CN102344638B - Method for reinforcing grafted diene rubber by in-situ sol-gel method - Google Patents
Method for reinforcing grafted diene rubber by in-situ sol-gel method Download PDFInfo
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Abstract
The invention discloses a method for reinforcing grafted diene rubber by an in-situ sol-gel method. The method comprises the following steps of: adding vinyl siloxanes and benzoyl peroxide into diene rubber latex, reacting for 2 to 6h at the temperature of between 68 and 80 DEG C to obtain vinyl siloxanes grafted and modified diene rubber latex, and adding tetraethoxysilane into the vinyl siloxanes grafted and modified diene rubber latex at the temperature of between 68 and 80 DEG C and performing sol-gel reaction to obtain in-situ reinforced butadiene styrene rubber. The silica-reinforced rubber prepared by the method has higher pure rubber and vulcanized rubber strength and good processability, and has a great significance for the processes of the rubber such as mixing, transportation, storage and the like. The problem of incompatibility of polar silica and rubber is solved to a certain degree, and a theoretical basis is provided for overcoming the contradiction between the reduction of rolling resistance of tyres and the improvement on wet skid resistance.
Description
Technical field
The present invention relates to a kind of Enhancement Method of diene class rubber, particularly relate to the method that a kind of IN-SITU SOL-GEL strengthens the diene class rubber of the standby grafting of the poly-legal system of breast.
Background technology
The styrene-butadiene rubber(SBR) that filler strengthens is used in many fields, as: sealing-ring, pad, tire etc.Recently, also have a wide range of applications at radial, but the rubber unvulcanizate when the radial-ply tyre moulding between the skeleton cord need to bear large ability to 3 times of deformation of its original size, for keeping the design accuracy of tire size, the performance of tyre cord being inserted glue has proposed higher requirement, namely requires sizing material to have sufficiently high green strength and stress energy to increase with the increase of deformation.
Document " Siti Hajjar; Che Man; Azanam S; et al; .Studies on the curing behaviour and mechanical properties of styrene/methylmethacylate grafted deprteinized natural rubber latex[J] .Journal of Polymer Research; 2008,15 (5): 357-364. " introduced the natural rubber that has obtained vinylbenzene and methyl methacrylate-grafted in the natural rubber latex Ruzhong.The method is simple to operate, easily realizes industrialization.
Document " Kazumasa Yshikai; Tesur hsaki; Mutsuhisa Furukawa.Silica Reinforcement of Synthetic Diene Rubbers by Sol-Gel Process in the latex[J] .Journal of Applied Polymer Science.2002; 85 (10): 2053-2063. " introduced in diene class rubber latex by tetraethoxy (TEOS) sol-gel method and realized respectively enhancing to styrene-butadiene rubber(SBR) and paracril rubber, by with TEOS, rubber latex, after 25% ammonia soln and water fully mix, at 40 ℃, react 24h under the microwave radiation condition, the last rubber that drying is enhanced under the certain pressure condition.Although the method has realized the silicon-dioxide enhancing of sol-gel method to rubber, required condition is harsh.For styrene-butadiene rubber(SBR), not having under the condition to its modification, along with the increase that strengthens the styrene butadiene rubber latex shelf-time, the silicon-dioxide that the TEOS sol-gel method generates is easily reunited and is caused stability of emulsion simultaneously.
In US7625971, the author has realized the enhancing to styrene-butadiene rubber(SBR) with the water glass sol-gel method in latex, and has obtained particle styrene-butadiene rubber(SBR), but the method needs to realize at strong acidic condition.
In US7619028, the author adopts two-step approach to realize silica-reinforced rubber, at first silicon-dioxide is dispersed in the organic solvent, then the silica suspension that obtains is mixed the rubber that cohesion is enhanced with rubber latex.
In CN99123553.3, form silicon-dioxide by transforming at the base catalysis sol-gel by tetraethoxysilane (TEOS), thereby realize the enhancing of rubber.
Japanese Patent Application Publication 93/02152:TEOS mixes in organic solvent with unvulcanized rubber.
Sol-gel method is a kind of take silicon ester as raw material, and gradually gel behind hydrolytie polycondensation is prepared highly uniformly material through aftertreatment.Tetraethoxysilane as the metal ring oxide compound, extensively is used in the enhancing to organic styrene-butadiene rubber(SBR), size of particles and its dispersiveness in styrene-butadiene rubber(SBR) that the method can generate by changing reaction conditions control.Document " Kazumasa Yshikai; Tesur hsaki; Mutsuhisa Furukawa.Silica Reinforcement of Synthetic Diene Rubbers by Sl-Gel Process in the latex[J] .Journal of Applied Polymer Science.2002; 85 (10): 2053-2063. " and " Huang Zuchang. with generated in-situ white carbon black reinforcement NR: with the contrast [J] of black-reinforced sizing material. rubber bibliography; 2002,32 (2): 668-6721. " carried out respectively relevant report.Divide two kinds according to report with the main method that the method strengthens styrene-butadiene rubber(SBR): the first is that TEOS after the swelling, is added acidity or basic catalyst and causes the styrene-butadiene rubber(SBR) that the sol gel reaction is enhanced in the styrene-butadiene rubber(SBR) blob of viscose; The second be with tetraethoxysilane directly to joining in the styrene butadiene rubber latex, carry out emulsification, then add the styrene-butadiene rubber(SBR) that basic catalyst generation sol gel reaction is enhanced.Above-mentioned first method shortcoming is owing to being subject to the impact of cross-linked rubber cross-linking density, has limited the swelling quantity of tetraethoxysilane in styrene-butadiene rubber(SBR).The shortcoming of second method is need to use a large amount of catalyzer, simultaneously the silicon dioxide granule that generates of tetraethoxysilane sol-gel method since the surface with a large amount of hydroxyls, thereby cause emulsion unstable along with the prolongation of time can interact.
Document " generates SiO with the sol-gel method original position
2Reinforced Rubber [J]. China Synthetic Rubber Industry .2000,23 (3): 148-152 " propose.In epoxy natural rubber, carry out precrosslink with γ aminopropyltriethoxy silane (APS) as precrosslinker, then carry out sol gel reaction.The method adopts mould pressing technology, utilizes to form a kind of Van der Waals force between γ aminopropyltriethoxy silane (APS) and the epoxy natural rubber (ENR), forms a precrosslink ENR.Then the wet method sulfuration obtains the ENR cross-linked rubber.The ENR sulfuration is through the abundant swelling of TEOS, and under conditions suitable, TEOS hydrolysis occurs obtains the ENR that silicon-dioxide strengthens.Its shortcoming is in Intermolecular Forces, Van der Waals force a little less than, cause APS and ENR to interact relatively poor.The mould pressing technology that adopts simultaneously, operating process is complicated.Last owing to being subject to the restriction of ENR state of vulcanization, the swelling ratio of TEOS in ENR is restricted.
Document " Sittiphan Torpong; Prasassarakich Pattarapan; Poompradub Sirilux.In situ silica filled styrene grafted natural rubber by the sol-gel process[J] .Advanced Materials Research.2010,93-94:525-528. " has been studied the natural rubber that the TEOS original position strengthens vinylbenzene (ST) grafting.This article has at first prepared the natural rubber latex of ST grafting, then adds TEOS, and the sol gel reaction rubber that is enhanced occurs under catalyst action.This article by first grafting after sol gel reaction obtained the natural rubber that silicon-dioxide strengthens.Document " P Satraphana; A Intasirib; V Tangpasuthadolb; et al; .Effects of methyl methacrylate grafting and in situ silica particle formation on the morphology and mechanical properties of natural rubber composite films.[J] .Polymers for advanced technologies.2009,20 (5): 473-486. " adopt to use the same method and studied the natural rubber of TEOS original position enhancing methyl methacrylate (MMA) grafting.But the document has adopted respectively ST and MMA in to natural rubber graft modification process be grafted monomer, grafting between the styrene-butadiene rubber(SBR) of ST and MMA and silicon-dioxide reactive force a little less than.
Summary of the invention
In order to overcome the shortcoming of prior art, enlarge simultaneously the application of diene class rubber in radial-ply tyre, the invention provides a kind of method for preparing the diene class rubber that strengthens by two-step approach.
The present invention adopts technical scheme as follows: in mass fraction, quality %:
(1) preparation of vinyl-based polysiloxane grafted diene class rubber latex:
Step 1 is in container, and the adding mass fraction is 300.00 parts～400.00 parts diene class rubber latex;
Step 2 is under the N2 protection, be warmed up to 60 ℃～80 ℃, in 40min～70min oil phase is added drop-wise in the styrene butadiene rubber latex of step 1, described oil phase is 5～12 parts vinyl-based siloxanes and 0.05 part～0.30 part organic peroxide evocating agent (such as benzoyl peroxide etc.);
Then step 3 after 2 hours～6 hours, obtains the diene class rubber latex of vinyl-based polysiloxane grafted modification 60 ℃～80 ℃ lower reactions.
(2) the diene class rubber latex preparation of the vinyl-based polysiloxane grafted modification of tetraethoxysilane sol-gel method enhancing:
Step 1: in container, adding mass fraction is the diene class rubber latex of 300.00 parts～400.00 parts vinyl-based polysiloxane grafted modification, is warmed up to 60 ℃～80 ℃;
Step 2: in 60min～90min, 5 parts～40 parts tetraethoxysilanes (TEOS) are added drop-wise in the material of step 1 the diene class rubber latex after discharging is enhanced behind generation sol gel reaction 2h～5h.
The preferred styrene-butadiene latex of diene class latex, nitrile rubber, polybutadiene latex etc. among the present invention.For guaranteeing stably rate of polymerization and reaction mechanism, select the diene class latex of 300.00 parts～400.00 parts of mass fractions, latex concentration is 15%～25%.
The vinyl-based siloxanes of the present invention can be selected from one or more in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, the vinyltriacetoxy silane.The preferred vinyl triethoxyl silane.Because this one type of silane can be carried out grafting with styrene-butadiene rubber(SBR), the chemical bond that simultaneously Ethoxysilane hydrolysis can be connected with silicon-dioxide Si-O-Si connects.For guaranteeing higher percentage of grafting, the add-on of vinyl-based siloxanes is 5 parts～12 parts.
Organic peroxide evocating agent of the present invention is preferably selected the thermolysis organic peroxide evocating agent, as being benzoyl peroxide (BPO), Diisopropyl azodicarboxylate, hydrogen phosphide cumene etc., for guaranteeing abundant two keys are arranged, the preferred benzoyl peroxide of initiator of the present invention in the sulfuration of later stage styrene-butadiene rubber(SBR).The initiator add-on is 0.05 part～0.30 part, because during the initiator Inducing Graft Polymerization, mainly is to attack allylic hydrogen, rather than two key, and guaranteeing like this has abundant two keys in the sulfuration of later stage diene class rubber.
The first step is that vinyl-based siloxanes carries out graft modification to rubber among the present invention, has intermolecularly formed the chemical b ` power stronger than Van der Waals force.Adopting simultaneously vinyl-based siloxanes is grafted monomer, can strengthen the reactive force between graft rubber and silicon-dioxide; Second step TEOS directly joins in the latex, and the add-on of TEOS is not subject to any restriction, and does not affect the rubber product shape.
The present invention has obtained the tetraethoxysilane IN-SITU SOL-GEL by two-step approach and has strengthened vinyl-based polysiloxane grafted diene class rubber, particularly styrene-butadiene rubber(SBR), paracril.Compared with prior art, the present invention does not add catalyzer, is directly to pass through the thermal initiation sol gel reaction, and under thermal initiation, the TEOS hydrolysis is slow, can guarantee the stability of latex, prevents that the rapid hydrolysis of TEOS causes the latex loss of stability under base catalysis; Mainly be to mix in water, environmental pollution is few, and is simultaneously economical and practical.
Major advantage of the present invention also is: the one, TEOS can well mix with latex, makes TEOS get not restriction of add-on; The 2nd, diene class rubber is by vinyl-based silicone-modified, strengthened reactive force between silicon-dioxide that TEOS generates and rubber molecular chain.
Owing to need not add catalyzer, sol gel generation silicon-dioxide directly occurs after the grafting of diene class rubber latex strengthen diene class rubber, because this diene class rubber passes through vinyl-based organic siloxane modified in early stage, therefore reactive force is larger between the silicon-dioxide of tetraethoxysilane sol gel generation and diene class rubber molecular chain, and the stability of diene class rubber latex better.Silicon-dioxide silicon utilization ratio is more than 78.85% in the diene class rubber that can be enhanced after cohesion, mixing and sulfuration for latex, and pure glue cross-linked rubber tensile strength is greater than the Reinforced Rubber of 6.81MPa.This Enhancement Method has improved the pure glue cross-linked rubber intensity of rubber, makes it have good processibility, and higher pure glue cross-linked rubber intensity helps the Rubber processing moulding.When for example going up tread rubber in the tire building, the tread rubber blank must be subject to larger stretching, if the pure glue green strength of tread rubber is low just yielding, moulding can't be carried out smoothly, simultaneously the techniques such as mixing, the transportation of rubber, storage are had great importance, and solved to a certain extent the consistency of polarity silicon-dioxide and rubber, proposed theoretically to solve and reduced tire drag and the contradiction that improves anti-slippery.
Description of drawings
Accompanying drawing is the morphology analysis figure of silica-reinforced rubber, wherein:
Fig. 1 is: pure styrene-butadiene rubber(SBR);
Fig. 2 is: TEOS strengthens the styrene-butadiene rubber(SBR) that does not have graft modification;
Fig. 3 is: TEOS strengthens the styrene-butadiene rubber(SBR) of vinyltriethoxysilane graft modification;
Fig. 4 is: TEOS strengthens the styrene-butadiene rubber(SBR) of vinyltriethoxysilane modification.
Embodiment
For effect of the present invention is described, enumerates embodiment the present invention is described in further detail, when the present invention is not limited in these embodiment.
1, analytical procedure
The enhancing sizing material that the analysis of dioxide-containing silica takes by weighing certain mass in the polymkeric substance is counted m
1, will strengthen sizing material and be placed in the retort furnace 800 ℃ of calcinations 8 hours, residuum with the dilute hydrochloric acid washing after the drying m that weighs to get
2, calculating at last dioxide-containing silica is w
1=m
1/ m
2* 100%.
Theoretical dioxide-containing silica (w in the analysis Reinforced Rubber of silicon-dioxide utilization ratio
4) comprise the dioxide-containing silica that vinyltriethoxysilane and tetraethoxysilane two one type of silane are converted to, use respectively w
2And w
3Expression, calculation formula is as follows:
The silicon-dioxide utilization ratio is w
4/ w
1* 100%.
M in the formula
3, m
4Represent respectively the vinyltriethoxysilane of adding and the quality of tetraethoxysilane; M
3,, M
4Represent respectively the vinyltriethoxysilane of adding and the molecular weight of tetraethoxysilane; 28,60 molecular weight that represent respectively element silicon and silicon-dioxide.
The preparation of pure glue cross-linked rubber is respectively with behind the rubber plastic steelmaking before and after the modification, carries out mixing according to the prescription of table 1:
Table 1 sulfurizing formula
At room temperature carry out mixingly, follow following program and carry out mixing:
(1) transfers roll spacing 1.1mm, press refining, 4min
(2) evenly add sulphur, 2min
(3) evenly add stearic acid, make 3/4 cutters once, 2min
(4) add zinc oxide, promotor, 3min
(5) thin-pass is 6 times, 2min, lower
After mixing, park more than 12 hours, curing time is definite according to vulcanization curve, and vulcanization curve is determined without the rotor vulkameter by the Jiangdu absolute sincerity JC-2000E of instrument plant, measure curing time under 160 ℃.At last in compression molding.
Analysis of tensile strength is measured the tensile strength of the pure glue cross-linked rubber of rubber according to GB528-1998.
The styrene-butadiene rubber(SBR) that the rubber morphology analysis strengthens-78 ℃ of lower brittle failures is then to the laggard line scanning electron microscopic analysis of surface of fracture metal spraying of the styrene-butadiene rubber(SBR) that strengthens.
2. raw material sources:
Styrene-butadiene rubber(SBR) (SBR1721) latex: CNPC's Lanzhou Petrochemical is produced, wherein divinyl 80% (wt).
Paracril (NBR32) latex: CNPC's Lanzhou Petrochemical is produced, wherein divinyl 68% (wt).
Polyhutadiene (BR9000) latex: commercially available industrial goods, wherein divinyl＞99.0% (wt).
Embodiment 1
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 68 ℃, add 11.00g vinyltriethoxysilane and 0.15g benzoyl peroxide, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 3.0h obtains the vinyltriethoxysilane graft modification under this temperature.Then under this temperature, add the 40g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gel reaction 4h that occur, latex is the styrene-butadiene rubber(SBR) that is enhanced after cohesion, mixing and sulfuration, dioxide-containing silica is 10.95% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 78.85%, and pure glue cross-linked rubber tensile strength is 6.81MPa.
Comparative Examples 1
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 68 ℃, 0.15g benzoyl peroxide and 11g vinyltriethoxysilane, 50min is reinforced complete, then reaction 7.0h obtains the styrene butadiene rubber latex of vinyltriethoxysilane graft modification under this temperature, and latex can obtain pure glue cross-linked rubber tensile strength after cohesion, mixing and sulfuration be the styrene-butadiene rubber(SBR) of 3.42MPa.
Embodiment 2
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 75 ℃, add 8.00g Vinyldimethylethoxysilane and 0.12g benzoyl peroxide, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 3.5h obtains the graft modification of methyl ethylene Ethoxysilane under this temperature.Then under this temperature, add the 6.00g tetraethoxysilane, 60min dropwises, at last at 80 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 4.76% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 88.86%, and pure glue cross-linked rubber tensile strength is 4.53MPa glue.
Comparative Examples 2
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 75 ℃, add 8.00g vinylbenzene and 0.12g benzoyl peroxide, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 3.5h obtains the styrene-grafted modification under this temperature.Then under this temperature, add the 6.00g tetraethoxysilane, 60min dropwises, at last at 80 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 2.56% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 78.86%, and pure glue cross-linked rubber tensile strength is 3.53MPa.
Embodiment 3
In container, add the 300.00g styrene butadiene rubber latex, be warmed up to 80 ℃, add 11.00g vinyltrimethoxy silane and 0.20g hydrogen phosphide cumene, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 2.5h obtains the vinyltrimethoxy silane graft modification under this temperature.Then under this temperature, add the 30g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 10.31% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 79.20%, and pure glue cross-linked rubber tensile strength is 6.50MPa.
Comparative Examples 3
In container, add the 300.00g styrene butadiene rubber latex, be warmed up to 80 ℃, add 11.00g methyl methacrylate and 0.20g hydrogen phosphide cumene, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 2.5h obtains the vinyltrimethoxy silane graft modification under this temperature.Then under this temperature, add the 30g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 5.95% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 68.85%, and pure glue cross-linked rubber tensile strength is 4.81MPa.
Embodiment 4
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 70 ℃, add 9.00g vinyltriacetoxy silane and 0.10g benzoyl peroxide, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 4h obtains the vinyltriacetoxy silane graft modification under this temperature.Then under this temperature, add the 15g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 6.26% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 81.74%, and pure glue cross-linked rubber tensile strength is 5.12MPa.
Comparative Examples 4
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 70 ℃, add 9.00g γ aminopropyltriethoxy silane (APS) and 0.10g benzoyl peroxide, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 4h obtains the vinyltriacetoxy silane graft modification under this temperature.Then under this temperature, add the 15g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 5.45% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 71.15%, and pure glue cross-linked rubber tensile strength is 3.25MPa.
Embodiment 5
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 68 ℃, add 10.00g vinyltrimethoxy silane and 0.20g hydrogen phosphide cumene, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 3.5h obtains the vinyltrimethoxy silane graft modification under this temperature.Then under this temperature, add the 20g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the styrene-butadiene rubber(SBR) that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 7.16% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 81.37%, and pure glue cross-linked rubber tensile strength is 5.89MPa.
Comparative Examples 5
In container, add the 380.00g styrene butadiene rubber latex, be warmed up to 68 ℃, add 10.00g vinyltrimethoxy silane and 0.20g hydrogen phosphide cumene, 50min is reinforced complete, then reacts the styrene butadiene rubber latex that 3.5h obtains the vinyltrimethoxy silane graft modification under this temperature.Then under this temperature, the styrene-butadiene rubber(SBR) that aggregation 4h is enhanced.Rubber adds the 20g tetraethoxysilane in sulfidation, dioxide-containing silica is 5.55% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 63.08%, and pure glue cross-linked rubber tensile strength is 3.46MPa.
Embodiment 6
In container, add 300.00g paracril latex, be warmed up to 60 ℃, add 10.00g Vinyldimethylethoxysilane and 0.12g benzoyl peroxide, 50min is reinforced complete, then reacts the paracril latex that 4.5h obtains the graft modification of methyl ethylene Ethoxysilane under this temperature.Then under this temperature, add the 6.00g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 5h that occur, the paracril that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 6.06% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 92.45%, and pure glue cross-linked rubber tensile strength is 5.3MPa.
Embodiment 7
In container, add 380.00g paracril latex, be warmed up to 70 ℃, add 8.00g vinyltrimethoxy silane and 0.20g hydrogen phosphide cumene, 50min is reinforced complete, then reacts the paracril latex that 4.0h obtains the vinyltrimethoxy silane graft modification under this temperature.Then under this temperature, add the 20g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the paracril that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 7.57% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 85.52%, and pure glue cross-linked rubber tensile strength is 5.95MPa.
Embodiment 8
In container, add the 380.00g content of polybutadiene rubber latex, be warmed up to 75 ℃, add 9.00g vinyltriacetoxy silane and 0.08g benzoyl peroxide, 50min is reinforced complete, then reacts the content of polybutadiene rubber latex that 4h obtains the vinyltriacetoxy silane graft modification under this temperature.Then under this temperature, add the 15g tetraethoxysilane, 60min dropwises, at last at 70 ℃ of lower sol gels reaction 4h that occur, the polybutadiene rubber that latex is enhanced after cohesion, mixing and sulfuration.Dioxide-containing silica is 6.45% in the rear rubber of enhancing, and the silicon-dioxide utilization ratio is 84.56%, and pure glue cross-linked rubber tensile strength is 7.5MPa.
Claims (4)
1. an IN-SITU SOL-GEL strengthens the method for the diene class rubber of grafting, it is characterized in that in mass fraction:
(1) preparation of vinyl-based polysiloxane grafted diene class rubber latex:
Step 1 is in container, and the adding mass fraction is 300.00 parts～400.00 parts diene class rubber latex;
Step 2 is at N
2Protection is lower, is warmed up to 60 ℃～80 ℃, in 40min～70min oil phase is added drop-wise in the diene class rubber latex of step 1, and described oil phase is 5～12 parts vinyl-based siloxanes and 0.05 part～0.30 part thermolysis organic peroxide evocating agent;
Then step 3 after 2 hours～6 hours, obtains the diene class rubber latex of vinyl-based polysiloxane grafted modification 60 ℃～80 ℃ lower reactions;
(2) the diene class rubber latex preparation of the vinyl-based polysiloxane grafted modification of tetraethoxysilane sol-gel method enhancing:
Step 1: in container, adding mass fraction is the diene class rubber latex of 300.00 parts～400.00 parts vinyl-based polysiloxane grafted modification, is warmed up to 60 ℃～80 ℃;
Step 2: in 60min～90min, 5 parts～40 parts tetraethoxysilanes are added drop-wise in the diene class rubber latex of vinyl-based polysiloxane grafted modification of step 1, the diene class rubber latex after discharging is enhanced behind sol gel reaction 2h～5h occurs.
2. method according to claim 1 is characterized in that diene class rubber latex is styrene-butadiene latex, nitrile rubber or polybutadiene latex.
3. method according to claim 1, it is characterized in that vinyl-based siloxanes be vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane one or more.
4. method according to claim 1 is characterized in that the thermolysis organic peroxide evocating agent is benzoyl peroxide, Diisopropyl azodicarboxylate or hydrogen phosphide cumene.
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| CN102676096B (en) * | 2012-05-23 | 2013-08-07 | 江苏省东泰精细化工有限责任公司 | Preparation method of organosilicon conductive adhesive containing nanorod-shaped zinc oxide |
| CN103665729B (en) * | 2012-09-18 | 2016-05-11 | 中国石油天然气股份有限公司 | Oil-extended styrene buadiene rubber, composition and method of making the same that nano silicon is contained on a kind of surface |
| US9976013B2 (en) | 2013-07-31 | 2018-05-22 | Toyo Tire & Rubber Co., Ltd. | Rubber-silica composite and method for producing same, and rubber composition and pneumatic tire |
| CN108424566A (en) * | 2018-03-30 | 2018-08-21 | 华南理工大学 | A method of it is condensed by Silica dehydration and realizes hot-press vulcanization epoxy natural rubber hybrid material |
| CN113388119B (en) * | 2021-06-04 | 2022-03-22 | 诚展（清远）鞋业有限公司 | Preparation method of polyhydroxysilane modified butadiene rubber and ozone aging resistant rubber |
| CN115806700A (en) * | 2021-09-15 | 2023-03-17 | 中国石油化工股份有限公司 | White carbon black reinforced styrene-butadiene rubber composite material and preparation method thereof |
| CN114685820B (en) * | 2022-04-28 | 2023-11-10 | 山东京博中聚新材料有限公司 | High-solid-content cationic styrene-butadiene latex for modifying road asphalt and preparation method thereof |
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