CN102020752A - Method of grafting and modifying rubber latex containing poly conjugated dialkene by in situ hybridization of silicon - Google Patents
Method of grafting and modifying rubber latex containing poly conjugated dialkene by in situ hybridization of silicon Download PDFInfo
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Abstract
A method of grafting and modifying rubber latex containing poly conjugated dialkene by in situ hybridization of silicon includes the following steps taking 100 parts by mass of rubber latex containing poly conjugated dialkene, adding from 4 to 25 parts of organic siloxane monomers with unsaturated bond into the rubber latex containing poly conjugated dialkene, stirring sufficiently to obtain uniform mixture, adding from 0.20 to 0.36 parts of initiators with stirring at the temperature of 5-85 DEG C for carrying out graft polymerization reaction for 5 to 8 hours, and agglomerating and drying the grafted and modified rubber latex. The structure formula of organo-sillicone monomers with unsaturated bond is Y-Si(R1R2R3), wherein Y- is unsaturated aliphatic chain segment with 2 to 18 carbons, R1- is alkoxy with 1 to 12 carbons, aryloxya with 6 to 12 carbons or silicide with 3 to 12 carbons, and R2 and R3 are the same groups as R1 or can also be saturated chain segment with 1 to 20 carbons or annular alkane or aromatic hydrocarbon with 1 to 8 carbons.
Description
Technical field
The present invention relates to a kind of method of modifying of latex, be specifically related to the method that silicon situ-formed graft hybrid modification contains poly-conjugated-diolefin latex.
Background technology
So-called in-situ hybridization is meant in disperse phase at compound system (strengthening body or functive) and the external phase (matrix), have at least once before Compound Machining, not existing mutually, but in compound processing course, under other one condition that has existed mutually, generate.The in-situ hybridization modification of rubber is meant by technologies such as graft copolymerization or cohydrolysis disperse phase silicon is dispersed in the rubber matrix with chemical bond or nano-scale, to improve its tear resistance, fall low-heat-generation and can improve the binding property of sizing material and other parts in the composite product.Because the rubber of silicon modification shows good low-rolling-resistance and anti-slippery after being applied to tire, so the scientific worker was exploring the method for preparing silicon modified rubber in the last few years always.
At present, the preparation method of domestic and international silicon modified rubber has a variety of, can be divided into two big classes on the whole: mechanically milling composite algorithm Reinforced Rubber; The in-situ hybridization method.Mechanically milling composite algorithm Reinforced Rubber comprises mixing compound enhancing behind the mixing compound enhancing of improved silica, the modified rubber again.Generally speaking, it is higher that mechanically milling composite algorithm ubiquity mixing power consumption of polymer processing, and nanoparticle is difficult to reach problems such as the equidistant homodisperse of ideal, reunion when mixing.And the in-situ hybridization method has not only well solved particle scattering problem of (particularly nonpolar rubber) in rubber matrix, and can realize the controllability of silicon dioxide granule particle diameter to a certain extent, this process can be carried out in cross-linked rubber or unvulcanised glue simultaneously.
Document " Y.IKEDA; Y.KAMEDA.Preparation of " Green " Composites by Sol-Gel Process:In Situ Silica Filled Natural Rubber[J] .Journal of Sol-Gel Science and Technology2004; 31 (1-3): 137～142. " introduced under alkaline condition, with tetraethoxysilane (TEOS) in natural rubber after the swelling, hydrolytic condensation takes place, sulfuration has obtained enhanced rubber then, compare with traditional blend, the dispersion of generated in-situ silicon-dioxide in rubber is comparatively even.Be to connect between the interface of the silicon-dioxide/rubber composite of this article preparation by physical action, rather than connect by chemical bond.
In US5665812, it is solvent that the author adopts toluene, cause divinyl and styrene polymerization with n-Butyl Lithium, add γ-(2,3 epoxies, third oxygen) propyl trimethoxy silicane then and the rubber that anionoid polymerization has obtained two ends or multiterminal functional siliconization takes place down at 60 ℃.This rubber shows good static state and dynamic properties, also butadiene-styrene-synthetic polyisoprene has been carried out the functional siliconization at two ends simultaneously in the patent.Also used similar method to use pregnancy basic ring cyclotrisiloxane and γ-(2 respectively among the US6013718,3 epoxies, third oxygen) propyl trimethoxy silicane has carried out styrene-butadiene rubber(SBR) terminated functional siliconization, and obtained not having the styrene-butadiene rubber(SBR) of functionalization with methyl alcohol, and reached 81% with the degree that HNMR has analyzed the functional siliconization of molecular chain, the Mooney viscosity test of three kinds of rubbers shows basic not variation, and the sulfuration back kinetic test SBR of Presentation Functionization as a result has hot Δ G ' of lower life (23 ℃) and dissipation factor tan δ (23 ℃).
People such as Daniel Edward Bowen has adopted the functionalization that TEOS carries out the chain end group of styrene-butadiene rubber(SBR) among the US7141622, the silicon-dioxide that has added the silane coupling agent processing has then carried out modification, compare with mechanical mixing, show better tensile strength and Young's modulus, particularly reduced the energy consumption when mixing, the price of TEOS is also comparatively cheap, this is important in industrialization, with this method enhanced rubber owing to will add a large amount of solvents, so, will inevitably increase production cost for industrialization.
In US4381377, the author adopts two-step approach to obtain the polybutadiene rubber of functional siliconization, the first step is the isomerization of polyhutadiene, second step is under high temperature (190～250 ℃), vinyltriethoxysilane and polyhutadiene are reacted the rubber that 4h obtains functional siliconization, but when with this method modified rubber latex, need very high energy consumption on the one hand, under hot conditions, also can cause breakdown of emulsion simultaneously.
US4822587 discloses under the condition that zinc oxide exists, and the method that adopts reaction to extrude is carried out the graft modification of organosilane to segmented copolymer.Concrete technical scheme is: the mixture with segmented copolymer and zinc oxide mixes in forcing machine with organosilane earlier, utilize the peroxide degradation polymkeric substance under 140 ℃ and cause Silanization reaction being not less than then, last at the graft reaction of after mixing after a while, finishing whole silane, this method complicated operating process, simultaneously under hot conditions, the graft modification agent is autohemagglutination and influence graft polymerization reaction probably.
Graft modification for emulsion polymerized rubber, be usually used in the grafted monomer ST (vinylbenzene), MMA (methyl methacrylate), MA (maleic acid), MAH (MALEIC ANHYDRIDE), MAA (methacrylic acid), AA (vinylformic acid) etc. are arranged, yet for the grafted monomer of organosilicon alkanes, the instability that causes emulsion owing to organosilane easy hydrolysis in mutually, present research reports that seldom the method that this patent adopts organosilane to drip has realized organosilane graft modification rubber.
Summary of the invention
The prepared rubber of prior art/silicon compound matrix material disperse phase is easily reunited in order to overcome, problems such as reactive force is low between the organic/inorganic interface, the invention provides a kind of from containing the latex of poly-conjugated-diolefin, in the preparation method of latex phase in-situ preparing rubber/silicon compound matrix material.
The technical solution adopted in the present invention is (dry glue quality in the latex that contains poly-conjugated-diolefin is 100 parts): 4～25 parts of the organo-siloxane monomers that will contain unsaturated link(age), preferred 10～15 parts, join in the latex that contains poly-conjugated-diolefin, fully mix, under 5～85 ℃ of temperature and agitation condition, add initiator and carry out graft polymerization reaction 5～8h for 0.20～0.36 part, at last with the emulsion condensation drying of graft modification; Its structural formula of organo-siloxane monomer that contains unsaturated link(age) is:
Wherein:
Y-contains the unsaturated aliphatic segment of 2～18 carbon, can be vinyl, propenyl, allyl group, sec.-propyl, pseudoallyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, ethynyl, 1-proyl, ethyl acetylene base, 1-pentynyl, 1-heptyne base, methacryloxypropyl, methacryloxy, preferred vinyl, methacryloxypropyl;
R
1-contain the alkoxyl group of 1～12 carbon, the aryloxy of 6～12 carbon, the siloxy of 3～12 carbon, can be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, hexyloxy, pentyloxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferred methoxyl group, oxyethyl group, isopropoxy;
R
2And R
3Can be and R
1Identical group can also be the saturated segment that contains 1～20 carbon, 1～8 cyclic alkane, aromatic hydrocarbon; Preferable methyl, ethyl, methoxyl group, oxyethyl group.
The organo-siloxane monomer that contains unsaturated link(age) of the present invention can be the vinyl siloxanes, in the methyl acrylic ester siloxanes one or more, preferred vinyl triethoxyl silane (VTES), vinyltrimethoxy silane (VTMS), vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, the vinyl tributanoximo silane, methyl tributanoximo silane, vinyl silane triisopropoxide, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane (MPS), in three (trimethylsiloxy group) the methacryloxypropyl silane (MPTS) one or more; More preferably one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) the methacryloxypropyl silane.
The latex that contains poly-conjugated-diolefin in the described method is that its homopolymer is content of polybutadiene rubber latex, chloroprene rubber latex, natural rubber latex etc. by prepared homopolymer or the multipolymer that contains the conjugated diolefine hydrocarbon compound of conventional emulsion polymerization; Its multipolymer is conjugated diolefine hydrocarbon compound and aryl ethylene compounds, the monoene compounds, acrylic compounds, the binary of acrylic ester compound or terpolymer, described aryl ethylene compounds can be a vinylbenzene, alpha-methyl styrene, the 2-phenylallene, 1-bromobenzene propylene, ethyl styrene and their derivative, described monoene compounds can be an ethene, vinylchlorid, propylene, 1-butylene, the 2-amylene, vinyl cyanide and their derivative, described acrylic compounds can be a vinylformic acid, methacrylic acid and their derivative, described acrylic ester compound can be methyl methacrylates, Jia Jibingxisuanyizhi, methyl acrylate, ethyl propenoate and their derivative; Multipolymer can be styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex etc.Homopolymer or the multipolymer that contains the polymerized conjugated diene hydrocarbon compound of the present invention is 100% in homopolymer or copolymer quality, and its conjugated diolefine hydrocarbon content is 50%～100%, preferred 60%～80%.
Initiator can be a thermal decomposition initiating in the described method, also can be redox initiator, and initiator is that those of ordinary skills are known.Thermal decomposition initiating can be an oil-soluble initiator, also can be water soluble starter; Oil-soluble initiator can be acyl peroxide class initiator or azo-initiator, preferred benzoyl peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, 1, the peroxidation-3 of 1-dual-tert-butyl, 3,5 trimethyl-cyclohexanes, ditertiary butyl peroxide, peroxidation-2-ethylhexyl tert-pentyl ester, tert-butyl peroxy acetate, tertbutyl peroxide, 2,5-dimethyl-2,5 di-t-butyl peroxy hexanes, dilauroyl peroxide, di-isopropylbenzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two isocapronitriles, dinitrogen (2,5-dimethyl-6-carboxyl) one or more in the own nitrile, more preferably benzoyl peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile); Water soluble starter can be persulphate or azo salt initiator, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, 2, two (the 2-amidine azoles quinoline propane) hydrochlorides, 2 of 2-azo, 2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride.Redox initiator can be persulphate-mercaptan, persulphate-hydrosulphite, oxymuriate-hydrosulphite, hydrogen peroxide-ferrous salt, in organic hydroperoxide-ferrous salt redox initiation system one or more, preferred Potassium Persulphate/S-WAT, lauroyl peroxide amine/N, the N-dibutyl aniline, benzoyl peroxide/N, N-dimethyl-para-totuidine, hydrop diisopropylbenzene(DIPB)/tetraethylene pentamine, di-isopropylbenzene hydroperoxide/ferrous sulfate redox initiation system, more preferably ammonium persulphate/sodium bisulfite, Potassium Persulphate/sodium bisulfite, Sodium Persulfate/sodium bisulfite, Potassium Persulphate/S-WAT and di-isopropylbenzene hydroperoxide/ferrous sulfate redox initiation system.Oxygenant and reductive agent mass ratio are 2～10: 1 in the redox initiator that is adopted.
When adopting oil-soluble initiator, preferably earlier oil-soluble initiator is dissolved in the emulsifier solution, emulsifier solution and initiator mass ratio are 60～70: 1, described emulsifying agent is one or more in the anionic emulsifier; If water soluble starter preferably is dissolved in the deionized water, deionized water and initiator mass ratio are 60～70: 1.Anionic emulsifier is that those of ordinary skills are known, for example metal carboxylate emulsifying agent or Sulfates emulsifying agent.
The present invention's advantage compared to existing technology is: directly adopt the method for chemical situ-formed graft hydridization to prepare rubber/silicon compound matrix material, organosilane monomer is grafted on the latex, organosilane monomer is dispersed in the rubber matrix with chemical bond or nano-scale, interface between organic rubber phase and silicon compound is tightr with bonded like this, easy agglomeration of silicon dioxide granule and white carbon black pollution problems in the direct mixing method have been avoided, and the phenomenon that needs greater energy consumption, also avoided simultaneously between the rubber/silicon compound matrix material of sol-gel method preparation the interface in conjunction with untight phenomenon.
This method is directly carried out graft copolymerization with unsaturated organosilicon oxygen alkane and rubber and is obtained organosilicon grafted and modified rubber, only need a spot of unsaturated organosilicon oxygen alkane just can make the tensile strength of rubber improve 20%～25%, and the mooney viscosity of silicon modified rubber rubber is not compared with former rubber significantly to be increased, and the utilization ratio of organosilane can reach 87%～95%; The SEM test result shows and does not occur oarse-grained silicon dioxide granule in the modified adhesive material, illustrates that organosilicon does not have a large amount of hydrolysis in emulsion; The thermotolerance of rubber has also had raising to a certain extent simultaneously.
Description of drawings
Fig. 1 does not adopt the infrared spectrum of SBR1500 after the SBR1500 of silicon modification and the embodiment 1 silicon in-situ hybridization modification, and wherein: 1-does not adopt the SBR1500 of silicon modification, the SBR1500 after the 2-embodiment 1 silicon in-situ hybridization modification; At 1050cm
-1And 1137cm
-1The place, strong peak, 1050cm have appearred in SBR1500 after the modification of silicon in-situ hybridization
-1Be the feature stretching vibration peak of Si-O key, 1137cm
-1Be the feature stretching vibration peak of Si-O-C key, illustrate that unsaturated organosilicon oxygen alkane successfully grafts in the styrene butadiene rubber latex, and original position generates siloxane bond in styrene-butadiene rubber(SBR), this is the key point of the increase of rubbery intensity.
Fig. 2 does not adopt the SBR1500 of silicon modification and the ash content infrared spectrum of embodiment 1 silicon in-situ hybridization modification SBR1500, and wherein: 1-does not adopt the SBR1500 of silicon modification, the SBR1500 after the 2-embodiment 1 silicon in-situ hybridization modification.Ash content is at 1050cm behind the silicon in-situ hybridization modification SBR1500 rubber
-1Has SiO
2Typical characteristic infrared absorption, illustrate that equally unsaturated organosilicon oxygen alkane graft modification styrene butadiene rubber latex is successful.
Fig. 3 does not adopt the weightless temperature curve of SBR1500 after the SBR1500 of silicon modification and the embodiment 1 silicon in-situ hybridization modification, and wherein: 1-does not adopt the SBR1500 of silicon modification, the SBR1500 after the 2-embodiment 1 silicon in-situ hybridization modification.T among Fig. 3
DcBe the fastest temperature section of thermal weight loss, it has embodied the thermotolerance of material.As seen from Figure 3, grafting unsaturated organosilicon oxygen alkane meets the T that can make rubber
DcImprove, this explanation latex grafting unsaturated organosilicon monomer can make the thermotolerance of material improve.
Embodiment
For effect of the present invention is described, enumerate embodiment the present invention is described in further detail, but the present invention is not limited in these embodiment.
1, analytical procedure:
The mensuration of mooney viscosity: shear the mensuration that viscometer is measured the part 1 mooney viscosity with disk according to GB/T 1232.1-2000 unvulcanized rubber.
The rubber performance test methods: rubber is after open refining glue (moulding) machine is at room temperature mixing with X (S) K-160 type (Shanghai rubber manufacturing machinery one factory), at 45 ℃, and 150kgf/cm
2Temperature and pressure under, be pressed into the thick thin slice of about 2mm with 45 tons of vulcanizing presses of G53-445D type, take out behind the 30min, owing to there is not the sulfurized rubber that the ability that can recover deformation is arranged, so the rubber that presses is discharged about 24h under certain weight, be cut into standard mechanics sample by standard dumbbell shape cut-off knife then, adopt the CMT5104 type microcomputer control electronics tension testing machine of Shenzhen Sans Material Detection Co., Ltd to carry out the mensuration of tensile strength at last, instrument parameter is 500mm/min.
Infrared testing method: the SBR latex after the modification, after cohesion, contain the homopolymer of some organo-siloxanes, the product and the responseless organo-siloxane monomer of a small amount of hydrolysis of organo-siloxane, adopt Soxhlet to extract and remove these products, with acetone as extraction agent, Soxhlet is extracted 24h, remove unreacted monomer and organo-siloxane auto-polymerization and from the product of hydrolysis, and the SBR of SBR and graft modification is insoluble to acetone.The SBR after will extracting through Soxhlet respectively and the SBR sample of modification dissolve with toluene, are added drop-wise to then on the KBr sheet, KBr is placed on to dry under the ultraviolet lamp removes toluene 30min, test then.Simultaneously with rubber in retort furnace, after the residuum that 800 ℃ of following calcination 10h obtain is washed with 5% dilute hydrochloric acid, adopt the infrared spectra of KBr pressed disc method testing rubber ash content behind the dry 2h.
The stable on heating analysis of rubber: adopt SDTQ600 (the being Simultaneous DSC-TGA) thermal analyzer of the U.S. TA company sample to be carried out thermogravimetric analysis, test condition: 20 ℃-800 ℃ of temperature, 20 ℃/min of temperature rise, nitrogen flow 100ml/min.
2, raw material sources:
Styrene-butadiene rubber(SBR) (SBR1500) latex: the CNPC Lanzhou Petrochemical is produced, divinyl 77.5% (wt) wherein, mooney viscosity 56;
Polybutadiene rubber (EBR) latex: the CNPC Lanzhou Petrochemical is produced, cis-1, and 4-configuration content is 10%～20%, anti-form-1,4-configuration content 58%～75%, 1,2-configuration content be less than 25%, mooney viscosity 99.
Paracril (N32) latex: the CNPC Lanzhou Petrochemical is produced, divinyl 66.5% (wt) wherein, mooney viscosity 45.
Chloroprene rubber (CR244) latex: the long-lived chemical industry in Chongqing company limited produces, divinyl 50% (wt) wherein, mooney viscosity 70.
Natural rubber (NR) latex, Yunnan natural rubber industry limited-liability company, mooney viscosity 66.
To contain the dried glue SBR1500 of 50g latex, 8gVTES joins in the four-hole boiling flask, fully mix, be warming up to 68 ℃, drip RA rosin acid (concentration the is 22%) mixing solutions of 0.1g benzoyl peroxide and 50g then, reaction is 350 minutes under agitation condition; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 90.4%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 238.8kpa has improved 21.7% after the modification, and mooney viscosity 62.9 has only improved 12.7%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
To contain the dried glue SBR1500 of 45g latex, 2.5gMPTS joins in the four-hole boiling flask, fully mixes, and is warming up to 65 ℃, adds the 0.13g benzoyl peroxide then, under agitation condition the reaction 420 minutes; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.0%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 236.9kpa has improved 20.7% after the modification, and mooney viscosity 61.2 has only improved 9.7%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 3
To contain the dried glue SBR1500 of 56g latex, 12gVTMS joins in the four-hole boiling flask, fully mixes, and is cooled to 8 ℃, adds 0.15g di-isopropylbenzene hydroperoxide and 0.015g ferrous sulfate then, under agitation condition the reaction 400 minutes; Reaction finishes emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 92.0%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 241.6kpa has improved 23.1% after the modification, and mooney viscosity 64.4 has improved 15.5%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 4
To contain the dried glue SBR1500 of 52g latex, 13gVTES joins in the four-hole boiling flask, fully mixes, and is warming up to 80 ℃, adds the 0.15g ammonium persulphate, reaction is 350 minutes under agitation condition; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 94.3%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 251.1kpa has improved 28.0% after the modification, and mooney viscosity 66 has only improved 17.8%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 5
To contain the dried glue SBR1500 of 48g latex, 10gVTES joins in the four-hole boiling flask, fully mixes, and is warming up to 85 ℃, adds the mixing solutions of 0.12g Potassium Persulphate and 8g deionized water, reaction is 360 minutes under agitation condition; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 92.9%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 245.2kpa has improved 25.0% after the modification, and mooney viscosity 65.7 has only improved 17.7%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 6
To contain the dried glue SBR1500 of 60g latex, 12gVTES joins in the four-hole boiling flask, fully mixes, and is warming up to 50 ℃, adds 0.15g Potassium Persulphate and 0.03g sodium bisulfite, reaction is 360 minutes under agitation condition; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 93.6%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), and rubber tensile strength 251.1kpa has improved 28.0% after the modification, and mooney viscosity 66.2 has only improved 18.3%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 7
To contain dried glue latex of 50gEBR and 5gMPTS and be added in the four-hole boiling flask, and fully mix, and be warming up to 80 ℃ then, adding 0.10g Potassium Persulphate stirs, and reaction 350min after reaction finishes lowers the temperature system, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.0% to be compared with crude rubber Mooney viscosity (99) with unmodified tensile strength (210kpa), and rubber tensile strength 260kpa has improved 23.8% after the modification, and mooney viscosity 112.9 improves 14.3%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 8
To contain the dried glue paracril of 50g latex, 4gVTES joins in the four-hole boiling flask, fully mixes, normal temperature (25 ℃) adds 0.10g hydrogen peroxide and 0.05g ferrous sulfate, reaction is 360 minutes under agitation condition; After reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 89.3%, compares with mooney viscosity (45) with unmodified rubber tensile strength (201.3kpa), and rubber tensile strength 242.3kpa has improved 20.3% after the modification, and mooney viscosity 51 has only improved 13.3%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
Embodiment 9
To contain the dried glue chloroprene rubber of 52g latex, 7.8gVTES joins in the four-hole boiling flask, fully mix, be warming up to 58 ℃, add 0.12g Potassium Persulphate and 0.025g sodium bisulfite, reaction is 360 minutes under agitation condition, after reaction finishes system is lowered the temperature, then with emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.4%, compares with mooney viscosity (70) with unmodified rubber tensile strength (284.6kpa), and rubber tensile strength 345.7kpa has improved 21.5% after the modification, and mooney viscosity 82 has only improved 17.1%.Oarse-grained silicon dioxide granule does not appear in the SEM test shows modification sizing material.
To contain in the dried glue NR of 50g latex, the 6gVTES adding four-hole boiling flask, and fully mix, and be warming up to 72 ℃, and add the 0.18g benzoyl peroxide then, reaction is 380 minutes under agitation condition; Then emulsion breaking is condensed, mixing vacuum-drying, after tested, the utilization ratio of VTES can reach 89%, compare with mooney viscosity (66) with the rubber tensile strength (981.0kpa) that does not have modification, rubber tensile strength 1180.7kpa after the modification provides high 20.4%, mooney viscosity brings up to 79, has improved 19.7%.
Comparative Examples 1
The styrene-butadiene rubber(SBR) (method is with reference to CN96107364.0) of mechanical blending legal system prepared silicon dioxide modification
Obtained silica modified styrene-butadiene rubber(SBR) by two-step approach, the one: wet processing silicon-dioxide, take by weighing 3.55g aerosil and 1.21gVTES, with toluene (120ml) is solvent, back flow reaction 24h, it is stand-by to remove the silicon-dioxide that obtains handling behind the solvent, the 2nd, with the silicon-dioxide 3.00g after handling (in silica volume, identical with theoretical silicone content among the embodiment) obtain the mixing enhancing modified of silicon-dioxide after the dried glue of 96.46gSBR1500 is mixing, compare with pure SBR1500, the tensile strength 210.3kpa of rubber after the modification only improves 7.2%.And in embodiment 1, under the condition that theoretical silicone content is the same in the rubber, modified rubber back draft intensity can improve 21.7%.
Claims (14)
1. a silicon situ-formed graft hybrid modification contains the method for poly-conjugated-diolefin latex, it is characterized in that: the dry glue quality in the latex that contains poly-conjugated-diolefin is 100 parts, the organo-siloxane monomer that will contain unsaturated link(age) joins in the latex that contains poly-conjugated-diolefin for 4～25 parts, fully mix, under 5～85 ℃ of temperature and agitation condition, add initiator and carry out graft polymerization reaction 5～8h for 0.20～0.36 part, at last with the emulsion condensation drying of graft modification; The organosilane monomer structural formula that contains unsaturated link(age) is:
Y-contains the unsaturated aliphatic segment of 2～18 carbon;
R
1-contain the aryloxy of the alkoxyl group of 1～12 carbon, 6～12 carbon or the siloxy of 3～12 carbon;
R
2-contain the aryloxy of the alkoxyl group of 1～12 carbon, 6～12 carbon, the siloxy of 3～12 carbon; The saturated segment of 1～20 carbon, the cyclic alkane or the aromatic hydrocarbon of 1～8 carbon;
R
3-contain the aryloxy of the alkoxyl group of 1～12 carbon, 6～12 carbon, the siloxy of 3～12 carbon; The saturated segment of 1～20 carbon, the cyclic alkane or the aromatic hydrocarbon of 1～8 carbon.
2. method according to claim 1, the latex that it is characterized in that containing poly-conjugated-diolefin is homopolymer or the multipolymer that contains the conjugated diolefine hydrocarbon compound, is 100% in homopolymer or copolymer quality, the conjugated diolefine hydrocarbon content is 50%～100%.
3. method according to claim 2 is characterized in that containing that the conjugated diolefine hydrocarbon content is 60%～80% in the latex of poly-conjugated-diolefin.
4. method according to claim 1, the organo-siloxane monomer that it is characterized in that containing unsaturated link(age) is 10～15 parts.
5. method according to claim 1 is characterized in that containing that Y is vinyl, propenyl, allyl group, sec.-propyl, pseudoallyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, ethynyl, 1-proyl, ethyl acetylene base, 1-pentynyl, 1-heptyne base, methacryloxypropyl or methacryloxy in the organo-siloxane monomer of unsaturated link(age).
6. method according to claim 1 is characterized in that containing R in the organo-siloxane monomer of unsaturated link(age)
1Be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, hexyloxy, pentyloxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group or trimethylsiloxy group.
7. method according to claim 1 is characterized in that containing that Y is vinyl or methacryloxypropyl in the organo-siloxane monomer of unsaturated link(age), R
1Be methoxyl group, oxyethyl group or isopropoxy, R
2Be methyl, ethyl, methoxy or ethoxy, R
3Be methyl, ethyl, methoxy or ethoxy.
8. method according to claim 1, the organo-siloxane monomer that it is characterized in that containing unsaturated link(age) are one or more in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributanoximo silane, methyl tributanoximo silane, vinyl silane triisopropoxide, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane, three (trimethylsiloxy group) methacryloxypropyl silane.
9. method according to claim 8, the organo-siloxane monomer that it is characterized in that containing unsaturated link(age) are one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) the methacryloxypropyl silane.
10. method according to claim 1 is characterized in that initiator is thermal decomposition initiating or redox initiator.
11. method according to claim 10 is characterized in that earlier oil-soluble initiator being dissolved in the emulsifier solution when adopting oil-soluble initiator, emulsifier solution and initiator mass ratio are 60～70: 1.
12. method according to claim 11 is characterized in that emulsifying agent is an anionic emulsifier.
13. method according to claim 10 is characterized in that earlier water soluble starter being dissolved in the deionized water when adopting water soluble starter, deionized water and initiator mass ratio are 60～70: 1.
14. method according to claim 10 is characterized in that oxygenant and reductive agent mass ratio are 2～10: 1 in the redox initiator.
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