CN107254076A - A kind of composite reinforced rubber and preparation method thereof - Google Patents
A kind of composite reinforced rubber and preparation method thereof Download PDFInfo
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- CN107254076A CN107254076A CN201710499516.9A CN201710499516A CN107254076A CN 107254076 A CN107254076 A CN 107254076A CN 201710499516 A CN201710499516 A CN 201710499516A CN 107254076 A CN107254076 A CN 107254076A
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- tio
- latex
- hydroxyapatite
- graphene oxide
- rubber
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 80
- 239000005060 rubber Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 84
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 71
- 229920000126 latex Polymers 0.000 claims abstract description 66
- 239000004816 latex Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000013049 sediment Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 239000002174 Styrene-butadiene Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920006174 synthetic rubber latex Polymers 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229920003049 isoprene rubber Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 229920003051 synthetic elastomer Polymers 0.000 claims 1
- 239000005061 synthetic rubber Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 30
- 235000019198 oils Nutrition 0.000 description 30
- 239000006229 carbon black Substances 0.000 description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 24
- 239000000843 powder Substances 0.000 description 19
- 239000003292 glue Substances 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 229920005610 lignin Polymers 0.000 description 9
- 239000012744 reinforcing agent Substances 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- 210000000481 breast Anatomy 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000008394 flocculating agent Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000010721 machine oil Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 229920000209 Hexadimethrine bromide Polymers 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PCJUMACLVAITCG-UHFFFAOYSA-N [C].C(CCC)C1=CC=CC=C1 Chemical compound [C].C(CCC)C1=CC=CC=C1 PCJUMACLVAITCG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08L7/02—Latex
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of composite reinforced rubber and preparation method thereof, method of the invention is：1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, then hydro-thermal reaction mixes the mixed liquor that hydro-thermal is obtained with graphene oxide suspension, condensing reflux, obtains hydroxyapatite/TiO2/ graphene oxide composite material；2) by plasticizer, operation oil add latex in, stir evenly to form latex mixed liquor, then add step 1) composite, 6 10h are stirred, coagulator is added, occurred coprecipitated, then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforced rubber.The reinforced rubber excellent in mechanical performance of the present invention, breaking strength is in more than 27.0MPa, and tearing strength is in more than 118.7MPa, and hardness (shore A) is more than 83.0.
Description
Technical field
The present invention relates to a kind of hydroxyapatite/TiO2/ graphene oxide composite material reinforced rubber and preparation method thereof.
Belong to chemical materials and its preparing technical field.
Background technology
Traditionally, production rubber needs to utilize the dress such as rubber internal mixer, mill, continuous screw kneading machine
It is standby, rubber and reinforcing agent, filler, vulcanization accelerator, age resistor, operation oil, function additive etc. are kneaded, imparting rubber
Elastomeric compound is with specific processing performance and the specific physical and chemical performance of vulcanizate, and this compounding process is also referred to as dry method mixing.This
Mixing process needs to expend substantial amounts of power.Reinforcing agent, operation oil be rubber industry consumption maximum auxiliary agent, kneading reinforcing agent,
Operation oil consumes power accounts for compounding rubber power more than 40%.For many years, people are seeking to prepare rubber mixed always
When toward the most rational method that larger addition, scattered more difficult reinforcing agent, operation oil are added in rubber.
There is provided a kind of charcoal for the patent of invention " preparation method of carbon black filled powder rubber " of Application No. 02152077.1
The preparation method of black filled powder rubber, comprises the steps：Contain dry glue: carbon black: carbon black emulsifying agent by the latex First Astronautic Research Institute for Measurement and Test: behaviour
Make oil: age resistor: fatty acid alkali metal salt emulsifying agent: flocculating agent: the weight ratio of deionized water be 100: 10~100: 0.5~
6.0: 0~70: 0.5~3.0: 1.0~6.0: 2.0~5.0: 300~2000 proportion ingredient；The emulsification of carbon black；The heat of latex
Processing；The agglomeration process of latex；The post processing of condensation product.Using the present invention prepare powdered rubber have covering addition compared with
Few, covered effect is good, and reliable and stable, the easy advantage of pulverisation process, the powder formation rate of carbon black filled powder rubber reaches
More than 99%, the particle diameter distribution of prepared carbon black filled powder rubber can be controlled by adjusting coherence condition, be made
Product physical and mechanical properties it is good, contactless contaminative, good fluidity, stable storing.
Patent of invention " rare earth or the transition metal doping carbon black filled powder rubber of Application No. 200710029871.6
Preparation method " there is provided the preparation method of a kind of rare earth or transition metal doping carbon black filled powder rubber, including following steps
Suddenly：Contain dry glue: carbon black: rare earth or transition metal oxide: carbon black emulsifying agent by the latex First Astronautic Research Institute for Measurement and Test: operation oil: age resistor: fat
Acid alkali metal salt emulsifying agent: flocculating agent: the weight ratio of deionized water is 100: 10~150: 0.01~15.0: 0.25~15.0: 0
~70: 0.5~3.0: 1.0~6.0: 1.5~5.0: 300~2500 proportion ingredient；The emulsification of carbon black；Rare earth compound or mistake
Cross the preparation of metallic compound doping carbon black；The heating of latex；The agglomeration process of latex；The post processing of condensation product.With biography
System prepares rare earth or transition using being compared undoped with carbon black filled powder rubber prepared by moditying polybrene test using the present invention
The powder formation rate of metal-doped carbon black filled powder rubber is high, contactless contaminative, good fluidity, stable storing；It is made
Vulcanized mechanical especially stress at definite elongation and tensile strength be significantly improved.
The patent of invention " preparation method of butadienestyrene rubber with superfine calcium caronate powder filling " of Application No. 97110667.3, is carried
For a kind of preparation method of butadienestyrene rubber with superfine calcium caronate powder filling, it is total to using the alternating of styrene-maleic anhydride
The saponified of polymers is covering, using the calcium carbonate superfine powder with strengthening action as filling interleaving agent, with univalent metal salt and two
Valency metal salt makees flocculating agent, and it is 0.45~0.9mm, storage stabilization, the calcium carbonate superfine powder powder filler of good fluidity that particle diameter, which is made,
Butadiene-styrene rubber.Powdered of the present invention is stable, reliable, dehydration is easy, and equipment is simple.
Application No. 02152078.X patent of invention " preparation method of powdered rubber in stuffing type with extra fine calcium carbonate " there is provided
A kind of preparation method of powdered rubber in stuffing type with extra fine calcium carbonate, comprises the steps：Contain dry glue: ultra-fine carbon by the latex First Astronautic Research Institute for Measurement and Test
Sour calcium: surfactant: operation oil: age resistor: fatty acid alkali metal salt emulsifying agent: flocculating agent: the weight ratio of deionized water is
100: 0~250: 0.2~8.0: 0~70: 0.5~3.0: 2.5~6.0: 2.0~5.0: 300~2000 proportion ingredient；It is ultra-fine
The emulsification of calcium carbonate；The heat treatment of latex；The agglomeration process of latex；The post processing of condensation product.Powder rubber is prepared using the present invention
Glue has covering addition less, and covered effect is good, reliable and stable, the easy advantage of pulverisation process, calcium carbonate superfine powder
The powder formation rate of filled powder rubber is up to more than 99%, and the particle diameter distribution of prepared powdered rubber in stuffing type with extra fine calcium carbonate can
To be controlled by adjusting coherence condition, the product physical and mechanical properties being made is excellent, non-dusting, good fluidity, storage
Deposit stabilization.
The patent of invention " method of rubber reinforcing filler is used as by the use of lignin " of Patent No. 89109494.6 discloses one
The method as nitrile rubber reinforcing agent with lignin formaldehyde resin is planted, addition formaldehyde is made wooden in the papermaking wastewater of concentration
Plain formaldehyde resin, then it is proportionally added into Sulfur, zinc oxide, stearic acid, vulcanizing agent, vulcanization accelerator, vulcanizing activator and rubber
Vulcanized at a certain temperature, can obtain and a large amount of lignin are filled in rubber and are not required to plus softening agent, a large amount of rubber of saving
And the vulcanizate of good properties.But the shortcoming of this method is that three sections of whole manufacturing processes point are carried out respectively, i.e. lignin first
The preparation of urea formaldehyde, mix with nitrile rubber, the boundary of lignin and nitrile rubber is handled, and adds process complexity, and
And the cost of this method is higher, it is necessary to add various auxiliary agents；In addition, this method is only applicable to nitrile rubber, in elastomer
In application it is also narrow.
Chinese patent disclosed above, or utilize carbon black as rubber reinforcing agent (in addition to using silica as
The white carbon of main component), or it is used as by the use of lignin the reinforcing agent of rubber.
Latex coprecipitation, i.e., add then coprecipitated solidification in latex by carbon black dispersion, operation fat liquor, be to traditional rubber
A kind of supplement of dry method compounding process.Using this method, the series of high temperature of SBR 1100 breast of commercialization has been produced at present
It is poly- to fill that carbon black butylbenzene masterbatch, the series of high temperature of SBR 1200 breast gather oil-filled butylbenzene masterbatch, the series of high temperature of SBR 1300 breast is poly- fills
The poly- carbon black butylbenzene masterbatch, SBR Series 1700s low temperature breast of filling of the serial low temperature breast of oil black carbon butylbenzene masterbatch, SBR 1600 gathers
The poly- gross butylbenzene masterbatch of the serial low temperature breast of oil-filled butylbenzene masterbatch, SBR 1800.
But prepare carbon black dispersion and need to use ball mill, liquid stream grinder or magnetic oscillator, and add surface work
Property agent and water, then with the intermediate during production emulsion polymerized styrene butadiene rubber --- styrene-butadiene latex, fat liquor according to certain plus
Material order is mixed, because above-mentioned mixed liquor is thermodynamically and unstable, and gained mixed liquor is needed in a short time, such as 20
In minute, appropriate coagulator (such as sodium chloride solution, acetum, dilute sulfuric acid) is added, is solidified, be then dehydrated, wash,
Dry, the butadiene-styrene rubber of the various trades mark is made.
Therefore, the reinforcing agent of rubber is utilized carbon black as, although in technique and economically with traditional method for mixing rubber
Compare, had the disadvantage that with certain superiority, but also：(1) because carbon black is hydrophobic material, carbon black dispersion is prepared
When, the shearing force that carbon black pellet is subject in ball mill is acted on much smaller than the shearing force being subject to when kneading, therefore carbon black is in life
The scattered yardstick that traditional compounding process can reach can not be reached in glue, causes some performances of rubber to weaken, such as pulls apart
Intensity can be reduced, and permanent deformation can increase.(2) amount of the carbon black added in latex also by larger limitation, mainly because
There is big, the hydrophobic property of density for carbon black, dispersion stability is poor, it is impossible to reach desired by rubber institute
The purpose that the most of carbon black needed is added in rubber by the method for latex coprecipitation.
The B of CN 102718995 disclose a kind of industrial lignin reinforced rubber and preparation method thereof, and it includes lignin point
Granular media, latex and a small amount of plasticizer, operation oil, it can merge while rubber mixed physical and mechanical properties is not reduced
Lignin and the drying process of rubber production process, reduce the power consumption of compounding rubber, still, its intensity and breaking strength etc.
Mechanical property is relatively poor, needs further raising.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of composite reinforced rubber
Preparation method, hydroxyapatite/TiO of the invention2/ graphene oxide composite material reinforced rubber, which not only overcomes, utilizes charcoal
The conventional dry mixing reduction compared with the coprecipitated reinforced rubber of rubber latex emulsion has elastomeric compound physical and mechanical properties of black dispersion
Shortcoming, and prior art prepares the shortcoming that energy consumption is big, dust pollution is big that rubber mixed process is present, and the rubber
Excellent in mechanical performance, have broad application prospects.
For up to above-mentioned purpose, the present invention uses following technical scheme：
A kind of preparation method of composite reinforced rubber, it is characterized in that：It the described method comprises the following steps：
(1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, adds in reactor, it is anti-in 160 DEG C of hydro-thermals
12-24h is answered, then mixes the mixed liquor that hydro-thermal is obtained with graphene oxide suspension, in 80-100 DEG C of condensing reflux 12-
24h, obtains hydroxyapatite/TiO2/ graphene oxide composite material；
(2) plasticizer, operation oil are added in latex, stirs evenly, then add hydroxyapatite/TiO2/ graphene oxide
Composite, stirs 6-10h, adds coagulator, occurs coprecipitated, formation sediment, then sediment is washed, taken off
Water, drying, that is, obtain hydroxyapatite/TiO2/ graphene oxide composite material reinforced rubber.
Preferably, in step (1), the hydroxyapatite and TiO2Mass ratio be (20-30)：(1-5), be, for example,
20：1、20：2、20：3、25：1、25：2、25：3、25：4、25：5、27：1、27：2、27：3、27：4、30：1、30：2、30：3 or
30：4.5 etc., preferably 25：3.
Preferably, in step (1), in the dispersion liquid, hydroxyapatite and TiO2Total molar concentration be 1-5mol/
L, for example, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L or 5mol/L etc..
Preferably, in step (1), the molar concentration of the graphene oxide suspension is 1mg/mL.
Preferably, in step (1), the mixed liquor and the volume ratio of graphene oxide suspension that hydro-thermal is obtained are 1：(10-
15)。
Preferably, in step (2), plasticizer, operation oil, latex and hydroxyapatite/TiO2/ graphene oxide composite wood
Material, mass ratio be 1：1：100：(5-10), for example, 1：1：100：5、1：1：100：6、1：1：100：7、1：1：100：7.5、
1：1：100：8、1：1：100：9 or 1：1：100：10 etc., preferably 1：1：100：8.
Preferably, in step (2), the latex is Heveatex or synthetic rubber latex.
Preferably, in step (2), in step (2), the latex is Heveatex, styrene-butadiene latex, NBR latex, isoamyl
Rubber latex, butyl rubber latex, Neoprene latex or other unlisted all synthesis produced with emulsion polymerisation process
The latex of rubber.
In the present invention, the mode that plasticizer and operation oil formation latex mixed liquor are added into latex can be following feelings
Condition：The fat liquor that rubber industry common plasticizers, operation oil are made, such as aromatic naphtha, epoxidized soybean oil, machine oil, castor oil, three
Line is oily, one or two or more kinds of combinations in high sulfone oil, dibutyl phthalate or dioctyl phthalate fat liquor, plus
Enter in latex, form latex mixed liquor；Or rubber industry common plasticizers, operation oil, such as aromatic hydrocarbons are directly added into latex
Oil, epoxidized soybean oil, machine oil, castor oil, third fractional oil, high sulfone oil, dibutyl phthalate or dioctyl phthalate
One or two or more kinds combination, forms latex mixed liquor.
The invention has the advantages that and beneficial effect：
(1) present invention is using hydroxyapatite, TiO2With graphene oxide composite wood is prepared in the method for hydro-thermal+water-bath
Material, and by the composite for preparing reinforced rubber, the mating reaction between this three produces synergy, can reply lifting
The mechanical property of obtained rubber, hydroxyapatite/TiO of the invention2/ graphene oxide composite material reinforced rubber is pulled apart
Intensity is in more than 27.0MPa, and tearing strength is in more than 118.7MPa, and hardness (shore A) is more than 83.0.
(2) method of the invention is simple, cost is low, energy consumption is small, and the dust pollution for reducing rubber mixing process is adapted to work
Industry metaplasia is produced.
Embodiment
In order to better illustrate the present invention, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment it is as follows：
Embodiment 1
Hydroxyapatite/TiO2/ graphene oxide composite material and the coprecipitated blending of Heveatex, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material：
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 5mol/L, and hydroxyapatite and TiO2Mass ratio be 25：2), add in reactor, in 160 DEG C of hydro-thermal reactions
24h, the mixed liquor for then obtaining hydro-thermal is with graphene oxide suspension according to 1：10 volume ratio mixing, is condensed back in 80 DEG C
24h is flowed, hydroxyapatite/TiO is obtained2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber：
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then adds hydroxyapatite/TiO2/
Graphene oxide composite material, stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, occurs coprecipitated, formation sediment,
Then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：5.
After testing, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 26.8MPa, tearing strength is 123.5KN/m, and hardness (shore A) is 82.6.
Embodiment 2
Hydroxyapatite/TiO2/ graphene oxide composite material and the coprecipitated blending of Heveatex, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material：
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 3mol/L, and hydroxyapatite and TiO2Mass ratio be 20：1), add in reactor, in 180 DEG C of hydro-thermal reactions
12h, the mixed liquor for then obtaining hydro-thermal is 1 according to volume ratio with graphene oxide suspension：12 mixing, in 100 DEG C of condensations
Flow back 12h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber：
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then adds hydroxyapatite/TiO2/
Graphene oxide composite material, stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, occurs coprecipitated, formation sediment,
Then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：7.
After testing, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 27.5MPa, tearing strength is 118.7KN/m, and hardness (shore A) is 83.1.
Embodiment 3
Hydroxyapatite/TiO2/ graphene oxide composite material and the coprecipitated blending of Heveatex, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material：
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 2.5mol/L, and hydroxyapatite and TiO2Mass ratio be 20：4), add in reactor, it is anti-in 170 DEG C of hydro-thermals
18h is answered, the mixed liquor for then obtaining hydro-thermal is 1 according to volume ratio with graphene oxide suspension：14 mixing, in 90 DEG C of condensations
Flow back 15h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber：
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then adds hydroxyapatite/TiO2/
Graphene oxide composite material, stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, occurs coprecipitated, formation sediment,
Then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：8.
After testing, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 28.0MPa, tearing strength is 123.5KN/m, and hardness (shore A) is 83.8.
Embodiment 4
Hydroxyapatite/TiO2/ graphene oxide composite material and the coprecipitated blending of Heveatex, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material：
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 1mol/L, and hydroxyapatite and TiO2Mass ratio be 30：3), add in reactor, in 165 DEG C of hydro-thermal reactions
20h, the mixed liquor for then obtaining hydro-thermal is 1 according to volume ratio with graphene oxide suspension：13 mixing, are condensed back in 85 DEG C
18h is flowed, hydroxyapatite/TiO is obtained2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber：
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then adds hydroxyapatite/TiO2/
Graphene oxide composite material, stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, occurs coprecipitated, formation sediment,
Then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：9.
After testing, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 27.0MPa, tearing strength is 120.2KN/m, and hardness (shore A) is 83.3.
Embodiment 5
Hydroxyapatite/TiO2/ graphene oxide composite material and the coprecipitated blending of Heveatex, for tire tread glue
Production.
(1) hydroxyapatite/TiO is prepared2/ graphene oxide composite material：
By hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid (wherein, hydroxyapatite and TiO2Total rub
Your concentration is 3.5mol/L, and hydroxyapatite and TiO2Mass ratio be 25：3), add in reactor, it is anti-in 175 DEG C of hydro-thermals
22h is answered, the mixed liquor for then obtaining hydro-thermal is 1 according to volume ratio with graphene oxide suspension：15 mixing, it is cold in 100 DEG C
Solidifying backflow 14h, obtains hydroxyapatite/TiO2/ graphene oxide composite material.
(2) hydroxyapatite/TiO is prepared2/ graphene oxide composite material reinforced rubber：
Plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then adds hydroxyapatite/TiO2/
Graphene oxide composite material, stirs 6-10h, adds appropriate dilute sulfuric acid, makes latex coagulation, occurs coprecipitated, formation sediment,
Then sediment washed, be dehydrated, being dried, that is, obtaining hydroxyapatite/TiO2/ graphene oxide composite material reinforcement rubber
Glue.
Hydroxyapatite/the TiO of the present embodiment2In/graphene oxide composite material reinforced rubber, plasticizer, operation oil,
Latex and hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：10.
After testing, the hydroxyapatite/TiO of the present embodiment2The breaking strength of/graphene oxide composite material reinforced rubber
For 29.0MPa, tearing strength is 132.5KN/m, and hardness (shore A) is 84.8.
Comparative example 1
Except by hydroxyapatite/TiO2/ graphene oxide composite material replaces with TiO2Outside, other preparation methods and condition
It is same as Example 1.
After testing, the breaking strength of the rubber of this comparative example is 19.9MPa, and tearing strength is 92.4KN/m, hardness (shore
A it is) 66.4.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of preparation method of composite reinforced rubber, it is characterized in that：It the described method comprises the following steps：
(1) by hydroxyapatite and TiO2It is distributed in water, forms dispersion liquid, adds in reactor, it is anti-in 160-180 DEG C of hydro-thermal
12-24h is answered, then mixes the mixed liquor that hydro-thermal is obtained with graphene oxide suspension, in 80-100 DEG C of condensing reflux 12-
24h, obtains hydroxyapatite/TiO2/ graphene oxide composite material；
(2) plasticizer, operation oil are added in latex, stirs evenly to form latex mixed liquor, then add hydroxyapatite/TiO2/ oxygen
Graphite alkene composite, stirs 6-10h, adds coagulator, occurs coprecipitated, formation sediment, then sediment is carried out
Wash, be dehydrated, dry, that is, obtain hydroxyapatite/TiO2/ graphene oxide composite material reinforced rubber.
2. the method as described in claim 1, it is characterized in that：In step (1), the hydroxyapatite and TiO2Mass ratio be
(20-30)：(1-5).
3. method as claimed in claim 1 or 2, it is characterized in that：In step (1), the hydroxyapatite and TiO2Mass ratio
For 25：3.
4. the method as described in claim any one of 1-3, it is characterized in that：In step (1), in the dispersion liquid, hydroxy-apatite
Stone and TiO2Total molar concentration be 1-5mol/L.
5. the method as described in claim any one of 1-4, it is characterised in that：In step (1), the graphene oxide suspension
Molar concentration be 1mg/mL.
6. the method as described in claim any one of 1-5, it is characterised in that：In step (1), mixed liquor and oxygen that hydro-thermal is obtained
The volume ratio of graphite alkene suspension is 1：(10-15).
7. the method as described in claim any one of 1-6, it is characterised in that：In step (2), plasticizer, operation oil, latex and
Hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：(5-10).
8. the method as described in claim any one of 1-7, it is characterised in that：In step (2), plasticizer, operation oil, latex and
Hydroxyapatite/TiO2The mass ratio of/graphene oxide composite material is 1：1：100：8.
9. the method as described in claim any one of 1-8, it is characterised in that：In step (2), the latex be Heveatex or
Synthetic rubber latex.
10. the method as described in claim any one of 1-9, it is characterised in that：In step (2), the latex is Heveatex,
Styrene-butadiene latex, NBR latex, isoprene rubber latex, butyl rubber latex, Neoprene latex or other are unlisted with emulsion
The latex of all synthetic rubber of polymerization production.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437321A (en) * | 2011-12-20 | 2012-05-02 | 中国科学院新疆理化技术研究所 | Graphene-TiO2(B) nanotube composite material and preparation method thereof |
| CN102569749A (en) * | 2012-03-06 | 2012-07-11 | 江苏大学 | Graphene/hydroxyapatite nano composite and preparation method thereof |
| CN105497986A (en) * | 2015-12-10 | 2016-04-20 | 青岛大学 | Synthesis method of graphene-hydroxyapatite composite material |
| WO2017059866A2 (en) * | 2015-10-09 | 2017-04-13 | Syddansk Universitet | Feedstock for 3d printing and uses thereof |
| CN106751163A (en) * | 2016-12-06 | 2017-05-31 | 安徽圣源橡塑科技有限公司 | A kind of heat-resistant PVC composite foamed plate high of graphene oxide hydroxyapatite reinforcement and preparation method thereof |
-
2017
- 2017-06-27 CN CN201710499516.9A patent/CN107254076B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437321A (en) * | 2011-12-20 | 2012-05-02 | 中国科学院新疆理化技术研究所 | Graphene-TiO2(B) nanotube composite material and preparation method thereof |
| CN102569749A (en) * | 2012-03-06 | 2012-07-11 | 江苏大学 | Graphene/hydroxyapatite nano composite and preparation method thereof |
| WO2017059866A2 (en) * | 2015-10-09 | 2017-04-13 | Syddansk Universitet | Feedstock for 3d printing and uses thereof |
| CN105497986A (en) * | 2015-12-10 | 2016-04-20 | 青岛大学 | Synthesis method of graphene-hydroxyapatite composite material |
| CN106751163A (en) * | 2016-12-06 | 2017-05-31 | 安徽圣源橡塑科技有限公司 | A kind of heat-resistant PVC composite foamed plate high of graphene oxide hydroxyapatite reinforcement and preparation method thereof |
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