CN101220127A - Nucleocapsid type rubber coordination crosslinking agent - Google Patents
Nucleocapsid type rubber coordination crosslinking agent Download PDFInfo
- Publication number
- CN101220127A CN101220127A CNA2007101645530A CN200710164553A CN101220127A CN 101220127 A CN101220127 A CN 101220127A CN A2007101645530 A CNA2007101645530 A CN A2007101645530A CN 200710164553 A CN200710164553 A CN 200710164553A CN 101220127 A CN101220127 A CN 101220127A
- Authority
- CN
- China
- Prior art keywords
- crosslinking agent
- oxide
- coordination
- nano
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 60
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 239000005060 rubber Substances 0.000 title claims abstract description 53
- 239000000843 powder Substances 0.000 claims abstract description 69
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 33
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 32
- 239000007822 coupling agent Substances 0.000 claims description 32
- -1 amino silicane Chemical compound 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 229960004643 cupric oxide Drugs 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 12
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004971 Cross linker Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000004873 anchoring Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000001149 thermolysis Methods 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000004132 cross linking Methods 0.000 abstract description 14
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 7
- 239000006229 carbon black Substances 0.000 abstract description 6
- 238000007731 hot pressing Methods 0.000 abstract description 3
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract 4
- 239000010954 inorganic particle Substances 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229920013649 Paracril Polymers 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000013536 elastomeric material Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a ligand cross-linking agent used in rubber, which is a cladding structure that a shell layer surrounds a core which consists of inorganic particles; the shell layer consists of organic high molecular polymer; a ligand center used for providing ligands is arranged on the organic high molecular polymer; the core is connected with the organic high molecular polymer by a covalent bond. The ligand center is transition metal ions and the inorganic particles are inorganic micron powder or inorganic nanoparticles. The core-shell ligand cross-linking agent can realize ligand cross linkage of nitrile rubber during hot-pressing process, which promotes the rigidity of the rubber as well as keeps good tenacity, thus substituting traditional sulfur carbon black reinforcing rubber cross linking system and obtaining rubber material that is not only reinforced but also rubbery.
Description
(1) technical field
The present invention relates to a kind of nucleocapsid type rubber coordination crosslinking agent, relate in particular to the hud typed coordination crosslinking agent of a kind of organic/inorganic.
(2) background technology
Crosslinkedly have great importance for the use properties of improving rubber.Being undertaken crosslinked as vulcanize by covalent linkage is the main method of rubber cross, has advantages such as Stability Analysis of Structures, technical maturity.Yet, bring serious " black pollution " problem because the stability and the non-reversibility of covalent linkage make vulcanized rubber reclaim difficulty; For obtaining the good mechanical mechanical property, vulcanization of rubber process often needs to combine with the black-reinforced means, causes processing environment relatively poor simultaneously.For solving above-mentioned deficiency, Chinese scholars has been carried out many researchs with regard to the non covalent bond of rubber is crosslinked.As utilize Van der Waals force effect faint between molecular chain to prepare thermoplastic elastomer, though good processibility capable of circulation is arranged since Van der Waals force, hydrogen bond action a little less than, system mechanical strength and high-temperature behavior are undesirable; On some main chains, contain in the rubber matrix of ionogen and can realize ionomer, as carboxy nitrile rubber/methacrylic acid zinc salt (ZDMA), carboxy nitrile rubber/metallic salts of unsaturated carboxylate etc., though good mechanical intensity and processibility capable of circulation are arranged, the ionic polymerization species is limited, crosslinking process control is harsh.
Coordination is the strongest reactive force in all non covalent bonds, and crosslinked existing research is primarily aimed in solution system about polymer complex.Li Hui etc. have studied the coordination cross-linked mechanism of paracril/copper sulfate system at hot pressing first, studies show that, can form three-dimensional net structure by coordination between cupric ion in the above-mentioned system and nitrogen-atoms, increase with copper sulfate content, the modulus of system and intensity are significantly improved under without the black-reinforced situation, and its mechanical behavior can be realized changing to the plastics attitude from rubbery state.Yet because the above-mentioned coordination cross-linked copper sulfate particle surface that mainly betides, complexing efficiency is lower, causes the copper sulfate amount of required interpolation bigger.In addition, when the system rigidity improved, toughness significantly descended, and is difficult to obtain the elastomeric material that the higher while of intensity keeps excellent toughness again.
(3) summary of the invention
The technical problem to be solved in the present invention is: by structure design, provide a kind of organic/inorganic hud typed coordination crosslinking agent, itself and rubber coordination are crosslinked, can obtain all elastomeric materials preferably of intensity and toughness.
Hud typed coordination crosslinking agent of the present invention is the clad structure that shell holds core; Described core is made up of inorganic particulate, and described shell is made up of organic high molecular polymer, has on the described organic high molecular polymer to supply the coordinate coordination center.Be connected by covalent linkage between described inorganic particulate and described organic high molecular polymer; Described organic high molecular polymer is one of following: polymethyl acrylic acid, polyacrylic acid, polymethylmethacrylate, polyvinyl acetate (PVA), described coordination center are transition metal ion, and described inorganic particulate is inorganic micro-powder or inorganic nano-particle.
Hud typed coordination crosslinking agent of the present invention is prepared as follows: choose organic monomer, with the inorganic particulate is core, by the polymer in situ polymerization technique, make described organic monomer carry out graft polymerization on the inorganic particulate surface and form organic high molecular polymer, described organic high molecular polymer is modified by side group and is introduced coordination center, obtain described hud typed coordination crosslinking agent, described organic monomer is one of following: methacrylic acid, vinylformic acid, methyl methacrylate, vinyl acetate.
Carboxylic monomer of the preferred side group of described organic monomer such as methacrylic acid, vinylformic acid.
Hud typed coordination crosslinking agent of the present invention is nuclear with the inorganic particulate, can introduce the thermolysis type initiator that maybe can produce living radical for organic monomer at the unsaturated carbon-carbon double bond of inorganic particulate surface grafting polymerization by finishing earlier.Described inorganic particulate surface modification method can adopt one of following method: surperficial coupling agent treatment, surperficial initiator positioning of anchor technology, ultrasonic wave elicitation technique, preferentially adopt the silane coupling agent preconditioning technique.
Particularly, described inorganic particulate finishing can be according to following processing: can handle the inorganic particulate surface by the silane coupling agent of terminal carbon-carbon double bonds, by the covalent linkage effect coupling agent molecule is grafted on particle surface, thereby introduce carbon-carbon double bond at particle surface; And thermolysis type initiator can be on coupling agent surface-treated basis, by with coupling agent molecule in the reactive group reaction initiator molecule is grafted on particle surface.
Described organic monomer forms organic high molecular polymer at the inorganic particulate surface grafting, and its polymerization implementation method can be selected one of following method: dispersion polymerization, mini-emulsion polymerization, emulsifier-free emulsion polymerization, ultrasonic initiated polymerization.Preferential dispersion polymerization, the emulsifier-free emulsion polymerization selected.
Described organic high molecular polymer is modified the introducing coordination center by side group, and described coordination center is one of following transition metal ion: cupric ion, cobalt ion, zine ion, mn ion, titanium ion, preferably copper ion or cobalt ion.
Further, described inorganic particulate is inorganic nano-particle or inorganic micro-powder, and inorganic nano-particle can be nano-oxide, as nano silicon oxide, nano-titanium oxide, nano zine oxide, nano aluminium oxide etc., also can be nano-calcium carbonate etc.; Inorganic micro-powder can be a micron oxide compound, as the micron order silicon oxide etc., also can be ordinary calcium carbonate, and ordinary calcium carbonate can be divided into common light calcium carbonate and common water-ground limestone again, preferred nano silicon oxide, nano zine oxide, ordinary calcium carbonate.
Further recommend the preparation method of described coordination crosslinking agent to comprise the steps:
(1) inorganic particulate after the purification process is scattered in the solvent, in the presence of initiator with silane coupling agent at 60～80 ℃ of back flow reaction 3～6h, aftertreatment obtains the inorganic particulate after the coupling agent treatment; The mass ratio that feeds intake of inorganic particulate after the described purification process and silane coupling agent is 1: 0.05～0.10;
(2) inorganic particulate after the coupling agent treatment is scattered in the solvent, with organic monomer under nitrogen protection in 60～80 ℃ of polyreaction 3～6h, aftertreatment obtains organic high molecular polymer grafting inorganic particulate powder; Described organic monomer quality is 1.5～2.5 times of inorganic particulate quality after the coupling agent treatment;
(3) reflux 2～4h in deionized water with organic high molecular polymer grafting inorganic particulate powder and transistion metal compound, aftertreatment obtains the hud typed coordination crosslinking agent of final product; The add-on of described transistion metal compound is 0.5～1.0 times of organic high molecular polymer grafting inorganic particulate powder quality.
The purification process of the described inorganic particulate of step (1) can adopt methods such as surperficial high temperature sintering;
Step (2) and the described solvent of step (3) can be dehydrated alcohol, toluene, Virahol etc.; Silane coupling agent can be the coupling agent that end contains unsaturated carbon-carbon double bond, as γ-methacryloxypropyl trimethoxy silane or N-(aminoethyl)-aminopropyl trimethoxysilane etc.
Step (3) can add initiator, and described initiator can be Diisopropyl azodicarboxylate, dibenzoyl peroxide (BPO) etc.
The described transistion metal compound of step (4) can be cupric oxide, thionamic acid cobalt etc.
The core of the described hud typed coordination crosslinking agent of concrete recommendation is a nano-oxide, and described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion, and described hud typed coordination crosslinking agent is made as follows:
(1) at first with nano-oxide in 600～650 ℃ of lower surface calcination 4～5h;
(2) nano-oxide powder after will handling is scattered in the toluene, adds the silane coupling agent γ-methacryloxypropyl trimethoxy silane (KH570) of hydrolysis in advance, is warming up to boiling, stir reflux condensation mode, logical nitrogen protection fast, finish behind reaction 4～6h, obtain suspension; The nano-oxide after described calcination is handled and the mass ratio that feeds intake of silane coupling agent γ-methacryloxypropyl trimethoxy silane (KH570) are 1: 0.05～0.10, and the add-on of toluene is that the nano-oxide after per 10 gram calcinations are handled adds 300～400ml;
(3) the logical nitrogen protection of the suspension that step (2) is obtained, progressively be warming up to 60～80 ℃, add radical initiator dibenzoyl peroxide (BPO), stir, slowly drip organic monomer methacrylic acid (MA), reaction 3～5h obtains product, and product gets polymethyl acrylic acid engrafted nanometer oxide powder after separation, washing, vacuum-drying; The quality that adds described methacrylic acid (MA) is 2.0～2.5 times of nano oxidized amount after calcination is handled, and the add-on of described dibenzoyl peroxide (BPO) is 0.01～0.02 times of described methacrylic acid quality;
(4) the polymethyl acrylic acid engrafted nanometer oxide powder after step (3) processing is added in the deionized water, slowly add cupric oxide or thionamic acid cobalt, stirring heating backflow 2～4h, the filtered while hot washing obtains final product after the drying; The quality that adds cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid engrafted nanometer oxide powder quality.
The core of described coordination crosslinking agent also can be the micron oxide compound, and described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion, and described hud typed coordination crosslinking agent is made as follows:
(1) at first with the micron oxide compound in 600～650 ℃ of lower surface calcination 4～5h;
(2) the micron oxide powder after will handling is scattered in the deionized water, add silane coupling agent γ-methacryloxypropyl trimethoxy silane (KH570), regulate between the pH value 4-5, be warming up to 80 ℃, stir fast, reflux condensation mode finishes behind reaction 4～6h, obtains coupling agent treatment rear oxidation thing powder after filtration, the drying; The micron oxide compound after described calcination is handled and the mass ratio that feeds intake of silane coupling agent γ-methacryloxypropyl trimethoxy silane are 1: 0.05～0.10, and the add-on of deionized water is that the micron oxide compound after per 10 gram calcinations are handled adds 300～400ml;
(3) the coupling agent treatment rear oxidation thing powder that step (2) is obtained is distributed in the toluene, be warming up to 60～80 ℃, add radical initiator dibenzoyl peroxide (BPO), stir, slowly drip the organic monomer methacrylic acid, nitrogen protection reaction 3～5h down obtains product, and product gets polymethyl acrylic acid grafting micron oxide powder after separation, washing, vacuum-drying; The add-on of toluene is that per 10 gram coupling agent treatment rear oxidation thing powder add 300～400ml, the quality that adds described methacrylic acid is 2.0～2.5 times of coupling agent treatment rear oxidation thing powder quality, and the add-on of described dibenzoyl peroxide is 0.01～0.02 times of methacrylic acid quality;
(4) the polymethyl acrylic acid grafting micron oxide powder after step (3) processing is added in the deionized water, slowly add cupric oxide or thionamic acid cobalt, stirring heating backflow 2～4h, the filtered while hot washing obtains final product after the drying; The quality that adds cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid grafting micron oxide powder quality.
The inorganic particulate of described coordination crosslinking agent core also adopts ordinary calcium carbonate or nano-calcium carbonate, and described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion; The preparation method of described hud typed coordination crosslinking agent is as follows:
(1) first ultra-sonic dispersion in Virahol with ordinary calcium carbonate or nano-calcium carbonate, under agitation condition, slowly drip amino silicane coupling agent and be warming up to 60～65 ℃ of reactions 3～5 hours, use acetone extract 24～36 hours behind the filtration drying, promptly get the calcium carbonate powders after coupling agent treatment; The mass ratio that feeds intake of described ordinary calcium carbonate or nano-calcium carbonate and amino silicane coupling agent is 1: 0.05～0.10, and the add-on of Virahol is that per 10 gram ordinary calcium carbonate or nano-calcium carbonate add 300～400ml;
(2) calcium carbonate powders, azo dicyano valeric acid and the sulfur oxychloride of adding after coupling agent treatment in reaction vessel, splash into α-Jia Jibiding, 25～30 ℃ were stirred 2～3 hours down, centrifugation obtains the throw out washed with isopropyl alcohol, and drying obtains the active carbonic acid calcium particle of anchoring azo initiator; Described calcium carbonate powders, azo dicyano valeric acid, sulfur oxychloride, the mass ratio that feeds intake of α-Jia Jibiding after coupling agent treatment is 10: 1: 50: 1;
Get the above-mentioned active carbonic acid calcium particle that obtains and place Virahol, add polyethylene of dispersing agent pyrrole network alkane ketone, ultra-sonic dispersion 5～10min, drip the organic monomer methacrylic acid after being warming up to 70～75 ℃ under stirring, polyreaction is 5～6 hours under the nitrogen protection, and reactant is centrifugal, obtain polymethyl acrylic acid grafting coated caco3 powder after the washing; The add-on of described Virahol is that every 3g active carbonic acid calcium particle adds 200～300ml, and described polyethylene pyrrole network alkane ketone is 0.1～0.2 times of treated carbonates particle mass, and the quality of described methacrylic acid is 1.5～2.0 times of treated carbonates particle mass;
(3) the polymethyl acrylic acid grafting coated caco3 powder that step (2) is obtained adds in the deionized water, slowly adds cupric oxide or thionamic acid cobalt, stirring heating backflow 2～3h, and the filtered while hot washing obtains the hud typed coordination crosslinking agent of final product after the drying; The add-on of described cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid grafting coated caco3 powder quality.
Described hud typed coordination crosslinking agent is as the application of a rubber crosslinker.
The present invention at the rubber base material molecular chain in contain and participate in the coordinate functional group, described coordination functional group group contains one of column element down: nitrogen-atoms, Sauerstoffatom, sulphur atom.One of described rubber matrix is preferred following: paracril, ethylene-vinyl acetate copolymer (EVA).
It is one of following that the blending means of described hud typed coordination crosslinking agent and rubber matrix can be selected: twin-roll mixing, banburying, screw rod are extruded.Crosslinked implementation method is that static hot pressing is crosslinked.
The present invention passes through structure design, synthetic have the organic/inorganic Composite Coordination Agents of nucleocapsid structure as a rubber crosslinker, its structure both had been different from inorganic metal salt such as copper sulfate, also was different from organic metal salt such as copper stearate, was expected to realize the comprehensive of two class material advantages.
Adopt above-mentioned compound coordination crosslinking agent to carry out coordination cross-linked to rubber with nucleocapsid structure, utilize that inorganic core provides favorable rigidity and intensity in the Composite Coordination Agents, utilizing organic shell is that macromolecular chain provides coordination cross-linked point and makes system keep good toughness, be expected to substitute traditional vulcanization of rubber and add black-reinforced technology, obtain all elastomeric materials preferably of intensity and toughness.
(4) description of drawings
Fig. 1 is hud typed organic/inorganic coordination crosslinking agent structural representation;
Fig. 2 is rubber/hud typed coordination cross-linked architectural schematic;
Fig. 3 is an inorganic metal salt coordination crosslinking agent structural representation;
Fig. 4 is the coordination cross-linked architectural schematic of rubber/inorganic metal salt, wherein 1. is inorganic core, 2. is organic high molecular polymer, 3. is coordination center, 4. is the coordinating group on the rubber matrix, 5. is rubber matrix;
Fig. 5 is the transmission electron microscope picture of the prepared hud typed coordination crosslinking agent of the embodiment of the invention 1;
Fig. 6 is the sem photograph of the prepared coordination crosslinking rubber section of the embodiment of the invention 1;
Fig. 7 is the sem photograph of the prepared coordination crosslinking rubber section of comparative example of the present invention 1;
Fig. 8 is the sem photograph of the prepared coordination crosslinking rubber section of comparative example of the present invention 2;
Fig. 9 is the stress-strain curve diagram of the embodiment of the invention 1 and comparative example 1,2 prepared elastomeric materials, and a, b, c are respectively the stress-strain(ed) curve of embodiment 1, comparative example 1, comparative example 2.
(5) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1:
The material that present embodiment adopts: inorganic particulate is selected nano silicon oxide, and the shell polymkeric substance is selected polymethyl acrylic acid (PMA), and the coordination of metal ion that shell is introduced is a cupric ion.Rubber matrix is Powdered acrylonitrile-butadiene rubber (NBR).
At first with nano silicon oxide in 600～650 ℃ of lower surface calcination 4～5h, with remove the surface a small amount of organic impurity.Take by weighing the powder 10g after the above-mentioned processing, be scattered in the 300ml toluene by ultra-sonic oscillation; Other claims silane coupling agent KH570 0.5g to pour in the small beaker, splashes into about 20 of deionized water, and normal temperature stirs 10min down and makes its hydrolysis in advance.Pour in the toluene the KH570 of above-mentioned hydrolysis in advance is disposable.Be warming up to boiling, quick mechanical stirring, reflux condensation mode, logical nitrogen protection finishes behind the reaction 4h.
With above-mentioned suspension 300ml, logical nitrogen protection progressively is warming up to 80 ℃, adds initiator B PO 0.20g, and mechanical stirring dropwise drips monomer M A 20g, 0.5ml/min, and reaction 5h gets product.Separate with the absolute ethanol washing recentrifuge after the product centrifugation, remove not grafted PMA, get 8.5g polymethyl acrylic acid engrafted nanometer silicon oxide powder SiO after the vacuum-drying
2-g-PMA.
With the powder SiO after the above-mentioned processing
2The about 8.0g of-g-PMA adds in the about 100ml of deionized water, slowly adds the 4.0g cupric oxide.Stirring heating backflow 2h.The filtered while hot washing, 75 ℃ of following dry 12h obtain the hud typed coordination crosslinking agent of 7.5g: SiO
2-g-PMA (Cu+).Its structural representation as shown in Figure 1, transmission electron microscope picture has tangible nucleocapsid shape structure as shown in Figure 5.
Take by weighing paracril powder 50g and the above-mentioned coordination crosslinking agent SiO for preparing
2-g-PMA (Cu+) powder 7.5g, disposable pouring in the torque rheometer mixing tank mixed after preliminary the mixing.Processing condition are: 150 ℃, and 60rpm, 10min.After mix finishing material is carried out on the compression molding instrument hot-forming, technology: temperature: 200 ℃, pressure: 15MPa, time: 15min, preheating: 5min.The structure of the rubber for preparing/hud typed coordination cross-linked system as shown in Figure 2, sem photograph is as shown in Figure 6.
The material that present embodiment adopts: inorganic particulate is selected nano zine oxide, and the shell polymkeric substance is selected polymethyl acrylic acid (PMA), and the coordination of metal ion that shell is introduced is a cupric ion.Rubber matrix is ethylene-vinyl acetate copolymer (EVA).
At first with nano zine oxide in 600～650 ℃ of lower surface calcination 4～5h, with remove the surface a small amount of organic impurity.Take by weighing the powder 10g after the above-mentioned processing, be scattered in the 400ml toluene by ultra-sonic oscillation; Other claims silane coupling agent KH570 1.0g to pour in the small beaker, splashes into about 25 of deionized water, and normal temperature stirs 10min down and makes its hydrolysis in advance.Pour in the toluene the KH570 of above-mentioned hydrolysis in advance is disposable.Be warming up to boiling, quick mechanical stirring, reflux condensation mode, logical nitrogen protection finishes behind the reaction 6h.
With above-mentioned suspension 400ml, logical nitrogen protection progressively is warming up to 80 ℃, adds initiator B PO 0.50g, and mechanical stirring dropwise drips monomer M A 25g, 0.5ml/min, and reaction 5h gets product.Separate with the absolute ethanol washing recentrifuge after the product centrifugation, remove not grafted PMA, get 8.5g polymethyl acrylic acid engrafted nanometer Zinc oxide powder ZnO-g-PMA after the vacuum-drying.
The about 8.0g of powder ZnO-g-PMA after the above-mentioned processing is added in the about 100ml of deionized water, slowly add the 8.0g cupric oxide.Stirring heating backflow 4h.The filtered while hot washing, 75 ℃ of following dry 12h obtain the hud typed coordination crosslinking agent of 7.5g: ZnO-g-PMA (Cu+).Transmission electron microscope results shows that it has tangible nucleocapsid shape structure.
Take by weighing EVA elastomerics 50g and above-mentioned coordination crosslinking agent ZnO-g-PMA (Cu+) the powder 7.5g that makes, in two roller mills, mix.Processing condition are: 150 ℃, and 10min.After mix finishing material is carried out on the compression molding instrument hot-forming, technology: temperature: 200 ℃, pressure: 15MPa, time: 15min, preheating: 5min.The test of the sample equilibrium swelling for preparing shows can only swelling and can not dissolve, and shows to have formed crosslinking structure.Scanning electron microscope, x-ray photoelectron power spectrum test shows system have formed the coordination interface interaction in addition, have formed coordination cross-linked structure in the explanation system.
Embodiment 3:
The present embodiment material therefor: inorganic particulate adopts common light calcium carbonate (325 orders, commercially available, celestial stone lime carbonate company limited in Jiande City, Zhejiang produces), and the polymkeric substance shell adopts polymethyl acrylic acid, and rubber matrix is a paracril, and the coordination center ion is a cupric ion.
Earlier with the common light calcium carbonate of 10.0g ultra-sonic dispersion in the 300ml Virahol, under agitation condition, slowly drip amino silicane coupling agent N-(aminoethyl)-aminopropyl trimethoxysilane and be warming up to 60 ℃ of reaction 3h, use acetone extract 24h behind the filtration drying, promptly get calcium carbonate powders through coupling agent treatment.In there-necked flask, add calcium carbonate powders, 1g azo dicyano valeric acid and the 50g sulfur oxychloride that 10g crosses through coupling agent treatment, splash into the 1g α-Jia Jibiding, 30 ℃ were stirred 2 hours down, centrifugation obtains throw out with washed with isopropyl alcohol for several times, and drying obtains the active carbonic acid calcium particle of 8.5g anchoring azo initiator.
Take by weighing the above-mentioned active carbonic acid calcium particle of 3g; place the 200ml Virahol; add 0.45g polyethylene of dispersing agent pyrrole network alkane ketone (PVP); ultra-sonic dispersion 5min; drip methacrylic acid 4.5g after being warming up to 70 ℃ under stirring; polyreaction is 5 hours under the nitrogen protection, and the reactant centrifuge washing obtains 4.5g polypropylene olefin(e) acid grafting coated caco3 powder CaCO for several times
3-g-PMA.
With the powder CaCO after the above-mentioned processing
3The about 3.0g of-g-PMA adds in the about 100ml of deionized water, slowly adds the 3.0g cupric oxide.Stirring heating backflow 2h.The filtered while hot washing, 75 ℃ of following dry 12h obtain the hud typed coordination crosslinking agent of 2.5g: CaCO
3-g-PMA (Cu+).Repeat above-mentioned preparation process 3 times, obtain 7.5g CaCO altogether
3-g-PMA (Cu+).Transmission electron microscope results shows that it has tangible nucleocapsid shape structure.
Take by weighing paracril powder 50g and the coordination crosslinking agent CaCO that makes according to aforesaid method
3-g-PMA (Cu+) powder 7.5g mixes in two roller mills.Processing condition are: 150 ℃, and 10min.After mix finishing material is carried out on the compression molding instrument hot-forming, technology: temperature: 200 ℃, pressure: 15MPa, time: 15min, preheating: 5min.The test of the sample equilibrium swelling for preparing shows can only swelling and can not dissolve, and shows to have formed crosslinking structure.Scanning electron microscope, x-ray photoelectron power spectrum test shows system have formed the coordination interface interaction in addition, have formed coordination cross-linked structure in the explanation system.
Embodiment 4:
The present embodiment material therefor: inorganic particulate adopts the micron order silicon oxide powder, and the shell polymkeric substance is a polymethyl acrylic acid, and rubber matrix is a paracril.Coordination center is a cobalt ion.
At first with silicon oxide powder in 600～650 ℃ of lower surface calcination 4～5h, with remove the surface a small amount of organic impurity.Take by weighing the powder 10g after the above-mentioned processing, be scattered in the 400ml deionized water by ultra-sonic oscillation; Other claims silane coupling agent KH570 1.0g to pour in the above-mentioned suspension, regulates between the pH value 4-5, is warming up to 80 ℃, quick mechanical stirring, and reflux condensation mode finishes behind the reaction 4h.By filter, obtain silane treatment rear oxidation Si powder 8.5g after the drying.
Silicon oxide powder 8.0g after the above-mentioned processing is scattered in the 300ml toluene; ultra-sonic dispersion 30min; after pour in the 1000ml there-necked flask, mechanical stirring is warming up to 80 ℃; nitrogen protection; disposable adding initiator B PO 0.30g dropwise adds monomer methacrylic acid (through underpressure distillation) 20g, finishes after about 60 minutes; continue to drip monomer 25g, add BPO 0.15g.Total reaction time was controlled at 3 hours, finished after-filtration, drying, got polymethyl acrylic acid grafting silicon oxide powder SiO
2-g-PMA 7.5g.
With the powder SiO after the above-mentioned processing
2The about 7.0g of-g-PMA adds in the about 200ml of deionized water, slowly adds 7.0g thionamic acid cobalt, stirring heating backflow 2h.The filtered while hot washing, 75 ℃ of following dry 12h obtain the hud typed coordination crosslinking agent of 6.5g: SiO
2-g-PMA (Co
+).Transmission electron microscope results shows that it has tangible nucleocapsid shape structure.
Take by weighing paracril powder 50g and the above-mentioned coordination crosslinking agent SiO that makes
2-g-PMA (Co+) powder 5.0g mixes in two roller mills.Processing condition are: 150 ℃, and 10min.After mix finishing material is carried out on the compression molding instrument hot-forming, technology: temperature: 200 ℃, pressure: 15MPa, time: 15min, preheating: 5min.The test of the sample equilibrium swelling for preparing shows can only swelling and can not dissolve, and shows to have formed crosslinking structure.Scanning electron microscope, x-ray photoelectron power spectrum test shows system have formed the coordination interface interaction in addition, have formed coordination cross-linked structure in the explanation system.
Comparative example 1: the coordination cross-linked material of rubber/inorganic metal salt
The material that present embodiment adopts: inorganic metal salt adopts anhydrous cupric sulfate, and rubber matrix adopts Powdered acrylonitrile-butadiene rubber.
At first with copper sulfate in 120 ℃ of following vacuum-dryings more than 4 hours, the back is levigate to 200um in high speed ball mill.After with paracril 100g with in double roll mill, carry out mixingly through pre-treatment copper sulfate 7.5g, temperature is 80-100 ℃, mixing time 10min.In the compression molding instrument, carry out after the slice hot-forming, temperature: 200 ℃, time: 15min, pressure: 15MPa.The structure of inorganic metal salt as shown in Figure 3, the structure of the coordination cross-linked system of rubber/inorganic metal salt for preparing as shown in Figure 4, sem photograph is as shown in Figure 7.
Comparative example 2: rubber/sulphur/carbon black system
The material that present embodiment adopts: rubber matrix adopts Powdered acrylonitrile-butadiene rubber, and linking agent is a sulphur, and strengthening agent is a carbon black.
With paracril 100g, sulphur 2.5g, zinc oxide 5.0g, altax 2.5g, anti-aging agent 5.0g, stearic acid 3.0g, carbon black 15g are mixing in blocks on double roll mill at first in proportion, and technological temperature is 80-100 ℃, mixing time 10min.Then sheet material is carried out in the compression molding instrument hot-forming, temperature: 160 ℃, time: 15min, pressure: 15MPa.The sem photograph of the rubber/sulphur for preparing/carbon black system as shown in Figure 8.
Among the embodiment 1 prepared coordination crosslinking agent structural representation as shown in Figure 1, transmission electron microscope picture has tangible nucleocapsid shape structure as shown in Figure 5.Compare (Fig. 8) with traditional sulphur carbon black system, in hud typed coordination cross-linked system (Fig. 6) and the coordination cross-linked system of inorganic metal salt (Fig. 7), all there is stronger interface interaction between coordination agent and rubber matrix, especially show more obvious drawing-off structure between prepared hud typed linking agent of the present invention and rubber matrix, show that the toughness of system keeps better.
The mechanical strength of present embodiment rubber is represented by stretch test result, and is provided in Fig. 9.As can be seen from Figure 9, comparative example 1 prepared inorganic metal salt coordination crosslinking rubber has higher rigidity and tensile strength, but toughness is very poor, only is 80%, has lost the advantage of rubber; The sulfuration that comparative example 2 makes also keeps good toughness through the elastomeric material of black-reinforced, but its rigidity and tensile strength are relatively poor; Compare with above-mentioned, the prepared hud typed coordination crosslinking rubber of present embodiment has rigidity and toughness preferably simultaneously, shows that the rubber that is obtained has mechanical property preferably.
Table 1 has provided the swelling equilibrium test-results of elastomeric material in embodiment 1 and the comparative example 1,2:
Table 1: the cross-linking density of the embodiment of the invention and comparative example 1,2 obtained elastomeric material
| | Embodiment | 1 | Comparative example 1 | Comparative example 2 |
| Cross-linking density 10 4v/mol.cm -3 | 10.05 | 15.54 | 12.25 |
The result shows that rubber has all formed three-dimensional net structure in three examples.Also show by the designed hud typed coordination crosslinking agent of the present invention and can realize successfully that rubber coordination is crosslinked.
Above-mentioned materials structure and performance evaluation are carried out by the following method:
1, TEM (transmission electron microscope) analysis: the 0.05g powder is scattered in the 50ml dehydrated alcohol, and sonic oscillation 30min observes after the copper mesh surface drying.Instrument: JEM-100 CXII.
2, scanning electron microscope analysis: rubber sample is freezing brittle failure in liquid nitrogen, and handle at the section part metal spraying back.Instrument: Hitach-4700.
3, tension test: (GB/T528-92) carry out tensile property by " rubber Erichsen test method " and test sample specification: 80 * 5 * 2mm, draw speed 500mm/min, 23 ± 2 ℃ of temperature.
4, equilibrium swelling test: with the methylene dichloride is solvent, carries out swelling equilibrium 7 days under 25 ℃, according to the cross-linking density of Flory-Rehner Equation for Calculating sample:
v＝[ln(1-v
r)+v
r+χ·v
r 2]/[-v
s(v
r 1/3-v
r/2)]
V is a cross-linking density in the formula; v
rBe the volume fraction of rubber phase in swollen rubber; v
sIt is the molecular volume of solvent; χ is the interaction parameter between solvent and polymkeric substance, gets experimental value 1.03 * 10
-5
Claims (12)
1. a hud typed coordination crosslinking agent is characterized in that described coordination crosslinking agent is the clad structure that shell holds core; Described core is made up of inorganic particulate, and described shell is made up of organic high molecular polymer, has on the described organic high molecular polymer for the coordinate coordination center, is connected by covalent linkage between described inorganic particulate and described organic high molecular polymer; Described organic high molecular polymer is one of following: polymethyl acrylic acid, polyacrylic acid, polymethylmethacrylate, polyvinyl acetate (PVA), described coordination center are transition metal ion, and described inorganic particulate is inorganic micro-powder or inorganic nano-particle.
2. hud typed coordination crosslinking agent as claimed in claim 1, it is characterized in that described coordination crosslinking agent is prepared as follows: choose organic monomer, with the inorganic particulate is core, by the polymer in situ polymerization technique, make described organic monomer carry out graft polymerization on the inorganic particulate surface and form organic high molecular polymer, described organic high molecular polymer is modified by side group and is introduced coordination center, obtain described hud typed coordination crosslinking agent, described organic monomer is one of following: methacrylic acid, vinylformic acid, methyl methacrylate, vinyl acetate.
3. hud typed coordination crosslinking agent as claimed in claim 2 is characterized in that described inorganic particulate maybe can produce the thermolysis type initiator of living radical at the unsaturated carbon-carbon double bond of inorganic particulate surface grafting polymerization for organic monomer by the finishing introducing.
4. hud typed coordination crosslinking agent as claimed in claim 1, it is characterized in that described inorganic particulate is nano-oxide or micron oxide compound, described nano-oxide is nano silicon oxide, nano-titanium oxide, nano zine oxide or nano aluminium oxide, and described micron oxide compound is the micron order silicon oxide.
5. hud typed coordination crosslinking agent as claimed in claim 1, it is one of following to it is characterized in that described inorganic particulate is selected from: nano-calcium carbonate, ordinary calcium carbonate.
6. the described coordination crosslinking agent of one of claim 1～3 is characterized in that described coordination center is one of following: cupric ion, cobalt ion, zine ion, mn ion, titanium ion.
7. claim 4 or 5 described coordination crosslinking agents is characterized in that the preparation method of described coordination crosslinking agent comprises the steps:
(1) inorganic particulate after the purification process is scattered in the solvent, with silane coupling agent at 60～80 ℃ of back flow reaction 3～6h, aftertreatment obtains the inorganic particulate after the coupling agent treatment; The mass ratio that feeds intake of inorganic particulate after the described purification process and silane coupling agent is 1: 0.05～0.10;
(2) inorganic particulate after the coupling agent treatment is scattered in the solvent, in the presence of initiator with organic monomer under nitrogen protection in 60～80 ℃ of polyreaction 3～6h, aftertreatment obtains organic high molecular polymer grafting inorganic particulate powder; Described organic monomer quality is 1.5～2.5 times of inorganic particulate quality after the coupling agent treatment;
(3) reflux 2～4h in deionized water with organic high molecular polymer grafting inorganic particulate powder and transistion metal compound, aftertreatment obtains the hud typed coordination crosslinking agent of final product; The add-on of described transistion metal compound is 0.5～1.0 times of organic high molecular polymer grafting inorganic particulate powder quality.
8. the described hud typed coordination crosslinking agent of claim 7, the core that it is characterized in that described coordination crosslinking agent is a nano-oxide, described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion, and described hud typed coordination crosslinking agent is made as follows:
(1) at first with nano-oxide in 600～650 ℃ of lower surface calcination 4～5h;
(2) nano-oxide powder after will handling is scattered in the toluene, adds the silane coupling agent γ-methacryloxypropyl trimethoxy silane of hydrolysis in advance, is warming up to boiling, stir reflux condensation mode, logical nitrogen protection fast, finish behind reaction 4～6h, obtain suspension; The nano-oxide after described calcination is handled and the mass ratio that feeds intake of silane coupling agent γ-methacryloxypropyl trimethoxy silane are 1: 0.05～0.10, and the add-on of toluene is that the nano-oxide after per 10 gram calcinations are handled adds 300～400ml;
(3) the logical nitrogen protection of the suspension that step (2) is obtained, progressively be warming up to 60～80 ℃, add the radical initiator dibenzoyl peroxide, stir, slowly drip the organic monomer methacrylic acid, reaction 3～5h obtains product, and product gets polymethyl acrylic acid engrafted nanometer oxide powder after separation, washing, vacuum-drying; The quality that adds described methacrylic acid is 2.0～2.5 times of nano oxidized amount after calcination is handled, and the add-on of described dibenzoyl peroxide is 0.01～0.02 times of described methacrylic acid quality;
(4) the polymethyl acrylic acid engrafted nanometer oxide powder after step (3) processing is added in the deionized water, slowly add cupric oxide or thionamic acid cobalt, stirring heating backflow 2～4h, the filtered while hot washing obtains final product after the drying; The quality that adds cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid engrafted nanometer oxide powder quality.
9. the described hud typed coordination crosslinking agent of claim 7, the core that it is characterized in that described coordination crosslinking agent is the micron oxide compound, described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion, and described hud typed coordination crosslinking agent is made as follows:
(1) at first with the micron oxide compound in 600～650 ℃ of lower surface calcination 4～5h;
(2) the micron oxide powder after will handling is scattered in the deionized water, add silane coupling agent γ-methacryloxypropyl trimethoxy silane, regulate between the pH value 4-5, be warming up to 80 ℃, stir fast, reflux condensation mode finishes behind reaction 4～6h, obtains coupling agent treatment rear oxidation thing powder after filtration, the drying; The micron oxide compound after described calcination is handled and the mass ratio that feeds intake of silane coupling agent γ-methacryloxypropyl trimethoxy silane are 1: 0.05～0.10, and the add-on of deionized water is that the micron oxide compound after per 10 gram calcinations are handled adds 300～400ml;
(3) the coupling agent treatment rear oxidation thing powder that step (2) is obtained is distributed in the toluene, be warming up to 60～80 ℃, add the radical initiator dibenzoyl peroxide, stir, slowly drip the organic monomer methacrylic acid, nitrogen protection reaction 3～5h down obtains product, and product gets polymethyl acrylic acid grafting micron oxide powder after separation, washing, vacuum-drying; The add-on of toluene is that per 10 gram coupling agent treatment rear oxidation thing powder add 300～400ml, the quality that adds described methacrylic acid is 2.0～2.5 times of coupling agent treatment rear oxidation thing powder quality, and the add-on of described dibenzoyl peroxide is 0.01～0.02 times of methacrylic acid quality;
(4) the polymethyl acrylic acid grafting micron oxide powder after step (3) processing is added in the deionized water, slowly add cupric oxide or thionamic acid cobalt, stirring heating backflow 2～4h, the filtered while hot washing obtains final product after the drying; The quality that adds cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid grafting micron oxide mass.
10. the described hud typed coordination crosslinking agent of claim 7, the inorganic particulate that it is characterized in that described coordination crosslinking agent core adopts ordinary calcium carbonate or nano-calcium carbonate, described organic high molecular polymer is a polymethyl acrylic acid, and described coordination center is cupric ion or cobalt ion; The preparation method of described hud typed coordination crosslinking agent is as follows:
(1) first ultra-sonic dispersion in Virahol with ordinary calcium carbonate or nano-calcium carbonate, under agitation condition, slowly drip amino silicane coupling agent and be warming up to 60～65 ℃ of reactions 3～5 hours, use acetone extract 24～36 hours behind the filtration drying, promptly get the calcium carbonate powders after coupling agent treatment; The mass ratio that feeds intake of described ordinary calcium carbonate or nano-calcium carbonate and amino silicane coupling agent is 1: 0.05～0.10, and the add-on of Virahol is that per 10 gram ordinary calcium carbonate or nano-calcium carbonate add 300～400ml;
(2) calcium carbonate powders, azo dicyano valeric acid and the sulfur oxychloride of adding after coupling agent treatment in reaction vessel, splash into α-Jia Jibiding, 25～30 ℃ were stirred 2～3 hours down, centrifugation obtains the throw out washed with isopropyl alcohol, and drying obtains the active carbonic acid calcium particle of anchoring azo initiator; Described calcium carbonate powders, azo dicyano valeric acid, sulfur oxychloride, the mass ratio that feeds intake of α-Jia Jibiding after coupling agent treatment is 10: 1: 50: 1;
Get the above-mentioned active carbonic acid calcium particle that obtains and place Virahol, add polyethylene of dispersing agent pyrrole network alkane ketone, ultra-sonic dispersion 5～10min, drip the organic monomer methacrylic acid after being warming up to 70～75 ℃ under stirring, polyreaction is 5～6 hours under nitrogen protection, and reactant is centrifugal, obtain polymethyl acrylic acid grafting coated caco3 powder after the washing; The add-on of described Virahol is that every 3g active carbonic acid calcium particle adds 200～300ml, and described polyethylene pyrrole network alkane ketone is 0.1～0.2 times of treated carbonates particle mass, and the quality of described methacrylic acid is 1.5～2.0 times of treated carbonates particle mass;
(3) the polymethyl acrylic acid grafting coated caco3 powder that step (2) is obtained adds in the deionized water, slowly adds cupric oxide or thionamic acid cobalt, stirring heating backflow 2～3h, and the filtered while hot washing obtains the hud typed coordination crosslinking agent of final product after the drying; The add-on of described cupric oxide or thionamic acid cobalt is 0.5～1.0 times of polymethyl acrylic acid grafting coated caco3 powder quality.
11. a hud typed coordination crosslinking agent as claimed in claim 1 is as the application of a rubber crosslinker.
12. the application of hud typed coordination crosslinking agent as claimed in claim 11 is characterized in that containing in the molecular chain of described rubber matrix and participates in the coordinate functional group, described functional group contains one of column element down: nitrogen-atoms, Sauerstoffatom, sulphur atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101645530A CN101220127B (en) | 2007-12-06 | 2007-12-06 | Nucleocapsid type rubber coordination crosslinking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101645530A CN101220127B (en) | 2007-12-06 | 2007-12-06 | Nucleocapsid type rubber coordination crosslinking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101220127A true CN101220127A (en) | 2008-07-16 |
| CN101220127B CN101220127B (en) | 2010-06-09 |
Family
ID=39630224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101645530A Expired - Fee Related CN101220127B (en) | 2007-12-06 | 2007-12-06 | Nucleocapsid type rubber coordination crosslinking agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101220127B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356129A (en) * | 2009-01-15 | 2012-02-15 | 康奈尔大学 | Nanoparticle organic hybrid materials (nohms) |
| CN104597113A (en) * | 2015-01-21 | 2015-05-06 | 华中师范大学 | Image acquisition semiconductor film for high-resolution mass-spectral imaging system, and preparation method and application of image acquisition semiconductor film |
| CN105384969A (en) * | 2015-12-14 | 2016-03-09 | 江苏爱特恩高分子材料有限公司 | High-dispersion zinc oxide and preparation method thereof |
| CN106243512A (en) * | 2016-10-21 | 2016-12-21 | 安徽江淮汽车股份有限公司 | A kind of preparation method and applications of modified micaceous powder |
| CN108264925A (en) * | 2017-12-25 | 2018-07-10 | 华东理工大学 | Nonacid crude oil metal remover with nucleocapsid and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4956398A (en) * | 1989-06-07 | 1990-09-11 | Polysar Limited | Nitrile rubber/vinyl chloride polymer/silica compositions |
| US20090230345A1 (en) * | 2004-12-02 | 2009-09-17 | Leo Saija | Aqueous Polymer Dispersion Useful for Preparing Base-Coat Composition for Embossed Leather |
-
2007
- 2007-12-06 CN CN2007101645530A patent/CN101220127B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356129A (en) * | 2009-01-15 | 2012-02-15 | 康奈尔大学 | Nanoparticle organic hybrid materials (nohms) |
| CN104597113A (en) * | 2015-01-21 | 2015-05-06 | 华中师范大学 | Image acquisition semiconductor film for high-resolution mass-spectral imaging system, and preparation method and application of image acquisition semiconductor film |
| CN104597113B (en) * | 2015-01-21 | 2015-12-09 | 华中师范大学 | A kind of high resolution mass spectrum imaging system image acquisition semiconductive thin film, preparation method and application |
| CN105384969A (en) * | 2015-12-14 | 2016-03-09 | 江苏爱特恩高分子材料有限公司 | High-dispersion zinc oxide and preparation method thereof |
| CN105384969B (en) * | 2015-12-14 | 2018-02-16 | 江苏爱特恩高分子材料有限公司 | A kind of high dispersive zinc oxide and preparation method thereof |
| CN106243512A (en) * | 2016-10-21 | 2016-12-21 | 安徽江淮汽车股份有限公司 | A kind of preparation method and applications of modified micaceous powder |
| CN106243512B (en) * | 2016-10-21 | 2018-09-07 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method and applications of modified micaceous powder |
| CN108264925A (en) * | 2017-12-25 | 2018-07-10 | 华东理工大学 | Nonacid crude oil metal remover with nucleocapsid and its preparation method and application |
| CN108264925B (en) * | 2017-12-25 | 2020-08-18 | 华东理工大学 | Non-acidic crude oil demetallizing agent with core-shell structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101220127B (en) | 2010-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rong et al. | Surface modification of nanoscale fillers for improving properties of polymer nanocomposites: a review | |
| CN103897434B (en) | The preparation method that plastic master batch is Nano calcium carbonate dedicated | |
| CN100371384C (en) | Reacting nano inorganic particle/polymer composite material | |
| CN101220127B (en) | Nucleocapsid type rubber coordination crosslinking agent | |
| CN101407601B (en) | Method for modifying water encounter swelling rubber by using hydrophobic monomer | |
| CN101456961B (en) | Method for preparing reactive nano calcium carbonate-native rubber composite material | |
| CN101392070B (en) | Industrial preparation method of PVC processing aid | |
| CN105949366A (en) | Metal antirust emulsion as well as preparation method and application thereof | |
| CN101314696A (en) | Nano-SiO2 modified aluminium section bar superior atmospheric corrosion resisting polyester powder paint and preparation method thereof | |
| CN103436976B (en) | The method of polyolefin-based composite fibre is prepared by organic modification nano particle | |
| CN102464839A (en) | Composite toughening modifier for plastics and preparation method thereof | |
| CN103554560B (en) | A kind of preparation method of generated in-situ unsaturated fatty acid zinc salt reinforcement natural rubber | |
| CN103554558A (en) | Preparation method of hydroxyethyl methylacrylate rubber grafted and modified clay-enhanced natural rubber composite material | |
| CN1189523C (en) | Surface treatment method for improving hydrophobicity of Nano particles of calcium carbonate | |
| CN108148354A (en) | A kind of hybrid particle modified polymer composites of self assembly and preparation method thereof | |
| CN101445646A (en) | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials | |
| CN101514247B (en) | High-efficiency multifunctional compound enforcing agent and preparation method thereof | |
| CN100462379C (en) | Preparation method of ultraviolet light stabilizer | |
| CN108285620B (en) | Vulcanization activator for blended rubber and preparation method thereof | |
| CN114044997B (en) | Polyethylene composite material for glass fiber reinforced thermoplastic pipeline | |
| CN101220122B (en) | Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same | |
| CN101585977B (en) | Preparation method of polypropylene reinforced plasticized modifier | |
| CN108276716A (en) | A kind of graphene/Acrylate rubber composite material and preparation method thereof | |
| CN111518337A (en) | Graphene/basalt fiber reinforced composite material and preparation method thereof | |
| CN104446073B (en) | A kind of preparation method of water soluble polymer surface graft modification Machine-made Sand |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100609 Termination date: 20131206 |