolactam is added
The modified graphene oxide solution that mass fraction is 0.05% ~ 5%, to 70 DEG C-100 DEG C to melted, is joined caprolactam and melts by heat
Melting and add a certain amount of catalyst in liquid, decompression distillation removes by-product in 30-60 minute, is eventually adding a certain amount of activator,
Pour in preheated mould after stirring rapidly, react 1-4 hour at 80-150 DEG C.
The preparation method of a kind of tear-resistant modified composite environmental-friendly rubber substrate the most as claimed in claim 5, it is characterised in that
Described catalyst is sodium hydroxide, and described activator is 2,4 toluene diisocyanate (TDI).
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