CN102229759B - Method for preparing white carbon black hybridized material prepared by modification with end chlorosilane polymer - Google Patents
Method for preparing white carbon black hybridized material prepared by modification with end chlorosilane polymer Download PDFInfo
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Abstract
The invention discloses a method for preparing a white carbon black hybridized material prepared by modification with an end chlorosilane polymer, belonging to the field of synthesis of hybridized materials. The method comprises the following steps of: (1) adding chlorosilane in an anionic reactive polymer, reacting at 30-60 DEG C for 10-40 minutes to obtain the end chlorosilane polymer, wherein the reactive polymer includes styrene polymers, polymers of derivatives of styrene, alkadiene polymers and mixtures of two or more than two of the styrene polymers, the polymers of derivatives of styrene and the alkadiene polymers; (2) mixing white carbon black and the end chlorosilane polymer uniformly, reacting at 25-100 DEG C for 1-48 hours, removing a solvent to obtain an organic/inorganic hybridized material of the end chlorosilane polymer bonded with white carbon black, wherein the mass ratio of the end chlorosilane polymer to the white carbon black is 20:1-1:10. According to the invention, the aggregation of the white carbon black is reduced, affinity between the white carbon black and the polymer is improved, phase separation is reduced obviously, and the prepared material has excellent comprehensive performance. The method is easy to operate, the grafting efficiency is between 50% and 90%, and the prepared white carbon black as an organic hybridized material has the grafting grade being about 0.025:1-9:1.
Description
Technical field
The invention belongs to the synthetic field that macromolecular compound grafting inorganics forms organic-inorganic hybrid material, be specifically related to the preparation method of the organic-inorganic hybrid material of a kind of polymer-based carbon chlorosilane and inorganic materials white carbon black.
Background technology
White carbon black is the nano material that a kind of particle diameter is little, specific surface area is large, surfactivity forms greatly and easily high structure aggregate.The white carbon black surface has a large amount of hydroxyls to exist, and these hydroxyls are divided into two kinds, and a kind of is the hydroxyl of Individual existence, is called the isolation hydroxyl; Another kind is the adjacent hydroxyl of adhesion, and these hydroxyls can form hydrogen bond each other.White carbon black mainly is used as rubber packing, in addition, also is widely used in industries such as plastic industry, coating.The white carbon black agglomeration occuring easily, and bad with the polymer phase capacitive, and then affects the performance of material when white carbon black and polymer blending.
Normally adopt the mode of twin-roll machine tool blend to add as the rubber reinforcing filler white carbon black.But the lip-deep hydroxyl of white carbon black causes reunion so that form easily each other hydrogen bond, and hydroxyl is weakened the effect of sulfurating stage promotor to the effect of promotor molecule strong adsorption, causes curing time to prolong.In order to improve the degree of scatter of white carbon black, promote sulfuration, usually can first white carbon black evenly be mixed with activator (such as glycol ether, glycerol etc.), and then and compounding rubber; Compare with the elastic body toughening plastics, the white carbon black toughened plastics can keep in toughness reinforcing process or the rigidity of reinforced plastics, thereby not affect the performances such as its intensity, wear resistance.Identical with white carbon black filled rubber goods, the dispersion of white carbon black and undesirable with the consistency of plastics will be carried out some processing to white carbon black before blend.For example using white carbon black modified poly (ether-sulfone) (PES) is first with white carbon black and Resins, epoxy pre-mixing, forms semi-solid mashed prod, then with this mashed prod and PES melt blending, can obviously improve the performance of PES; Reuniting when white carbon black is used for coating still exists, and the consistency of itself and resin is relatively poor, for this reason, also will carry out some processing to white carbon black.Common processing means are with organism (mainly being macromolecule wax) elder generation and white carbon black blend, make white carbon black surface adsorption one deck coat, and then add in the coating; Other has the method for carrying out the polymer overmold of monomer polymerization on the white carbon black surface, its basic step is to make first SURFACTANT ADSORPTION on the white carbon black surface, then add the organic monomer of solvation and make monomer generation in-situ polymerization, remove at last the part surface promoting agent.
Above-mentioned several method is the physical method of white carbon black blend, these methods generally speaking all are first with white carbon black and certain material blend, make white carbon black adsorb this material, weaken the reunion of white carbon black, and improve the consistency of itself and polymkeric substance and then and polymer blending.Although process the consistency that rear white carbon black can suitably weaken the reunion of white carbon black and strengthen white carbon black and polymkeric substance with these methods, the effect of improving that the mode of this dependence white carbon black absorption plays is not desirable especially.
Mode by the chemical modification white carbon black also has a lot, normally introduces some organic micromolecule compounds on the white carbon black surface.Add coupling agent during for example with the white carbon black reinforced rubber.The aqueous favoring group of coupling agent can with the lip-deep hydroxyl effect of white carbon black, and close organic phase group can be combined with rubber, thereby between white carbon black and rubber, play the effect of " molecular bridge ", be separated thereby improve the affinity between white carbon black and the rubber and effectively reduce.CN101220177 discloses a kind of preparation method of white carbon black/solution polymerized butadiene styrene rubber nano-composite material.The method is with after silane coupling agent fully mixes with the Nano carbon white powder, condensation reaction is carried out at high temperature thermal treatment, obtain joining in the solution polymerized butylbenzene glue behind the Nano carbon white powder of organic modification, stirring, desolvation, oven dry obtain the white carbon black/solution polymerized butadiene styrene rubber nano-composite material that co-agglomeration prepares.Be actually that the white carbon black surface is coupling agent modified with the amino chlorosilane, then be filled in the solution polymerized butadiene styrene rubber.This method can only suitably improve white carbon black dispersion and with being separated of polymkeric substance.
The people such as Eike Hubner (Macromolecules, 2010,2 (43): 856～867), taked first white carbon black to be used the chlorosilane modification, then with the white carbon black after the modification and reactive polymer reaction, made the matrix material of polymkeric substance and white carbon black.Prucker and R ü he (Macromolecules,
1998,3 (31): 592～601) by traditional radical polymerization modified white carbon black.Its method is the radical initiator that the white carbon black surface grafting is nitrogenous, then causes radical polymerization with the silica particles after this modification, and polymer chain is received on the white carbon black.Above-mentioned modified-reaction is complicated, and efficient is low, and catalyst system therefor is difficult to remove, unsuitable use of large-scale production.
If can directly set up chemical bonding polymer-modified with the white carbon black surface, modifying process will be simple and effective many so, simultaneously because the existence of polymer long-chain, will inevitably " widen " the interparticle distance of white carbon black, its agglomeration with and and polymkeric substance between be separated and will inevitably obviously reduce, the over-all properties of material can be greatly improved.The present invention reacts the chemical bonding that this method realizes polymkeric substance long-chain and white carbon black by utilization with polymkeric substance and the white carbon black surface hydroxyl of chlorosilane end, and percentage of grafting reaches as high as 90%, thereby solve preferably the white carbon black scattering problem, and reduce being separated of polymkeric substance and white carbon black from molecular level, and operating procedure is simple.
Summary of the invention
The object of the invention is to solve white carbon black and polymer blending in the prior art, the problem that consistency is undesirable, and the preparation method of the simple polymer-based carbon chlorosilane one white carbon black organic-inorganic hybrid material of a kind of technique is provided.The organic-inorganic hybrid material of being prepared by the method, weaken significantly the reunion of white carbon black in polymkeric substance, and reduced being separated of polymkeric substance and white carbon black from molecular level, can effectively improve simultaneously the over-all properties of material by the strong interaction of strengthening white carbon black and polymeric matrix.
A kind of polymkeric substance of terminal chlorosilane and method that the white carbon black chemical bonding prepares organic-inorganic hybrid material of adopting provided by the present invention may further comprise the steps:
(1) in the living anion polymerization thing, adds chlorosilane, in 30～60 ℃ of lower reactions 10～40 minutes, make the polymkeric substance of terminal chlorosilane.
(2) mixed with polymers with white carbon black and terminal chlorosilane is even, and 25 ℃～100 ℃ are reacted down 1～48h, make the organic-inorganic hybrid material of the polymer-bound white carbon black of terminal chlorosilane behind the desolvation.In the ultrasonic lower reaction of 80～100Hz, can promote white carbon black to disperse; Adding amines catalyst in the reaction process can fast reaction speed.
The reaction equation synoptic diagram of above-mentioned steps 2 is:
Reactive polymer comprises the polymkeric substance, diene polymer of Styrene and its derivatives and the mixture that is made of two or more polymkeric substance wherein in the above-mentioned steps (1), such as polyhutadiene (PB), polyisoprene (PI), polystyrene (PS), Butadiene/Styrene random copolymers (PSB), isoprene-butylbenzene copolymer (PI-PSB), Butadiene/Styrene segmented copolymer (SBS) etc., molecular chain can be linearity, branching shape or star.Its number-average molecular weight is 5000～200000.
The chlorosilane structural formula is R in the above-mentioned steps (1)
xSiCl
y(wherein R is alkyl, and the carbon atoms number is 1～4; X represents the alkyl number, is 0～2; Y represents the number of Cl, is 2～4).
White carbon black is thermal silica or precipitated silica in the above-mentioned steps (2), its particle diameter 10～200nm.
The amines catalyst that adds in the above-mentioned steps (2) comprises triethylamine, Tetramethyl Ethylene Diamine, pentamethyl-diethylenetriamine, N-N-dimethyl tetrahydro chaff amine etc.
The blending method of white carbon black and terminal chlorosilane fluidized polymer in the above-mentioned steps (2) comprises that the white carbon black powder adds in the polymkeric substance, the organic solution of white carbon black drips in the polymkeric substance, polymers soln dropping in the white carbon black powder, polymers soln drip in the organic solution of white carbon black.Wherein solvent comprises that alkanes (such as normal hexane, hexanaphthene etc.), ester class (such as ethyl acetate, butylacetate etc.) etc. are without the hydroxy kind organic solvent.
The inventive method adopts the chlorosilane that contains at least two chlorine in the molecule, is to contain at least a chlorine in order to make in the terminal chlorosilane fluidized polymer that obtains.Could react with the hydroxyl on white carbon black surface like this.
In the inventive method, the mass ratio of [white carbon black]/[terminal chlorosilane fluidized polymer] is 20: 1～1: 10.
In the inventive method, supersound process is in order to promote better the dispersion of white carbon black.
Adding amines catalyst in the inventive method is in order to promote the reaction between white carbon black surface hydroxyl and the polymer ends chlorosilyl group.
The molecular weight of anionic polymer of the present invention is tested by gel permeation chromatography (SEC); Polymer ends chlorosilane degree adopts the recently expression of mole of chlorine and polymer ends, tests sign by ultimate analysis and X-ray photoelectron spectroscopic analysis (XPS); The polymkeric substance that produces chemical bonding with white carbon black accounts for the mass percent employing grafting efficiency that institute adds terminal chlorosilane fluidized polymer and represents, does not weigh to test behind the graftomer by isolating; Adopt the grafting degree to represent with the polymkeric substance of white carbon black chemical bonding and the mass ratio of white carbon black, test sign by gel permeation chromatography (SEC) and thermogravimetric analysis (TG).The dispersiveness of white carbon black is tested sign by scanning electronic microscope (SEM), projection electron microscope (TEM).
The inventive method can effectively be controlled the chlorosilane degree of polymer ends, can make each polymer ends contain 1～3 Cl; The grafting efficiency of polymkeric substance on white carbon black can be controlled in 50%～90%, reaches as high as 90%; The grafting degree of polymkeric substance on white carbon black can be controlled in 0.025: 1～and 9: 1; The section transmission electron microscope photo of the material that makes can be clearly seen that the white carbon black good dispersion, without large aggregate.The stereoscan photograph of breaking section can be clearly seen that according to the prepared material of the inventive method, section is level and smooth, without hole, makes carbon black clear and is combined closely with polymer interface.
Compare with the polymer blending complete processing with traditional white carbon black, the present invention has following beneficial effect:
1) according to the prepared organic-inorganic hybrid material of method provided by the present invention, effectively weakened the agglomeration of white carbon black, and greatly improved affinity between white carbon black and the polymkeric substance, and obviously reduce the material excellent combination property that obtains so that be separated.
2) simple, the easy handling of preparation method provided by the invention starts from suitability for industrialized production, has good economic and social benefit.
3) grafting efficiency of the inventive method can reach 50%～90%, can make the grafting degree to be about 0.025: 1～white carbon black-organic Hybrid Materials of 9: 1.
The invention will be further described below in conjunction with embodiment.
Description of drawings
Fig. 1: curve 1 is the SEC spectrogram of terminal chlorosilane fluidized polymer, and curve 2 is the SEC spectrograms behind terminal chlorosilane fluidized polymer and the white carbon black bonding.
Fig. 2: (1) is the transmission electron microscope photo of hybrid material, and (2) are the stereoscan photographs of hybrid material.
Embodiment
Thermal silica among the embodiment is bought from a day Bender mountain company, and precipitated silica is bought from goldschmidt chemical corporation, and the living anion polymerization thing is bought from Sinopec Group, but raw material of the present invention is not limited to this.
1) gets a there-necked flask, with C
4H
9SiCl
3Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Tetramethyl Ethylene Diamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 100g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active butadiene-styrene unregulated polymer 20g, sampling 1.Get 23.5ml C with transfer pipet
4H
9SiCl
3Cyclohexane solution join in the polymerization bottle, 30 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) get the cyclohexane solution that contains the terminal chlorosilane fluidized polymer of 10g and join in the 100g white carbon black, and mix, add the cyclohexane solution of 2.4ml Tetramethyl Ethylene Diamine with transfer pipet in the system.Reaction 1h, reaction conditions: 25 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 1.7 ten thousand, is distributed as 1.06.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 1.8: 1.Sample 4 is weighed as 1.909g, and calculating its grafting efficiency is 50.3%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.051: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～60nm.
1) gets a there-necked flask, with CH
3SiCl
3Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Triethylamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 80g precipitated silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active butadiene-styrene unregulated polymer 20g, sampling 1.Get 18.6ml CH with transfer pipet
3SiCl
3Cyclohexane solution join in the polymerization bottle, 40 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) get terminal chlorosilane fluidized polymer/hexanaphthene that 10g makes and join in the 80g white carbon black, and mix, in system, add 1.9ml triethylamine/cyclohexane solution with transfer pipet.Reaction 2h, reaction conditions: 30 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 4.3 ten thousand, is distributed as 1.10.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 1.8: 1.Sample 4 is weighed as 1.893g, and calculating its grafting efficiency is 51.8%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.065: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 100～400nm.
Embodiment 3
1) gets a there-necked flask, with CH
3SiCl
3Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 20g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active butadiene-styrene unregulated polymer 20g, sampling 1.Get 13ml CH with transfer pipet
3SiCl
3Cyclohexane solution join in the polymerization bottle, 50 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) get the hexanaphthene of the terminal chlorosilane fluidized polymer that 10g makes, the 20g white carbon black is added wherein, and mix, reaction 5h, reaction conditions: 50 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 6.2 ten thousand, is distributed as 1.08.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 1.9: 1.Sample 4 is weighed as 1.695g, and calculating its grafting efficiency is 54.3%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.272: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 4
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Triethylamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 10g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 88.8ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 60 ℃ of lower reactions 15 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) hexanaphthene of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the 10g white carbon black, and mixes, and the cyclohexane solution of getting the 8.9ml triethylamine with transfer pipet joins in the reaction system.Reaction 26h, reaction conditions: 40 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 8.1 ten thousand, is distributed as 1.12.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.9: 1.Sample 4 is weighed as 1.820g, and calculating its grafting efficiency is 90.1%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 9: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
The SEC spectrogram of sample 1, sample 4 is seen figure (1), figure (2).
Embodiment 5
1) gets a there-necked flask, with (CH
3)
2SiCl
2Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 20g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 23.3ml (CH with transfer pipet
3)
2SiCl
2Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 15 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the cyclohexane solution of 20g white carbon black, and mixes, reaction 4h, and reaction conditions: 60 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 10.3 ten thousand, is distributed as 1.09.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 0.8: 1.Sample 4 is weighed as 1.513g, and calculating its grafting efficiency is 70.8%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 3.54: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 6
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.With N, N-dimethyl tetrahydro chaff amine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 50g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 60.9ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 60 ℃ of lower reactions 15 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the 50g white carbon black, and mixes, and adds 6.1ml N, the cyclohexane solution of N-dimethyl tetrahydro chaff amine with transfer pipet in system.Reaction 8h, reaction conditions: 50 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 11.8 ten thousand, is distributed as 1.12.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.765g, and calculating its grafting efficiency is 82.4%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 1.65: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.Its TEM photo, SEM photo are as shown in Figure 2.
Embodiment 7
1) gets a there-necked flask, with (CH
3)
2SiCl
2Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 33g precipitated silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 46.6ml (CH with transfer pipet
3)
2SiCl
2Cyclohexane solution join in the reactor, 40 ℃ of lower reactions 15 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the butylacetate solution of 20g white carbon black, and mixes, reaction 10h, and reaction conditions: 70 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 12.5 ten thousand, is distributed as 1.11.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 0.8: 1.Sample 4 is weighed as 1.664g, and calculating its grafting efficiency is 77.6%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 2.33: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 100～300nm.
Embodiment 8
1) gets a there-necked flask, with CH
3SiCl
3Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.With N, N-dimethyl tetrahydro chaff amine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 12.5g gas-phase silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 46.2ml CH with transfer pipet
3SiCl
3Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 20 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) ethyl acetate solution with the 12.5g white carbon black joins in the cyclohexane solution of the terminal chlorosilane fluidized polymer of 100g that makes, and mixes, and adds 4.6ml N, the cyclohexane solution of N-dimethyl tetrahydro chaff amine with transfer pipet in system.Reaction 12h, reaction conditions: 30 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 15.6 ten thousand, is distributed as 1.13.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 1.9: 1.Sample 4 is weighed as 1.392g, and calculating its grafting efficiency is 65.8%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 5.27: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 9
1) gets a there-necked flask, with (CH
3)
2SiCl
2Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 17g precipitated silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 15.6ml (CH with transfer pipet
3)
2SiCl
2Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 20 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) the 17g white carbon black is joined in the cyclohexane solution of the terminal chlorosilane fluidized polymer of 100g that makes, and mix, reaction 14h, reaction conditions: 55 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 15.4 ten thousand, is distributed as 1.12.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 0.7: 1.Sample 4 is weighed as 1.607g, and calculating its grafting efficiency is 77.1%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 4.62: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 100～300nm.
Embodiment 10
1) gets a there-necked flask, with (CH
3)
2SiCl
2Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 20g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active butadiene-styrene unregulated polymer 120g, sampling 1.Get 38.9ml (CH with transfer pipet
3)
2SiCl
2Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) the 20g white carbon black is joined in the cyclohexane solution of the terminal chlorosilane fluidized polymer of 100g that makes, and mix, reaction 24h, reaction conditions: 70 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-styrene-butadiene polymer hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 18.5 ten thousand, is distributed as 1.15.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 0.9: 1.Sample 4 is weighed as 1.725g, and calculating its grafting efficiency is 83.5%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 4.18.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 11
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Pentamethyl-diethylenetriamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 200g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active polyhutadiene 20g, sampling 1.Get 156.9ml SiCl with transfer pipet
4Cyclohexane solution join in the polymerization bottle, 50 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 10g makes joins in the 200g white carbon black, and mixes, reaction 48h, and with the cyclohexane solution of transfer pipet adding 15.7ml pentamethyl-diethylenetriamine in the system.Reaction conditions: 60 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyhutadiene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 0.51 ten thousand, is distributed as 1.05.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.991g, and calculating its grafting efficiency is 90.3%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.045: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～70nm.
Embodiment 12
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 200g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active polyhutadiene 20g, sampling 1.Get 21.1ml SiCl with transfer pipet
4Cyclohexane solution join in the polymerization bottle, 50 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 10g makes joins in the 200g white carbon black, and mixes, reaction 3h, and reaction conditions: 30 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyhutadiene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 1.9 ten thousand, is distributed as 1.09.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.7: 1.Sample 4 is weighed as 1.953g, and calculating its grafting efficiency is 50.2%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.025: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 100～400nm.
Embodiment 13
1) gets a there-necked flask, with CH
3SiCl
3Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Triethylamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 120g gas-phase silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 250ml there-necked flask, add anion active polyhutadiene 20g, sampling 1.Get 37.5ml CH with transfer pipet
3SiCl
3Cyclohexane solution join in the polymerization bottle, 50 ℃ of lower reactions 10 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) ethyl acetate solution of 120g white carbon black is joined in the cyclohexane solution of the terminal chlorosilane fluidized polymer of 10g that makes, and mix, add the cyclohexane solution of 3.8ml triethylamine with transfer pipet in the system.Reaction 18h, reaction conditions: 25 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyhutadiene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 3.2 ten thousand, is distributed as 1.03.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 1.9: 1.Sample 4 is weighed as 1.942g, and calculating its grafting efficiency is 62.3%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 0.052: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～60nm.
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Tetramethyl Ethylene Diamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 10g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active polyisoprene 120g, sampling 1.Get 57.1ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the 10g white carbon black, and mixes, and adds the cyclohexane solution of 5.7ml Tetramethyl Ethylene Diamine in the reaction system with transfer pipet.Reaction 6h, reaction conditions: 50 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyisoprene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 12.6 ten thousand, is distributed as 1.08.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.7: 1.Sample 4 is weighed as 1.435g, and calculating its grafting efficiency is 68.9%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 6.88: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 15
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 20g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active polyisoprene 120g, sampling 1.Get 49.7ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the 20g white carbon black, and mixes, reaction 15h, and reaction conditions: 40 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyisoprene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 14.5 ten thousand, is distributed as 1.09.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.537g, and calculating its grafting efficiency is 72.2%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 3.62: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Triethylamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 10g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active polystyrene 120g, sampling 1.Get 36.4ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 40 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the 10g white carbon black, and mixes, and adds the cyclohexane solution of 3.6ml triethylamine in the reaction system with transfer pipet.Reaction 30h, reaction conditions: 100Hz is ultrasonic, 60 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-Polystyrene Hybrid Material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 19.8 ten thousand, is distributed as 1.12.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.9: 1.Sample 4 is weighed as 1.625g, and calculating its grafting efficiency is 79.4%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 7.93: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 17
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.With N, N-dimethyl tetrahydro chaff amine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 33g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add anion active polyisoprene-butylbenzene 120g, sampling 1.Get 31ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the hexane solution of 33g white carbon black, and mixes, and adds 3.1ml N, the cyclohexane solution of N-dimethyl tetrahydro chaff amine with transfer pipet in system.Reaction 12h, reaction conditions: 90Hz is ultrasonic, 80 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyisoprene-butylbenzene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 16.3 ten thousand, is distributed as 1.07.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.253g, and calculating its grafting efficiency is 80.2%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 2.41: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Triethylamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 20g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add negatively charged ion double activated end polystyrene-butadiene-styrene (Li-SBS-Li) 120g, sampling 1.Get 46.5ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the hexane solution of 20g white carbon black, and mixes, and adds the cyclohexane solution of 4.7ml triethylamine in the reaction system with transfer pipet.Reaction 13h, reaction conditions: 80Hz is ultrasonic, 100 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polystyrene-butadiene-styrene-white carbon black hybridized material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 15.5 ten thousand, is distributed as 1.18.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.692g, and calculating its grafting efficiency is 81.5%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 4.08: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Embodiment 19
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Pentamethyl-diethylenetriamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 25g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add negatively charged ion double activated end polyhutadiene (Li-PB-Li) 120g, sampling 1.Get 33.6ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 20 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of getting the terminal chlorosilane fluidized polymer that 100g makes joins in the cyclohexane solution of 20g white carbon black, and mixes, and adds the cyclohexane solution of 3.4ml pentamethyl-diethylenetriamine in the system with transfer pipet.Reaction 15h, reaction conditions: 60 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-polyhutadiene-white carbon black hybridized material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 14.3 ten thousand, is distributed as 1.06.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.8: 1.Sample 4 is weighed as 1.662g, and calculating its grafting efficiency is 78.9%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 3.16: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
1) gets a there-necked flask, with SiCl
4Be mixed with 5 * 10
-5The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Tetramethyl Ethylene Diamine is made into 5 * 10
-4The cyclohexane solution of mol/ml, and inflated with nitrogen, for subsequent use.Other gets a there-necked flask, and weighing 10g thermal silica is put into wherein, then there-necked flask is placed the about 0.1MPa of relative vacuum pressure, and baking is 2 hours in 120 ℃ the vacuum drying oven, and rear inflated with nitrogen is for subsequent use.
2) in the 2L reactor, add the star-like polyisoprene of anion active-poly-butylbenzene (S-PI-PSB-Li) 120g, sampling 1.Get 225ml SiCl with transfer pipet
4Cyclohexane solution join in the reactor, 50 ℃ of lower reactions 30 minutes, make terminal chlorosilane fluidized polymer, sampling 2.
3) cyclohexane solution of 20g white carbon black is joined in the cyclohexane solution of the terminal chlorosilane fluidized polymer of 100g that makes, and mix, add the cyclohexane solution of 2.3ml Tetramethyl Ethylene Diamine with transfer pipet in the system.Reaction 10h, reaction conditions: 100Hz is ultrasonic, 50 ℃ of heating in water bath, whole reaction process is carried out under nitrogen atmosphere.
4) adopt the water vapour stripping that the solvent in the product is removed, drying obtains white carbon black-star-like polyisoprene-poly-butylbenzene hybrid material (sample 3).From wherein getting 2.000g with toluene dissolving (concentration 4 ‰), slowly add methyl alcohol to producing muddiness, be warming up to muddy the disappearance, cool overnight, the precipitation and centrifugal separation of separating out, vacuum-drying obtains sample 4.
5) characterize: measure with gel permeation chromatography (SEC) after sample 1 vacuum-drying, its number-average molecular weight is 3.2 ten thousand, is distributed as 1.88.Measure with ultimate analysis and x-ray photoelectron power spectrum after sample 2 vacuum-dryings, the mol ratio that calculates chlorine and polymer ends is 2.9: 1.Sample 4 is weighed as 1.538g, and calculating its grafting efficiency is 74.6%;
Employing gel permeation chromatography (SEC) and thermogravimetric analysis (TG) are tested, and calculate its grafting degree and are: 7.45: 1.Sample 3 can be found out prepared material by SEM, tem observation, and section is level and smooth, without hole, makes carbon black clear and is combined with polymer interface closely, and the white carbon black aggregation size is at 10～50nm.
Each embodiment data of table 1 gather
Claims (5)
1. the method for a preparing white carbon black hybridized material prepared by modification with end chlorosilane polymer is characterized in that, may further comprise the steps:
(1) in the living anion polymerization thing, adds chlorosilane, in 30～60 ℃ of lower reactions 10-40 minute, make the polymkeric substance of terminal chlorosilane;
Reactive polymer comprises the polymkeric substance, diene polymer of Styrene and its derivatives and the mixture that is made of two or more polymkeric substance wherein,
The chlorosilane structural formula is R
xSiCl
y, wherein R is alkyl, the carbon atoms number is 1～4; X represents the alkyl number, is 0～2; Y represents the number of Cl, is 2～4;
(2) mixed with polymers with white carbon black and terminal chlorosilane is even, and 25 ℃～100 ℃ are reacted down 1～48h, make the organic-inorganic hybrid material of the polymer-bound white carbon black of terminal chlorosilane behind the desolvation; The mass ratio of white carbon black/terminal chlorosilane fluidized polymer is 20: 1～1: 10.
2. method according to claim 1 is characterized in that: white carbon black is thermal silica or precipitated silica in the step (2), its particle diameter 10～200nm.
3. method according to claim 1 is characterized in that: add amines catalyst in the step (2).
4. method according to claim 3 is characterized in that: the amines catalyst that adds in the step (2) is triethylamine, Tetramethyl Ethylene Diamine, pentamethyl-diethylenetriamine or N-N-dimethyl tetrahydro chaff amine.
5. method according to claim 1, it is characterized in that: reactive polymer is polyhutadiene PB, polyisoprene PI, polystyrene PS, Butadiene/Styrene random copolymers PSB, isoprene-butylbenzene copolymer PI-PSB, the one or more kinds of mixtures of Butadiene/Styrene block copolymer SBS in the step (1), and molecular chain is linearity, branching shape or star; Its number-average molecular weight is 5000～200000.
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| EP1243619A1 (en) * | 1999-08-13 | 2002-09-25 | Asahi Kasei Kabushiki Kaisha | Organic domain/inorganic domain composite material |
| CN1970648A (en) * | 2006-12-04 | 2007-05-30 | 浙江大学 | Method for preparing dispersive type carbon black adopting surface graft modification method |
| CN101220177A (en) * | 2008-01-25 | 2008-07-16 | 北京化工大学 | Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material |
| CN101735633A (en) * | 2009-11-26 | 2010-06-16 | 同济大学 | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof |
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| EP1243619A1 (en) * | 1999-08-13 | 2002-09-25 | Asahi Kasei Kabushiki Kaisha | Organic domain/inorganic domain composite material |
| CN1970648A (en) * | 2006-12-04 | 2007-05-30 | 浙江大学 | Method for preparing dispersive type carbon black adopting surface graft modification method |
| CN101220177A (en) * | 2008-01-25 | 2008-07-16 | 北京化工大学 | Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material |
| CN101735633A (en) * | 2009-11-26 | 2010-06-16 | 同济大学 | Functionalized organic/inorganic hybridized asymmetric structure particle and synthesis method thereof |
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