CN106832457B - A kind of nano-silica filled anti-form-1,4- butadiene-isoprene copolymer compounded rubber and preparation method thereof - Google Patents
A kind of nano-silica filled anti-form-1,4- butadiene-isoprene copolymer compounded rubber and preparation method thereof Download PDFInfo
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- CN106832457B CN106832457B CN201710122534.5A CN201710122534A CN106832457B CN 106832457 B CN106832457 B CN 106832457B CN 201710122534 A CN201710122534 A CN 201710122534A CN 106832457 B CN106832457 B CN 106832457B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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Abstract
A kind of nano-silica filled anti-form-1, 4- butadiene-isoprene copolymer compounded rubber, the nano silica by vacuum drying or high-temperature calcination processing is dispersed in isoprene-butadiene mix monomer in advance, sequentially add alkyl aluminum, external electron donor, high-speed stirred is uniformly mixed, Ziegler-Natta Catalyst is further added, said mixture material is added in polymeric kettle, it is catalyzed isoprene-butadiene combined polymerization synthesis of trans -1, 4- structural content is greater than the butadiene-isoprene copolymer compounded rubber of 85mol%, anti-form-1 in the compounded rubber, 4- butadiene isoprene copolymer mass content 50-99.9%, nano silica mass content 0.1-50%；Copolymer is made of the butadiene monomer unit of isoprene monomer unit and 2-50% that molar fraction is 50-98%.The trans- copolymerized rubber is remarkably improved wearability, the anti-slippery of product since nano silica is evenly dispersed with nanoscale, at the same product resistance to breach it is induced can increase substantially, be suitable for high-performance rubber product and light-colour rubber product.
Description
Technical field
The invention belongs to synthetic rubber field, in particular to the nano-silica filled copolymerized rubber of trans- fourth penta
And its in-situ polymerization method for preparing.
Background technique
The key performances such as intensity, wearability for raising rubber product, need to add a large amount of filler such as carbon black, white carbon black
Deng.In rubber add filler method it is usual there are two types of, dry and wet.Traditional adding method is by rubber and filler physics
Mechanical blending, although physical blending method is easy, mixed effect is poor, and power consumption is big, and carbon black, white carbon black etc. fly upward pollution
Environment, and dispersion effect of the filler in rubber is undesirable, easily partially forms large-sized aggregate, to influence fatigability
Energy, heat, wear-resisting property etc..
Compared to dry packing material, flushing material is total to by after the fillers humidifying such as carbon black, white carbon black, then with rubber
It is mixed.For example, after filling carbon black emulsion polymerized styrene butadiene rubber using adding water to mix carbon black and dispersing agent, then it is newborn with emulsion polymerized styrene butadiene rubber
Liquid mixing, then goes cohesion to obtain carbon black extended SBR (high polymer synthesis technology, 1997, Chemical Industry Press) again.
Chinese invention patent CN 104211837A, CN 103524802A etc., which are disclosed, fills carbon black or carbon black/white carbon black butadiene-styrene rubber mother
Styrene-butadiene latex, carbon black, water, operation oil etc. are prepared carbon black suspension, then carry out co-agglomeration and handle by the preparation method of glue
It arrives.This method is substantially better than dry blending, but needs complicated cohesion process.
Patent (US 5,100,965, WO.Pat.97,23521, US 4,020.115, US5,844,044, UK
Pat.Appl.2,029,426, Journal Applied Polymer Science2004,92:2941-2948；Macromolecule is logical
Report 2016,10:70-76；Macromolecule journal, 2015,12:1387-1394) report high trans-Isosorbide-5-Nitrae-structure butadiene
(Bd)-isoprene (Ip) copolymer (TBIR) has excellent physical and mechanical property, especially endurance and breach growth property
Can be excellent, it is the ideal sizing material for developing high-performance tire.The synthesis of TBIR mainly uses coordination polymerization catalysts such as nickel system
(Rom.Pat.63,446), vanadium system (Promst.Sint.Kauch.1982, (8): 4-8；US2005/0222348A1), cadmium system
(Dokl.Akad.Nauk SSSR, 1973,209:369-71), group of the lanthanides/lithium system (JP 0260,907) and Titanium series catalyst solution
It polymerize (Journal Applied Polymer Science2003,89:1800-1807).Patent (US 4020115,5,100,
965) barium/lithium bicomponent catalyst agent Butadiene-isoprene polymerization is used, trans- Isosorbide-5-Nitrae-structure of butadiene unit contains
50-80% is measured, for the contents of ethylene in butadiene unit less than 30%, molecular weight of copolymer distributed pole is wide.Nickel system, vanadium system, cadmium
There is the problems such as catalytic efficiency is low or trans content is low in the catalyst systems such as system and lithium system.Patent (201210138621.7) uses
It is total that supported titanium catalyst Butadiene-isoprene by Coordination copolymerization conjunction prepares high trans-Isosorbide-5-Nitrae-butadiene-isoprene
Inorganic filler is not present in the polymerization technique of the patent for polymers, while the TBIR prepared is pure polymer, and non-polymer/
The composite material of filler.
Chinese invention patent CN104212108 B discloses a kind of technology of preparing of white carbon black wet process rubber compound, using pre-
Processing first is functionalized to rubber molecule main chain, hydrophilic radical is introduced and is allowed to have autoemulsification, while to silica
It is modified with lipophilicity to carry out surface, then carries out the blending of rubber latex and white carbon black lotion again, is prepared for wet process rubber compound.
Although the more traditional wet process mixing technology of this method has better filler dispersibility, it still has modified rubber, white
Carbon black modified equal complicated technique, route are cumbersome.103224659 B of CN discloses filler mixing integrated with synthetic rubber
Technique is prepared for rubber and is filled out using three step continuous process such as the preparation of white carbon black, the preparation of rubber solutions, blending co-agglomerations
The Blend rubber of material.Japan Patent JP 2013062996 discloses the lotion of conjugated diene polymer and point of silica
Preparation wet process rubber compound is blended in dispersion liquid, but it needs respectively to pre-process alkadiene polymer and silica in advance,
Improve its compatibility.The above patent is all made of wet process mixing technology and prepares rubber-compounded rubber, has compared to dry method certain
Advantage, but the disadvantage is that need the rubber for obtaining polymerization technique to be separated or dissolved or preparatory emulsification treatment, increase
Equipment and process route；While in order to obtain good dispersibility, it is also necessary to be carried out before mixing to rubber and silica
Pretreatment.
Situ aggregation method is a kind of filler fill method that new development is got up, and can be added to filler in monomer polymerization
In polymerization system, while monomer polymerization is at polymer, filler carries out original position with the polymer of generation and mixes, and reaches filler
Good dispersion effect.There is document report to be prepared for polybutyl methacrylate/nanometer calcium carbonate, poly- first by situ aggregation method
The polyalcohol-filling materials nanocomposite such as base methyl acrylate/nanoclay, PVC/ nanoclay, PS/ titanium dioxide (J
PolymSci(Part A):PolymChem,2000；Polymer,2000；Journal of Applied Polymer
Science,2003).Chinese invention patent CN 101475672 B, CN 101851308 B etc. disclose nano silica original
The preparation method of position polymeric modification pvc material: nano-silica surface is repaired through the modifier containing polymerizable carbon-carbon double bond
Decorations or modified, the fully dispersed in the mixed solvent to organic solvent and water, to obtain reactable nano silica cream
Then the lotion and vinyl chloride are carried out home position polymerization reaction, or are distributed to vinyl chloride in advance using modified silica by liquid
Polymerization reaction is carried out after in polymerization system, obtains SiO2/ PVC in-situ composite.The addition of filler usually requires in water
Good dispersion is carried out, therefore above-mentioned polymerization is all made of free radical emulsion or suspension polymerization synthesis.In addition, Chinese invention is special
Sharp 102603999 B of CN etc., which is disclosed, is prepared for silicon dioxide polyester composite material using condensation polymerization method, and silica exists
The different phase of polycondensation is added.
And for coordination polymerization, since its catalyst system is very sensitive to water, oxygen etc., it usually needs anhydrous
The polymerizing condition of anaerobic, therefore the in situ of filler difficult to realize is added.There is document report PP/ nanometer calcium carbonate In-situ reaction nanometer
The preparation of material, but the addition concentration of its filler is very low, once calcium carbonate concentration is got higher, under the polymerization speed of propylene is obvious
Drop, the molecular weight and polymerization yield of polymerization product be substantially reduced (synthetic resin and plastics, 2003；Chinese Plastics, 2003).Cause
This, in spite of document report be prepared in situ rubber/silica filler composite material (Guangdong chemical industry, 2015；CN
101418063 B), the side substantially or using silica or the silica of modification being co-precipitated with rubber latex
Method preparation realizes the nanofillers such as silica without fundamentally solution alkene or diolefinic monomer during coordination polymerization
In-situ polymerization the problems such as.
To develop high-performance novel rubber material, high efficiency synthesizes the fourth two of nano-silica filled high trans structure
Alkene-isoprene copolymer compounded rubber, the present invention largely can poison coordination polymerization for nano-silica surface presence and urge
The reactive group (- OH ,-COOH) of agent passes through alkyl aluminum and a large amount of outer electrons before polymerization system is added in major catalyst
The pre-reaction of body, remove nano-silica surface can reactive group, thus the effective protection activity of catalyst, using this
The nano-silica filled anti-form-1 of body process for copolymerization fabricated in situ, the compound rubber of 4- structure butadiene-isoprene copolymer
Glue.Feature: simple process, solvent-free, without cohesion process, solvent-free recycling and refining step, low energy consumption, and process is short, effectively real
Existing nano silica is evenly dispersed in a polymer matrix with nanoscale；Pass through pretreated nano silica pair simultaneously
The catalyst of Ziegler-Natta load does not have apparent inhibition, can keep the high catalytic efficiency, trans- of former polymerization system
The features such as structural content is high；Simultaneously by the control of polymerization technique, can regulate and control trans- copolymer rubber composition gradient composition or
Form more uniform product；The trans- copolymerized rubber, can be significant since nano silica is evenly dispersed with nanoscale
Wearability, the anti-slippery, flexing fatigue for improving product, improve the resilience of product, are suitable for high-performance and light-colour rubber
Product.
Summary of the invention
An object of the present invention is a kind of nano silica with the equally distributed anti-form-1 of nanoscale, 4- fourth two
Alkene-isoprene copolymer compounded rubber new material.
The second object of the present invention is to provide the synthesis equally distributed anti-form-1 of nano silica, 4- butadiene-isoamyl
The synthetic method of the copolymerized rubber of diene, the advantage of this method are simple processes, solvent-free, without cohesion process, solvent-free time
Receipts and refining step, low energy consumption, and process is short, effectively realizes that nano silica is dispersed in polymeric matrix with nanoscale
In.
The third object of the present invention is to provide a kind of situ catalytic technology of compounded rubber, and the technology is in a large amount of nano-silicas
Butadiene-isoprene copolymer closes in the presence of SiClx, keeps the high catalytic efficiency of former catalyst system, while can pass through
The features such as its high trans structural content of the structure regulating of silica.
The fourth object of the present invention is to provide a kind of novel trans--Isosorbide-5-Nitrae-butadiene-isoprene copolymer compounded rubber, can
Applied to high-performance rubber product, flexing fatigue, wearability, the anti-slippery of product are significantly improved, the rebound of product is improved
Property, it is suitable for high-performance and light-colour rubber product.
Nano-silica filled anti-form-1 of the invention, 4- butadiene-isoprene copolymer compounded rubber wherein should
Anti-form-1 in copolymerized rubber, 4- butadiene isoprene copolymer mass content 50%~99.9%, nano silica
Mass content 0.1%~50%；Anti-form-1,4- butadiene isoprene copolymer by molar fraction be 50%~98% it is different
Pentadiene monomeric unit and 2%~50% butadiene monomer unit composition, the anti-form-1 of copolymer, 4- structure is greater than
85mol%, weight average molecular mass are 100,000~1,100,000, molecular weight distribution 3~20.
Nano-silica filled anti-form-1 of the invention, 4- butadiene-isoprene copolymer compounded rubber is to pass through
In-situ polymerization preparation, nano silica are dispersed in anti-form-1,4- butadiene-isoprene copolymer glue with nanoscale
In, there is no the large scale aggregations of nano silica.
Nano-silica filled anti-form-1 of the invention, the preparation of 4- butadiene-isoprene copolymer compounded rubber
Method one:
1) nano silica, the purification of vacuum drying treatment or high-temperature calcination processing are successively added into super mixer
Isoprene and butadiene, purification operation oil, purification hydrogen, high-speed stirred mix 1~30min；
2) organo-aluminum compound, external electron donor are added into high speed agitator, in 0~90 DEG C of high-speed stirred reaction 1~
30min；
3) after Ziegler-Natta Catalyst is passed through in the bottom of high speed agitator, with above-mentioned steps (1) and
(2) material is added in polymer reactor, carries out bulk copolymerization reaction, and polymeric reaction temperature is 0 DEG C~90 DEG C, polymerization time
It is 1~72 hour；
The wherein molar ratio 0.05~30: 100 of butadiene and isoprene, nano silica are total with two monomers
Mass ratio is 0.08~40:100, and transition metal element and two kinds of monomers always rubs in Ziegler-Natta Catalyst
You are than being 1~1000: 10000000, Al element and transition in Ziegler-Natta Catalyst in organo-aluminum compound
The molar ratio of metallic element is 5~500: 1, transition metal member in external electron donor and Ziegler-Natta Catalyst
The molar ratio of element is 0~500: 1, and the total mass ratio of hydrogen and two monomers is 0~1:100, operation oil and nano silica
Mass ratio is 0~0.5:1；
4) after the polymerization of step (3) reaches predetermined polymerization time, material is transported to extruder by material-handling pump, together
When to extruder terminator, anti-aging agent and other auxiliary agents is added, terminate polymerization, remove unreacted monomer, extruding pelletization is weighed
Benefit requires 1 anti-form-1,4- butadiene-isoprene copolymer compounded rubber.
Nano-silica filled anti-form-1 of the invention, the preparation of 4- butadiene-isoprene copolymer compounded rubber
Method two:
1) nano silica, the purification of vacuum drying treatment or high-temperature calcination processing are successively added into super mixer
Isoprene and butadiene, purification operation oil, purification hydrogen, high-speed stirred mix 1~30min；
2) organo-aluminum compound, external electron donor are added into high speed agitator, in 0~90 DEG C of high-speed stirred reaction 1~
30min；
3) after Ziegler-Natta Catalyst is passed through in the bottom of high speed agitator, with above-mentioned steps (1) and
(2) material is added in polymer reactor, carries out bulk copolymerization reaction, during the reaction by add divinylic monomer with
The initial molar ratio of butadiene and isoprene in reaction system is kept to be basically unchanged, polymeric reaction temperature is 0 DEG C~90
DEG C, polymerization time is 1~72 hour；
The wherein molar ratio 0.05~30: 100 of butadiene and isoprene, nano silica are total with two monomers
Mass ratio is 0.08~40:100, and transition metal element and two kinds of monomers always rubs in Ziegler-Natta Catalyst
You are than being 1~1000: 10000000, Al element and transition in Ziegler-Natta Catalyst in organo-aluminum compound
The molar ratio of metallic element is 5~500: 1, transition metal member in external electron donor and Ziegler-Natta Catalyst
The molar ratio of element is 0~500: 1, and the total mass ratio of hydrogen and two monomers is 0~1:100, operation oil and nano silica
Mass ratio is 0~0.5:1；
4) after the polymerization of step (3) reaches predetermined polymerization time, material is transported to extruder by material-handling pump, together
When to extruder terminator, anti-aging agent and other auxiliary agents is added, terminate polymerization, remove unreacted monomer, extruding pelletization is weighed
Benefit requires 1 anti-form-1,4- butadiene-isoprene copolymer compounded rubber.
The nano silica needs to first pass through pretreatment before being added to polymerization system.
The vacuum drying treatment condition of the nano silica: true in vacuum degree -0.05~-0.1Mpa vacuum oven
It manages 24-120 hours in vacancy；The high-temperature calcination treatment conditions of the nano silica: 200~700 DEG C of vacuum bakings, time is
0.1~10 hour；The granular size of the nano silica is 10-800 nanometers.
The Ziegler-Natta Catalyst is to contain titanium compound or vanadium using magnesium dichloride as carrier
Close the spherical or aspherical catalyst of object, internal electron donor, wherein Ti or V element account for Ziegler-Natta Catalyst
The 1%~5% of gross mass, internal electron donor account for the 0%~20% of Ziegler-Natta Catalyst gross mass；
The internal electron donor be esters, ethers, ketone, anhydride compound, preferably benzoic acid, to methoxybenzene first
Acid, paraethoxybenxoic acid, phenylacetic acid, diisobutyl phthalate, di-n-butyl phthalate, benzoquinones, benzoic acid first
Ester, ethyl benzoate, tetrahydrofuran, ethyl methane sulfonate, ethyl benzenesulfonat, triphenylphosphine, ether, triphenyl phosphate, phosphorous acid
One of triphenylmethyl methacrylate is a variety of；The titanium compound is selected from TiCl4、TiBr4、TiI4One of.
The vfanadium compound is selected from VCl3、VBr3、VOCl3、VOBr3、VCl4、VBr4、V2O5It is one or more；It is described
Organo-aluminum compound be triethyl aluminum, triisobutyl aluminium, dimethylaluminum chloride, dichloromethyl aluminium, diethyl aluminum chloride, dichloro
It is aluminium ethide, diisobutyl aluminum chloride, dichloro aluminium isobutyl, diethylaluminum hydride, ethyl aluminum hydride, isobutylaluminiumhydride, two different
One of butyl aluminum hydride is a variety of.
The external electron donor is selected from cyclohexyl trimethoxy silane, tert-butyl trimethoxy silane, tertiary hexyl front three
Oxysilane, diisopropyl dimethoxy silane, methylcyclohexyl dimethoxymethane, dimethoxydiphenylsilane, methyl
T-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- t-butyldimethoxysilane, 1,
1,1- trifluoro propyl -2- ethyl piperidine base-dimethoxysilane, ethyl trimethoxy silane, propyl trimethoxy silicane, phenyl
Trimethoxy silane, Dicyclohexyldimethoxysilane, tetrahydrofuran, ethyl methane sulfonate, ethyl benzenesulfonat, triphenylphosphine, second
One of ether, triphenyl phosphate, triphenyl phosphite are a variety of.
The operation oil is one of environment-friendly aromatic oil, paraffin oil, naphthenic oil or a variety of.
Batch process, semi-continuous process, continuity method production can be used in preparation method of the invention.
In preparation method of the invention, polymerization can be to be carried out in one, two or more reactors；The polymerization
Reactor is any one or two kinds of combinations in autoclave or horizontal reactor.
The present invention has synthesized composition, structure and performance by heterogeneous Ziegler-Natta catalyst can be in larger model
Enclose the interior loading for adjusting nano silica.By the concentration of butadiene in control polymerization process, anti-form-1,4- can control
Composition gradient in butadiene-isoprene copolymer glue is formed or is formed more uniform.By controlling different nano silicas
Type and dosage, the copolymerized rubber microstructure of available regulation and transconfiguration content, so that it is multiple to reach regulation copolymerization
Close the target of rubber performance.
Copolymerized rubber of the invention can be with natural gum, cis-butadiene cement, butadiene-styrene rubber, neoprene, EP rubbers, butyl
Rubber, brombutyl, nitrile rubber and other rubber compoundings use.
Copolymerized rubber of the invention is remarkably improved flexing fatigue, wearability, the anti-slippery of product, improves system
The resilience of product is suitable for high-performance and light-colour rubber product.
Specific embodiment
Embodiment 1
Silica (30nm), the 1500mL of 150 grams of 700 DEG C of vacuum bakings processing 6h are sequentially added into super mixer
Isoprene monomer, 100ml butadiene, mixing speed 1500r/min stir 5 minutes, 15mmol triisobutyl are then added
Aluminium, mixing speed 2000r/min stir 5 minutes, the heterogeneous Ziegler-Natta catalyst of 0.43g then are added (wherein,
Titanium compound is selected from TiCl4；The mass content of titanium is 2.0%, internal electron donor ethyl benzoate mass content 6%), above-mentioned object
Material is transported in the polymeric kettle of 3L, and copolymerization temperature is 10 DEG C, and the molar ratio of hydrogen and two monomers is 0.01:100, copolymerization
Time is 71 hours.Material is transported to extruder, while 200ml ethyl alcohol, 10 grams of antioxidant 264s is added to extruder, terminates poly-
It closes, removes unreacted monomer, extruding pelletization obtains anti-form-1,545 grams of 4- butadiene-isoprene copolymer compounded rubber.As a result
It is shown in Table 1.
Embodiment 2
Operation handles monomer with embodiment 1, in addition to silica, isoprene and butadiene are added into super mixer
Except, it is additionally added environment-friendly aromatic oil 30g and hydrogen, wherein the molar ratio of hydrogen and two monomers is 0.001:100.It the results are shown in Table 1.
Embodiment 3
Sequentially added into super mixer 5 grams of vacuum drying pre-process nano silica (30nm) for 24 hours,
1500mL isoprene monomer, 250ml butadiene, mixing speed 2000r/min stir 5 minutes, it is different that 25mmol tri- are then added
The dimethoxydiphenylsilane of butyl aluminium and 10mmol, mixing speed 2000r/min stir 5 minutes, are then added 1.2g's
(wherein, titanium compound is selected from TiCl to heterogeneous Ziegler-Natta catalyst4；The mass content of titanium is 4%) above-mentioned material
In the horizontal self-cleaning reactor for conveying 5L, copolymerization temperature is 10 DEG C, and the molar ratio of hydrogen and two monomers is 0.08:
100, the copolymerization time is 9 hours.Material is transported to extruder, while 200ml water, 5 grams of antioxidant 264s is added to extruder, eventually
Only it polymerize, removes unreacted monomer, extruding pelletization obtains anti-form-1,325 grams of 4- butadiene-isoprene copolymer compounded rubber.
It the results are shown in Table 1.
Embodiment 4
Silica (30nm), the 30L that 1500 grams of 400 DEG C of vacuum bakings processing 6h are sequentially added into super mixer are different
Pentadiene monomer, 0.3L butadiene, mixing speed 2000r/min, stir 15 minutes, then be added 56mmol triisobutyl aluminium and
The dimethoxydiphenylsilane of 10mmol, mixing speed 2000r/min stir 5 minutes, the heterogeneous of 3g are then added
(wherein, titanium compound is selected from TiCl to Ziegler-Natta catalyst4；The mass content of titanium is that 4%), above-mentioned material conveys 50L
Horizontal self-cleaning reactor in, copolymerization temperature is 40 DEG C, and the molar ratio of hydrogen and two monomers is 0.08:100, is copolymerized
Time is 4 hours, adds divinylic monomer 0.5L, 50 DEG C of continuation combined polymerization 8h.Material is transported to extruder, while to extruder
2000ml water, 150 grams of antioxidant 264s is added, terminates polymerization, removes unreacted monomer, extruding pelletization obtains anti-form-1,4- fourth
Diene-isoprene copolymer compounded rubber 11.6Kg.It the results are shown in Table 1, specific physical and mechanical property is shown in Table 2.
Embodiment 5
Silica (200nm), the 30L of 1500 grams of 400 DEG C of vacuum bakings processing 12h are sequentially added into super mixer
Isoprene monomer, 2L butadiene, mixing speed 2000r/min, stir 15 minutes, then be added 40mmol triethyl aluminum and
20mmol ethyl methane sulfonate, mixing speed 2000r/min stir 5 minutes, the heterogeneous Ziegler-Natta of 2g are then added
(wherein, titanium compound is selected from TiCl to catalyst4；The mass content of titanium is 4%) the horizontal automatically cleaning of above-mentioned material conveying 50L
In reactor, copolymerization temperature is 40 DEG C, and the molar ratio of hydrogen and two monomers is 0.08:100, and the copolymerization time is 4 hours,
Add divinylic monomer 0.5L, 50 DEG C of continuation combined polymerization 8h.Material is transported to extruder, at the same to extruder be added 500ml water,
80 grams of antioxidant 264s terminate polymerization, remove unreacted monomer, and extruding pelletization obtains anti-form-1, and 4- butadiene-isoprene is total
Poly- compounded rubber 7.32kg.It the results are shown in Table 1.
1 Examples 1 to 5 of table
The mechanical property of 2 embodiment 4 of table
Formula: a) 100 SSBR/BR, ZnO 3.5, stearic acid 1.5, antioxidant 4,020 2.0, antioxidant RD 1.5, hard charcoal
Black 70, Si-69 7.2, accelerator TBBS 1.5, diphenylguanidine PG 1.0, sulphur 1.6, other 10.5
B) SSBR/BR/ embodiment 4 100, ZnO 3.5, stearic acid 1.5, antioxidant 4,020 2.0, antioxidant RD 1.5,
White carbon black 70, Si-69 7.2, accelerator TBBS 1.5, diphenylguanidine PG 1.0, sulphur 1.6, other 10.5
Vulcanization: 150 DEG C × t90。
Claims (10)
1. a kind of anti-form-1, the preparation method of 4- butadiene-isoprene copolymer compounded rubber synthesize according to the following steps:
(1) successively into super mixer be added vacuum drying treatment or high-temperature calcination processing nano silica, purification
The hydrogen that the operation of isoprene and butadiene, purification is oily, refines, high-speed stirred mix 1~30min；
(2) organo-aluminum compound, external electron donor are added into high speed agitator, in 0~90 DEG C of high-speed stirred reaction 1~
30min；
(3) after Ziegler-Natta Catalyst is passed through in the bottom of high speed agitator, with above-mentioned steps (1) and (2)
Material be added polymer reactor in, carry out bulk copolymerization reaction, polymeric reaction temperature be 0 DEG C~90 DEG C, polymerization time be 1~
72 hours；
The wherein molar ratio 0.05~30: 100 of butadiene and isoprene, the gross mass of nano silica and two monomers
Than being 0.08~40: 100, the total moles of transition metal element and two kinds of monomers ratio in Ziegler-Natta Catalyst
It is 1~1000: 10000000, Al element and transition metal in Ziegler-Natta Catalyst in organo-aluminum compound
The molar ratio of element is 5~500: 1, transition metal element in external electron donor and Ziegler-Natta Catalyst
Molar ratio is 0~500: 1, and the total mass ratio of hydrogen and two monomers is 0~1: 100, the quality of operation oil and nano silica
Than being 0~0.5: 1；
(4) after the polymerization of step (3) reaches predetermined polymerization time, material is transported to extruder by material-handling pump, simultaneously
Terminator, anti-aging agent and other auxiliary agents are added to extruder, terminate polymerization, remove unreacted monomer, extruding pelletization obtains nanometer
Silica-filled anti-form-1,4- butadiene-isoprene copolymer compounded rubber.
2. a kind of anti-form-1, the preparation method of 4- butadiene-isoprene copolymer compounded rubber synthesize according to the following steps:
(1) successively into super mixer be added vacuum drying treatment or high-temperature calcination processing nano silica, purification
The hydrogen that the operation of isoprene and butadiene, purification is oily, refines, high-speed stirred mix 1~30min；
(2) organo-aluminum compound, external electron donor are added into high speed agitator, in 0~90 DEG C of high-speed stirred reaction 1~
30min；
(3) after Ziegler-Natta Catalyst is passed through in the bottom of high speed agitator, with above-mentioned steps (1) and (2)
Material is added in polymer reactor, bulk copolymerization reaction is carried out, during the reaction by adding divinylic monomer to keep
The initial molar ratio of butadiene and isoprene is basically unchanged in reaction system, and polymeric reaction temperature is 0 DEG C~90 DEG C, is gathered
Closing the time is 1~72 hour；
The wherein molar ratio 0.05~30: 100 of butadiene and isoprene, the gross mass of nano silica and two monomers
Than being 0.08~40: 100, the total moles of transition metal element and two kinds of monomers ratio in Ziegler-Natta Catalyst
It is 1~1000: 10000000, Al element and transition metal in Ziegler-Natta Catalyst in organo-aluminum compound
The molar ratio of element is 5~500: 1, transition metal element in external electron donor and Ziegler-Natta Catalyst
Molar ratio is 0~500: 1, and the total mass ratio of hydrogen and two monomers is 0~1: 100, the quality of operation oil and nano silica
Than being 0~0.5: 1；
(4) after the polymerization of step (3) reaches predetermined polymerization time, material is transported to extruder by material-handling pump, simultaneously
Terminator, anti-aging agent and other auxiliary agents are added to extruder, terminate polymerization, remove unreacted monomer, extruding pelletization obtains nanometer
Silica-filled anti-form-1,4- butadiene-isoprene copolymer compounded rubber.
3. according to claim 1 with 2 any preparation methods, characterized in that it is described nano-silica filled anti-
Anti-form-1 in formula-Isosorbide-5-Nitrae-butadiene-isoprene copolymer compounded rubber, 4- butadiene isoprene copolymer mass content
50%~99.9%, nano silica mass content 0.1%~50%；Anti-form-1,4- butadiene isoprene copolymer by
Molar fraction is 50%~98% isoprene monomer unit and 2%~50% butadiene monomer unit composition, copolymer
Anti-form-1,4- structure be greater than 85mol%, weight average molecular mass be 100,000~1,100,000, molecular weight distribution 3~20.
4. according to claim 1 with 2 any preparation methods, characterized in that the vacuum drying of the nano silica
Treatment conditions: it is vacuum-treated 24-120 hours in vacuum degree -0.05~-0.1MPa vacuum oven；The nano silica
High-temperature calcination treatment conditions: 200~700 DEG C of vacuum bakings, the time be 0.1~10 hour；Of the nano silica
Grain size is 10-800 nanometers.
5. according to claim 1 with 2 any preparation methods, it is characterized in that: the support type Ziegler-Natta is urged
Agent is the spherical or aspherical catalysis containing titanium compound or vfanadium compound, internal electron donor using magnesium dichloride as carrier
Agent, wherein Ti or V element account for the 1%~5% of Ziegler-Natta Catalyst gross mass, and internal electron donor accounts for load
The 0%~20% of type Ziegler-Natta catalyst gross mass；The internal electron donor is ketone, anhydride compound, neighbour
Phthalic acid diisobutyl ester, di-n-butyl phthalate, methyl benzoate, ethyl benzoate, tetrahydrofuran, methanesulfonic acid second
One of ester, ethyl benzenesulfonat, ether, triphenyl phosphate, triphenyl phosphite are a variety of；The titanium compound is selected from
TiCl4、TiBr4、TiI4One of；The vfanadium compound is selected from VCl3、VBr3、VOCl3、VOBr3、VCl4、VBr4、V2O5's
It is one or more；The organo-aluminum compound is triethyl aluminum, triisobutyl aluminium, dimethylaluminum chloride, dichloromethyl aluminium, two
It is ethylmercury chloride aluminium, ethyl aluminum dichloride, diisobutyl aluminum chloride, dichloro aluminium isobutyl, diethylaluminum hydride, ethyl aluminum hydride, different
One of butyl aluminum hydride, diisobutyl aluminium hydride are a variety of.
6. according to claim 1 with 2 any preparation methods, it is characterized in that: the external electron donor is selected from cyclohexyl
Trimethoxy silane, tert-butyl trimethoxy silane, tertiary hexyl trimethoxysilane, diisopropyl dimethoxy silane, methyl
Cyclohexyl dimethoxymethane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl
Silane, 2- ethyl piperidine base -2- t-butyldimethoxysilane, 1,1,1- trifluoro propyl -2- ethyl piperidine base-dimethoxy silicon
Alkane, ethyl trimethoxy silane, propyl trimethoxy silicane, phenyltrimethoxysila,e, Dicyclohexyldimethoxysilane, four
One of hydrogen furans, ethyl methane sulfonate, ethyl benzenesulfonat, triphenylphosphine, ether, triphenyl phosphate, triphenyl phosphite or
It is a variety of.
7. according to claim 1 with 2 any preparation methods, it is characterized in that: the operation oil is environment-friendly aromatic oil, stone
One of wax oil, naphthenic oil are a variety of.
8. according to claim 1 with 2 any preparation methods, it is characterized in that: using batch process, semi-continuous process, continuity method
Production.
9. according to claim 1 with 2 any preparation methods, it is characterized in that: polymerization is in one, two or more reactions
It is carried out in device；The polymer reactor is any one or two kinds of combinations in autoclave or horizontal reactor.
10. a kind of anti-form-1 obtained by any preparation method of claim 1-2,4- butadiene-isoprene copolymer
Compounded rubber, it is characterized in that: nano silica is evenly dispersed with nanoscale, the resistance to breach of product is induced significantly to be mentioned
Height is suitable for high-performance rubber product and light-colour rubber product.
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