CN108912250A - A kind of high-damping, high wet-sliding resistant, the ionomer of low-heat-generation and preparation method - Google Patents
A kind of high-damping, high wet-sliding resistant, the ionomer of low-heat-generation and preparation method Download PDFInfo
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- CN108912250A CN108912250A CN201810926792.3A CN201810926792A CN108912250A CN 108912250 A CN108912250 A CN 108912250A CN 201810926792 A CN201810926792 A CN 201810926792A CN 108912250 A CN108912250 A CN 108912250A
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- 238000013016 damping Methods 0.000 title claims abstract description 48
- 229920000554 ionomer Polymers 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005865 alkene metathesis reaction Methods 0.000 claims abstract description 18
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 12
- 239000005065 High vinyl polybutadiene Substances 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 230000021523 carboxylation Effects 0.000 claims abstract description 6
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000000693 micelle Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- -1 hydrogen Zinc oxide Chemical class 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 235000011837 pasties Nutrition 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011984 grubbs catalyst Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 1
- 239000011987 hoveyda–grubbs catalyst Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 238000005649 metathesis reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 229920000642 polymer Polymers 0.000 abstract description 19
- 239000000945 filler Substances 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 8
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012496 blank sample Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010358 mechanical oscillation Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/26—Incorporating metal atoms into the molecule
Abstract
The present invention provides a kind of high-damping, high wet-sliding resistant, the ionomer of low-heat-generation and preparation methods.Carboxylation modification is carried out to high vinyl polybutadiene rubber using olefin metathesis reaction, and then with metal oxide or metal hydroxides complexing at salt.The present invention overcomes relying solely on polymer or filler and being blended to improve the limitation of damping capacity, avoid between polymer or between polymer and filler the problem of poor compatibility.Ionomer produced by the present invention is expected to become a kind of new function rubber product for meeting high-performance tire and damping material requirement.
Description
Technical field
The present invention relates to a kind of high-damping, high wet-sliding resistant, the ionomer of low-heat-generation, preparation and applications, belong to rubber
Preparation, modification and the manufacture field of material.
Background technique
With the development of railway traffic, rail vehicle speed is continuously improved, but the vibration that generates of when bullet train works and
Noise not only pollutes environment, but also influences level of comfort and physical and mental health that people take.Therefore, to ensure vehicle part just
It is often used, improves the comfort and reduce influence of the vehicle noise to environment that people take, vehicle need to be carried out at damping noise reduction
Reason.Mitigating mechanical oscillation using the capacity loss for increasing mechanical system or structure and reducing the damping research of noise is always state
The hot spot of inside and outside concern.
Damping material be one kind can absorb vibration mechanical energy, sound energy and them can be converted to thermal energy, electric energy, magnetic energy or
Other forms energy and a kind of functional material consumed can be used for damping and sound absorption device.Wherein, polymer damping material,
Especially rubber material is because that nearby can generate in-fighting by the interior friction of macromolecular chain segment in glass transition temperature (Tg), not only
It can effectively reduce mechanical noise and mitigate mechanical oscillation, improve working efficiency, and be also beneficial to improve product quality, therefore,
Rubber damping material is just being widely used in communications and transportation, building, machinery and aerospace field.
High damping material should meet the higher losses factor (tan δ) and wider effective damping temperature range (tan δ>0.3) want
It asks.However, the glassy transition area of general homopolymer and copolymer is relatively narrow, the temperature range substantially glass of effective damping is generated
Change ± (10~15) DEG C near transition temperature, greatly limits its range for using temperature.The glass transition of rubber type of material
Area mostly occurs in room temperature hereinafter, and resinous material cannot fully meet practical high-damping then more than room temperature
The requirement of material.Therefore, under the premise of guaranteeing material tan δ value, the study on the modification for how widening effective damping temperature range range draws
The extensive concern of researcher is played.
In recent years, using blend rubber (Shi X Y, Weina B, Shugao Z.Study on the damping of
EVM based blends[J].Journal of Applied Polymer Science,2011,120(2):1121-
1125.) (Chinese patent 201610147275.7), filler modified (Chinese patent 201410378563.4), small point organic, are copolymerized
Sub- hydridization damping (Chinese patent 201510362988.0) and interpenetrating polymer networks (Qin C L, Tang D Y, Zhang J
S,et al.Study on Damping Properties of PU/VER IPN Materials[J].Journal of
Materials Engineering, 2003.) etc. technologies widen damping material to reach by widening its glass transition section
The purpose using temperature range and frequency range of material, although above-mentioned method of modifying can improve the power of damping material to a certain extent
Performance or damping capacity are learned, but leads to two-phase or multiphase between polymer or due to differences such as polarity between polymer and filler
Mixing is uneven, therefore selected material is extremely restricted.
From aggressiveness (ionomer), also known as ionomer, refer on macromolecular main chain containing it is a small amount of (mole
Score<10%) acid group hung, and these acid groups are partly or entirely neutralized into a quasi polymer of salt, due to metal ion
Between the p- ion clustering architecture of multiple ion, this unique state of aggregation knot can be gathered by electrostatic interaction or complexing
Structure can assign substrate material certain special performances, such as excellent mechanical strength, heat resistance, rheological characteristic, compatibility.So
And currently without about from aggressiveness damping capacity research and report.
Summary of the invention
In view of the drawbacks of the prior art, high-damping, high wet-sliding resistant, low life are prepared the purpose of the present invention is to provide a kind of
The new method of thermion polymer, to overcome the limitation for relying solely on polymer or filler blending raising damping capacity.
To achieve the goals above, the present invention uses following technical method：
A kind of high-damping, high wet-sliding resistant, low-heat-generation ionomer, it is poly- to high-vinyl using olefin metathesis reaction
Butadiene rubber carries out Carboxylation modification, and then with metal oxide or metal hydroxides complexing at salt.
Preferably, the high vinyl polybutadiene rubber is vinyl structure content>80% unformed elastomer.
Preferably, the organic solvent that the olefin metathesis reaction is selected is saturated alkanes and the first such as hexamethylene, n-hexane
One of aromatic hydrocarbon such as benzene, ethylbenzene, dimethylbenzene and/or several.
Preferably, solvent selected by olefin metathesis reaction is benzene, toluene, ethylbenzene, dimethylbenzene, propyl benzene, acetone, tetrahydro furan
It mutters, one kind of methylene chloride, chloroform and/or several.
Preferably, the catalyst that the olefin metathesis reaction is selected is Zhan1-B catalyst, Hoveyda-Grubbs is urged
Agent, Sigma-Aldrich catalyst, Grubbs catalyst, one kind of Sigma-Aldrich catalyst and/or several.
Preferably, grafted monomers selected by olefin metathesis reaction be acrylic acid, methacrylic acid, methyl methacrylate,
Ethyl methacrylate, one kind of butyl methacrylate and/or several.
Preferably, the Carboxylation modified monomer selected is acrylic acid.
Preferably, the metal oxide is sodium oxide molybdena, magnesia, zinc oxide, aluminium oxide, and metal hydroxides is hydrogen-oxygen
Change sodium, magnesium hydroxide, zinc hydroxide, one kind of aluminium hydroxide and/or several.
Preferably, olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, acrylic acid 2-16
Part, catalyst Grubbs Π is 0.1-5 parts, and reaction temperature is 10-70 DEG C, reaction time 0.5-5h, mixing speed 200-
1000rad/min。
Preferably, olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, acrylic acid 8-12
Part, catalyst Grubbs Π is 0.5-2 parts, and reaction temperature is 40-60 DEG C, reaction time 1.5-2.5h, and mixing speed is
500-700rad/min。
It is further preferred that olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, and acrylic acid is
10 parts, catalyst Grubbs Π be 1 part, reaction temperature be 2h, mixing speed 600rad/min in 50 DEG C of reaction time.
Preferably, the high-damping, high wet-sliding resistant, low-heat-generation ionomer, which is characterized in that preparation method packet
Include following steps：
A) HVBR (shredding, convenient for dissolution) is added in the reaction vessel, is put into magneton, is vacuum-treated, solvent is added, is placed in
Accelerate HVBR dissolution at 60 DEG C of magnetic stirrer.
B) grafted monomers-cyclohexane solution and catalyst that are made into are added to the HVBR toluene solution being completely dissolved
In, it is placed in the magnetic stirrer of required temperature, wait react to required time, is drawn off and is put into freezing chamber cooling rapidly
To room temperature.
C) enough dehydrated alcohols are added into reaction product, and are constantly stirred with glass bar, until obtaining solid micelle
Until, then after being washed twice with dehydrated alcohol, be drawn off drying.
D) micelle after drying then is pressed into thin slice, be coated in nickel screen, be placed in Soxhlet extractor acetone reflux for 24 hours
Purification, to remove the impurity such as remaining initiator and unreacted grafted monomers.
E) graft product after purification is placed in 60 DEG C of vacuum oven drying until constant weight, can be obtained pure horse anhydridization
HVBR。
Preferably, by HVBR-g-COOH be placed in double roller begin to pratise in be pressed into thin slice, weigh according to the ratio solid metal oxide or
Hydroxide, which is put into mortar, to be ground into powder and is mixed into paste with appropriate aromatic naphtha, then uniformly applies pasty mixture
It is overlying on thin slice, and the 5-20min that plasticates repeatedly on the double roll mill, to guarantee that NaOH can spread uniform and and graft polymers
Carboxylate radical complete neutralization on strand, can be prepared by HVBR ionomer.
Preferably, the vulcanizate of the HVBR ionomer, which is characterized in that proportion is as follows：
Compared with prior art, the beneficial effect that the present invention reaches is：
1. carrying out polarityization to HVBR using olefin metathesis to be modified, improves conventional free radical and react low grafting rate, height
The shortcomings that gel content.
It is modified 2. the present invention carries out polarityization to HVBR by using acrylic acid (AA), obtains Carboxylation HVBR (HVBR-g-
COOH it), and is further complexed through sodium hydroxide, has obtained damping capacity and mechanical property is excellent, while damping temperature domain range
Wider HVBR ionomer, and compared with the existing technology, the invention avoids between polymer or polymer and filler
Between poor compatibility the problem of, be applicable to the high butadiene-styrene rubber of contents of ethylene.
3. damping capacity and mechanical strength not only can be improved in HVBR ionomer prepared by the present invention, while can also improve
The anti-slippery of the polymer, anti-dry slip, low-heat-generation and low rolling resistance, therefore, HVBR ionomer are expected to become a kind of full
The new function rubber product that sufficient high-performance tire and damping material require.
Detailed description of the invention
Fig. 1-2 is respectively the SEM microscopic appearance of embodiment 1HVBR-g-MAH Yu comparative example 1HVBR ionomer.
Fig. 3 and Fig. 4 is the fissipation factor figure of 2 vulcanizate of embodiment 1 and embodiment.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1：
HVBR (shredding, convenient for dissolution) is added in polymerization bottle, is put into magneton, is vacuum-treated, solvent is added, is placed in magnetic force
Accelerate HVBR dissolution at 60 DEG C of blender.Then 10phr acrylic acid and 1phr Grubbs Π catalyst are dissolved in toluene respectively
In, it is added in the HVBR toluene solution being completely dissolved, is placed in 50 DEG C of magnetic stirrer, after reacting 2h, be drawn off
And it is put into freezer compartment of refrigerator rapidly and is cooled to room temperature.Enough dehydrated alcohols are added into reaction product, and constantly use glass bar
Stirring is drawn off drying until obtaining solid micelle, then after being washed twice with dehydrated alcohol.Then after drying
Micelle is pressed into thin slice, is coated in filter paper, is placed in acetone reflux in locking-type extractor and purifies for 24 hours, to remove remaining initiator
Equal impurity.The graft product after purification is finally placed in 60 DEG C of vacuum oven drying until constant weight, can be obtained purifying
HVBR-g-COOH by HVBR-g-COOH processed be placed in double roller begin to pratise in be pressed into thin slice, by n (- the COOH of grafting):N (NaOH)=1:
2, which weigh solid sodium hydroxide, is put into mortar and is ground into powder and is mixed into paste with appropriate aromatic naphtha, then mixes paste
Close object to be evenly applied on thin slice, and the 20min that plasticates repeatedly on the double roll mill, with guarantee NaOH can spread uniformly and with connect
Carboxylate radical complete neutralization on branch polymer molecular chain, can be prepared by HVBR ionomer.
Comparative example 1：It is not grafted modified blank sample HVBR.
Fig. 1 is the SEM microscopic appearance of embodiment 1HVBR-g-COOH and comparative example 1HVBR ionomer.Analysis chart 1 can
Know, the Tensile fracture of HVBR is more smooth, and SEM Tensile fracture of the sodium from aggressiveness has a large amount of bulge-structure, and protrusion
Structure is connected to each other, and illustrates sodium from occurring the p- ion clustering architecture of multiple ion in aggressiveness, and molecule interchain active force increases
Greatly.
It is analyzed by Fig. 2 it is found that compared to for comparative example 1HVBR, embodiment 1HVBR ionomer is in 0 DEG C and 30 DEG C
Fissipation factor (tan δ) value increase, and tan δ value at 60-80 DEG C reduces, and illustrates the anti-slippery of HVBR ionomer
Property, anti-dry slip, low-heat-generation and low rolling is resistive is improved.Meanwhile (effective damping temperature range is -14.9 compared to comparative example HVBR
~17.8 DEG C) for, the effective damping temperature range of embodiment 1HVBR ionomer is widened from -8.8 DEG C to 30.1 DEG C, and more
Close to room temperature range, illustrate that the damping capacity of HVBR ionomer is also improved.
1 HVBR and HVBR ionomer mechanical property table of table
As shown in Table 1, compared to for comparative example 1HVBR, the tensile strength of embodiment 1HVBR ionomer is stretched surely and is answered
Power and tearing strength are significantly increased, and illustrate that the mechanical strength of HVBR ionomer improves.
Embodiment 2：
The same terms preparation embodiment 2HVBR-g-COOH is reacted according to Solution Free Radical in example 1.It will HVBR-g- processed
COOH be placed in double roller begin to pratise in be pressed into thin slice, by n (acrylic acid of grafting):N (NaOH)=1:1, which weighs solid sodium hydroxide, is put into
It is ground into powder in mortar and is mixed into paste with appropriate aromatic naphtha, then pasty mixture is evenly applied on thin slice,
And the 10min that plasticates repeatedly on the double roll mill, with guarantee NaOH can spread uniformly and with the carboxylic on graft polymers strand
Acid group complete neutralization can be prepared by HVBR ionomer.
It is analyzed by Fig. 3 it is found that in comparison with comparative example 1HVBR, embodiment 2HVBR ionomer is in 0 DEG C and 30 DEG C
When fissipation factor (tan δ) value increase, and tan δ value at 60-80 DEG C reduces, and illustrates the anti-slippery of HVBR ionomer
Property, anti-dry slip, low-heat-generation and low rolling is resistive is improved.Meanwhile with blank sample HVBR (effective damping temperature range be -14.9~
17.8 DEG C) in comparison, the effective damping temperature range of HVBR ionomer is widened from -11.2 DEG C to 26.5 DEG C, and closer room
Warm range illustrates that the damping capacity of HVBR ionomer is also improved.
2 HVBR and HVBR ionomer mechanical property table of table
As shown in Table 2, compared to for comparative example 1HVBR, the tensile strength of embodiment 2HVBR ionomer is stretched surely and is answered
Power and tearing strength are significantly increased, and illustrate that the mechanical strength of HVBR ionomer improves.
The present invention overcomes relying solely on polymer or filler blending to improve the limitation of damping capacity, polymer is avoided
Between or polymer and filler between poor compatibility the problem of.A kind of ionomer, the preparation method include first using alkene
Metathesis reaction carries out Carboxylation modification to high vinyl polybutadiene rubber HVBR, and acrylic monomers is grafted to HVBR molecule
On chain, then it is complexed by two-roll mill and sodium hydroxide into salt.Ionomer forms more because of the introducing of metal ion
The p- ion clustering architecture of heavy ion, intermolecular force enhancing, not only increases the mechanical strength and damping capacity of polymer, together
When so that its anti-slippery and anti-dry slip is improved while is reduced heat and rolling resistance.Ionomer produced by the present invention
It is expected to become a kind of new function rubber product for meeting high-performance tire and damping material requirement.
Claims (10)
1. the ionomer of a kind of high-damping, high wet-sliding resistant, low-heat-generation, it is characterised in that：Using olefin metathesis reaction pair
High vinyl polybutadiene rubber (abbreviation HVBR) carries out Carboxylation modification, so with metal oxide or metal hydroxides network
Synthesize salt.
2. the ionomer of a kind of high-damping according to claim 1, high wet-sliding resistant, low-heat-generation, it is characterised in that：Institute
Stating high vinyl polybutadiene rubber is vinyl structure content>80% unformed elastomer.
3. the ionomer of a kind of high-damping according to claim 1, high wet-sliding resistant, low-heat-generation, it is characterised in that：Institute
State olefin metathesis reaction selection organic solvent be hexamethylene, n-hexane, benzene, toluene, ethylbenzene, dimethylbenzene, propyl benzene, acetone,
Tetrahydrofuran, methylene chloride, one kind of chloroform and/or several.
4. the ionomer of a kind of high-damping according to claim 1, high wet-sliding resistant, low-heat-generation, it is characterised in that：Institute
The catalyst for stating olefin metathesis reaction selection is Zhan1-B catalyst, Hoveyda-Grubbs catalyst, Sigma-
Aldrich catalyst, Grubbs catalyst, one kind of Sigma-Aldrich catalyst and/or several.
5. the ionomer of a kind of high-damping according to claim 1, high wet-sliding resistant, low-heat-generation, it is characterised in that：Alkene
Grafted monomers selected by hydrocarbon metathesis reaction are acrylic acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, first
One kind of base butyl acrylate and/or several.
6. the ionomer of a kind of high-damping according to claim 1, high wet-sliding resistant, low-heat-generation, it is characterised in that：Institute
Stating metal oxide is sodium oxide molybdena, magnesia, zinc oxide, aluminium oxide, and metal hydroxides is sodium hydroxide, magnesium hydroxide, hydrogen
Zinc oxide, one kind of aluminium hydroxide and/or several.
7. according to claim 1-6 any high-dampings, high wet-sliding resistant, low-heat-generation ionomer, it is characterised in that：
Olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, and acrylic acid is 2-16 parts, and olefin metathesis is urged
Agent is 0.1-5 parts, and reaction temperature is 10-70 DEG C, reaction time 0.5-5h, mixing speed 200-1000rad/min；
Preferably, olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, and acrylic acid is 8-12 parts, is urged
Agent Grubbs Π is 0.5-2 parts, and reaction temperature is 40-60 DEG C, reaction time 1.5-2.5h, mixing speed 500-
700rad/min；
It is further preferred that olefin metathesis reaction condition is：High vinyl polybutadiene rubber is 100 parts, and acrylic acid is 10 parts,
Catalyst Grubbs Π be 1 part, reaction temperature be 2h, mixing speed 600rad/min in 50 DEG C of reaction time.
8. the method for preparing -6 any ionomers according to claim 1, which is characterized in that include the following steps：
A) HVBR (shredding, convenient for dissolution) is added in reaction flask, is put into magneton, is vacuum-treated, solvent is added, is placed in magnetic force and stirs
It mixes and accelerates HVBR dissolution at 60 DEG C of machine；
B) cyclohexane solution for the grafted monomers being made into and catalyst are added in the HVBR solution being completely dissolved, are placed in
The magnetic stirrer of required temperature is drawn off and is put into freezer compartment of refrigerator rapidly being cooled to room wait react to required time
Temperature；
C) enough dehydrated alcohols are added into reaction product, and are constantly stirred with glass bar, until obtaining solid micelle,
After being washed twice with dehydrated alcohol again, it is drawn off drying；
D) micelle after drying then is pressed into thin slice, is coated in nickel screen, is placed in acetone reflux in Soxhlet extractor and mentions for 24 hours
It is pure, to remove the impurity such as remaining initiator and unreacted grafted monomers；
E) graft product after purification is placed in the drying of 60 DEG C of vacuum ovens until constant weight, can be obtained pure carboxy-modified
HVBR(HVBR-g-COOH)。
9. according to the method described in claim 8, it is characterized in that, further including following steps：HVBR-g-COOH is placed in double roller
Thin slice is pressed into beginning to pratise, weigh solid metal oxide according to the ratio or hydroxide be put into mortar be ground into powder and with it is suitable
Amount aromatic naphtha is mixed into paste, and then pasty mixture is evenly applied on thin slice, and plasticates repeatedly on the double roll mill
5-20min, with guarantee NaOH can spread uniformly and with the carboxylate radical complete neutralization on graft polymers strand, can be prepared by
HVBR ionomer.
10. a kind of vulcanizate using the ionomer as described in claim 1-7 is any, which is characterized in that proportion is as follows：
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| CN110577783A (en) * | 2019-02-15 | 2019-12-17 | 艾夫特斯有限公司 | Sulfur-free liquid rubber composition |
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| CN113912915A (en) * | 2021-12-01 | 2022-01-11 | 中国科学技术大学 | High-strength anti-aging rubber material and preparation method thereof |
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| CN109867751B (en) * | 2019-02-28 | 2021-08-10 | 青岛科技大学 | Preparation method of 1, 2-polybutadiene rubber containing multiple ionic bond networks |
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