CN109384926A - A kind of unsaturated ring oxidation polysiloxanes and its preparation method and application - Google Patents
A kind of unsaturated ring oxidation polysiloxanes and its preparation method and application Download PDFInfo
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- CN109384926A CN109384926A CN201710655345.4A CN201710655345A CN109384926A CN 109384926 A CN109384926 A CN 109384926A CN 201710655345 A CN201710655345 A CN 201710655345A CN 109384926 A CN109384926 A CN 109384926A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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Abstract
The present invention relates to a kind of unsaturated ring oxidation polysiloxanes and preparation method thereof and application, the polysiloxanes to be modified to Polybutadiene-styrene active lithium polymer.Unsaturated ring oxidation polysiloxanes provided by the present invention contains unsaturated double-bond and has multiple epoxy groups of greater activity, not active si-h bond, epoxy group and styrene butadiene random copolymer end active lithium efficiently can be subjected to coupling or end capping reaction, obtain a kind of multiple functionalized solution polymerized butadiene styrene rubber, this multiple functionalized SSBR raw rubber is used as meridian half steel tire tread glue, its tyre surface vulcanizate has lower dynamic heat, while rolling resistance rate of descent is up to 28% or more.Unsaturated ring of the invention aoxidizes polysiloxanes preparation method, whether the ammonia esterification of silicon-addition reaction of hydrogen or remaining silicon-hydrogen and isocyanates, belongs to that homogeneous reaction, preparation method are simple, react easily controllable, are easy to industrialize.
Description
Technical field
The invention belongs to the modified preparation fields of epoxidation organic silicone oil, and in particular to a kind of poly- silicon oxygen of unsaturated ring oxidation
Alkane and preparation method thereof and preparation is modified to the random active lithium polymer of Polybutadiene-styrene using the polysiloxanes
Multiple functionalized SSBR.
Background technique
Functionalization SSBR is usually to be obtained by that will be reacted with the butadiene-styrene random copolymer of active lithium,
If 287 020A of JP2009 is described in the presence of double tetrahydro chaff propane and butyl lithium, butadiene and styrene are placed in ring
It polymerize in hexane, with 3-N, bis- (trimethylsilyl) aminopropyl (methyl) diethoxy silanes of N- are modified
Rubber, such method belong to coupling type, and polarity nitrogen-atoms is also in the interlude of polymer.Such as David F.Lawson,
It describes and adopts in the US5616704A Solubilized cnionic polymerization such as Uniontown inttiators
Secondary-amine compound is used to react the initiator for generating secondary amine lithium as styrene and polymerizing butadiene with butyl lithium, finally with three
Alkyl monochlor(in)ate tin or 4,4 "-bis (diethylamino) benzophenone or other N, N "-dialkyl group-amido-alkyl
Ketone or aldehyde compound or N, N "-dialkyl group-amido-alkyl alkenes substance synthesize SSBR to terminate polymerization reaction.?
Carlo kanz, Mamer (LU) etc. describe to close using amine-containing silication in US2012/0123018A1 to be drawn to be coupled butyl lithium
The polymer of the butadiene-styrene of hair, this kind of coupling agent have a N, the bis- trimethyl silicon substrates of N--amido trimethylene-triethoxysilane,
N, N- bis- trimethyl silicon substrates-amido ethylene-triethoxysilane, N, the bis- trimethyl silicon substrates of N--amido trimethylene-methyl dimethoxy oxygroup
Silane, N, classes compound such as the bis- trimethyl silicon substrates of N--amido trimethylene-methyl dimethoxysilane etc..I.e. by oxygen, nitrogen, silicon, sulphur,
The former molecular group such as organotin is introduced into SSBR molecule the rubber material for preparing functionalization.
Functional solution polymerized butadiene styrene rubber also has using organic siloxane modified SSBR, as Trinseo is novel multiple functionalized
SPRINTANTM SLR4633-Schkopau、SPRINTANTMSLR4630-Schkopau, Asahi Kasei Corporation produce HPR-
850 series of products etc., above-mentioned this kind of product are made compared with the universal SSBR VSL-5025 series of products that Lang Sheng company produces
At the rolling resistance of radial make moderate progress, however its improved limited extent.
Existing silicone oligomer or polysiloxane, with methyl-silicone oil and ethyl silicon oil (also referred to as poly- silicon in commodity
Oxygen alkane oligomer) be it is common, vinyl silicone oil is divided into low vinyl silicone oil and high-vinyl silicone oil, and vinyl silicone oil mainly has end
Vinyldimethicone and end-vinyl Polymethyl methacrylate, there is the quotient of different viscosities and contents of ethylene
Product, are add-on type liquid silicon rubber, silicon gel, the modifying agent of mixing rubber, plastic additive and are used for tire reinforcing material
Material etc..
Commonly use oligomeric alkylsiloxane because of no epoxy group or not can with the active group in conjunction with Organoalkyl lithium, so nothing
Polysiloxanes is connected in styrene-butadiene copolymer (SSBR) molecule by method with chemical bond.If by highly polarization
Epoxidation polysiloxanes chain link introduce SSBR strand middle-end or end, the polysiloxane-modified SSBR of this epoxidation with it is white
The tread rubber of radial made of the material matings such as carbon black meets " Payne " principle, in modified SSBR it is highly polar compared with
Long chain polysiloxanes has and White Carbon black mixed refining process and dispersion performance be good, low temperature resistant, cyclic deformation dynamic loss
The features such as small, resistance to ozone is not available for universal SSBR.
Epoxidation polysiloxanes has the unsaturated type in saturation type and strand containing unsaturated double-bond；Such as commercially available saturation
Type ring oxidized organosilicon oil man's name of an article has IOTA-105 series of products, for example, formula (I) is 105-1 type, formula (II) be 105-2 type,
Formula (III) is 105-3 type；
The usual degree of polymerization is 200-300；Viscosity is 1000-60000mpa.s, and it is incomplete also to contain part in molecular structure
The activated silica hydrogen of conversion.
Epoxidation polysiloxanes in above-mentioned formula (I~III) is saturation type, is mainly used for printing and dyeing assistant and epoxy resin
Toughener.
In " Tianjin Polytechnic University's journal ", 2012,31 (1): synthesis [J] text for 61-64 allyl alcohol polyether modified silicon oil
In describe using chloroplatinic acid as catalyst, control reaction temperature and reaction time, constant pressure titration is low hydrogeneous into allyl alcohol polyether
Polyetherpolysilicone is made in silicone oil, is 1: 1.2 in allyl alcohol polyether and silicon oil of low hydrogen content molar feed ratio；Catalyst amount is
33μg/g；Reaction temperature is 110 DEG C；Under the conditions of reaction time is 8h etc., silicon oil of low hydrogen content conversion ratio is had studied less than 88%.
Zhang Zhaogui professor with low hydrogen silicone oil and allyl glycidyl ether in the research for preparing epoxidation silicon oil, low
Hydrogen silicone oil/allyl glycidyl ether is 1:1.25 (mol), under conditions of the addition reaction time reaches 5-6h, low hydrogen silicone oil
Conversion ratio less than 85%.Still have 15% in the product containing epoxy group i.e. after low hydrogen silicone oil and allyl glycidyl ether addition
Silicon hydrogen, this silicon hydrogen activity is high, easily with active lithium occur terminate react, cause the amount of activated lithium in polymerization system to lose
It is living, it cannot be all connected with silicone oligomer with chemical bond, coupling efficiency substantially reduces, and partially loses chemical modification SSBR
Purpose.
Simultaneously because the epoxy polysiloxane of saturation type structure is used as coupling or terminated polystyrene-butadiene copolymer is living
Property lithium when, wet steam etc. reason also results in Polystyrene-Butadiene Copolymer activity lithium inactivation and terminates when because of polymerization, or
Say it is that excessive epoxy polysiloxane can be free in polymer, because of highly polar epoxy polysiloxane and low polar polyphenyl second
Alkene-butadiene copolymer poor compatibility, the free epoxy polysiloxane in polymer raw rubber or product can be migrated from polymer
Out, the tire product especially made will appear " bloom " phenomenon, influence the appearance and physical property of product.
Insatiable hunger type epoxidation silicon oil usually carries out silicon-hydrogen by unsaturated silicon oil of low hydrogen content and double bond containing epoxide
Addition reaction synthesizes, such as unsaturated silicon oil of low hydrogen content has the vinyl double seal head containing hydrogen silicone oil of structural formula (1), formula
(2) the trade name vinyl norbornene hydridization that the silicone oil of structure is produced by Shanghai Ji Laide new material Science and Technology Ltd. contains
Hydrogen silicone oil etc..
Wherein, R is methyl or ethyl.
Wherein, R ' is vinyl norbornene base, and R is methyl or ethyl.
Epoxidation polysiloxanes containing unsaturated double-bond, by the unsaturated low hydrogen silicone oil and 1 in above-mentioned formula (1) or formula (2),
The epoxide containing unsaturated double-bond such as 2- epoxy -4- vinyl thiacyclohexane or allyl glycidyl ether carries out silicon-hydrogen and adds
It is completed at reaction.However in the epoxidation polysiloxanes for preparing unsaturated double-bond, equally exists silicon hydrogen conversion ratio deficiency, deposits
A large amount of activated silica hydrogen the problem of.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of unsaturated epoxies without activated silica hydrogen
Change polysiloxanes and its preparation method and application.Unsaturated ring oxidation polysiloxanes is applied to coupling SSBR end active
After lithium, then use multiple functionalized SSBR production meridian half steel tire tread vulcanizate and universal SSBR phase after coupling
Lower than dynamic heat build up, rolling resistance rate of descent reaches 28% or more.
A kind of unsaturated ring of the present invention aoxidizes polysiloxanes, and viscosity is 10000~60000mPas, and vinyl is
0.20~1.0mol%, epoxide number are 0.01~0.30mol/100g, have the structure of formula A:
Wherein, m=100~300, b=1~10；B≤5.6a, R1For in vinyl or vinyl norbornene base extremely
Few one kind, R2For at least one of methyl, ethyl, vinyl；R3For the group containing epoxy group, R4For the base containing imide
Group, wherein the carbon in acyl group is connected with silicon, and the content of silicon hydrogen is 0 in structure.
Preferably, the substituent R3Selected from one of formula a or formula b:
Preferably, the substituent R4Selected from formula c:
Wherein R5It is a kind of in alkyl composed by the hydrocarbon chain link that is made of C1~C10 or aromatic radical or naphthene group.
As a further preference, the substituent R4Selected from one of formula d, formula e, formula f:
Preferably, unsaturated ring aoxidizes polysiloxanes, viscosity 15000-60000mPas, vinyl in the present invention
For 0.20~1.0mol%, epoxide number is 0.015~0.25mol/100g.
A kind of preparation method of unsaturated ring oxidation polysiloxanes of the present invention, comprising the following steps:
Step 1: the preparation of the epoxidation polysiloxanes of unsaturated siliceous-hydrogen
Unsaturated hydrogen containing siloxane is dissolved in organic solvent, platinum catalyst is added, under inert gas protection, control
50~90 DEG C of temperature, unsaturated epoxy compound is added dropwise, after having reacted, is washed, water phase and then distillation is divided to mention at room temperature
It is pure, that is, obtain the epoxidation polysiloxanes of unsaturated siliceous-hydrogen；
Step 2: the preparation of unsaturated ring oxidation polysiloxanes
By the resulting unsaturation of step 1 it is siliceous-the epoxidation polysiloxanes of hydrogen is dissolved in organic solvent, in inert gas
Under protection, controlled at 75-85 DEG C, the compound containing isocyano is added, after reacting 8h or more, distilation obtains
Unsaturated ring aoxidize polysiloxanes, the additional amount of the compound containing isocyano according to the molar ratio, obtained in step 1
Remaining active hydrogen in the epoxidation polysiloxane molecule of unsaturated siliceous-hydrogen: isocyano 1: 1.05~1.10.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the hydrogeneous poly- silicon of unsaturation
Oxygen alkane, viscosity be 10000~60000mPas, vinyl be 0.20~1.0mol%, hydrogen content be 0.02~
0.10mol% has following general formula (I):
Wherein m=100~300, n=1~10, R1For at least one of vinyl or vinyl norbornene base, R2For
At least one of methyl, ethyl, vinyl.
As a further preference, the unsaturated hydrogen containing siloxane, is selected from end-vinyl poly dimethyl Silicon Containing Hydrogen oxygen
The poly- methyl ethylene hydrogen-containing siloxane of alkane, end-vinyl, the poly- diethyl hydrogen-containing siloxane of end-vinyl, end-vinyl polyvinyl
One of hydrogen-containing siloxane and vinyl norbornene hydridization hydrogen-containing siloxane.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the organic solvent is toluene,
The toluene is before using first through Non-aqueous processing.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the platinum catalyst is chlorine platinum
Acid, the chloroplatinic acid additional amount are counted in mass ratio, chloroplatinic acid: unsaturated hydrogen containing siloxane is 2~5:100000；The chlorine
Platinic acid is diluted in toluene and uses.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the unsaturation epoxy compound
Object is the epoxide containing vinyl, and according to the molar ratio, unsaturation contains the additional amount of the epoxide containing vinyl
Silicon-hydrogen in hydrogen polysiloxanes: the vinyl in the epoxide containing vinyl is 1: 1.10~1.25.As further
It is preferred that the unsaturated epoxy compound is one of 1,2- epoxy -4- vinyl thiacyclohexane, allyl glycidyl ether.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the reaction temperature is 50-
85 DEG C, the reaction time is 5.5~8h.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, gained unsaturation is siliceous-hydrogen
Epoxidation viscosity of polysiloxane be 10000~60000mPas, vinyl be 0.20~1.0mol%, epoxide number 0.01
~0.3mol/100g.As further preferred, gained unsaturation is siliceous-and the epoxidation viscosity of polysiloxane of hydrogen is 10000~
60000mPas, vinyl are 0.20~1.0mol%, and epoxide number is 0.01~0.20mol/100g.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, gained unsaturation is siliceous-hydrogen
Epoxidation polysiloxanes, remaining active hydrogen content be 3~15mmol%.Remaining active hydrogen refers to the ring of unsaturated siliceous-hydrogen
The hydrogen in polysiloxanes in silicon-hydrogen bond is aoxidized, the hydrogen in the silicon-hydrogen bond of addition reaction is had neither part nor lot in step 1.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1, the epoxy compound containing vinyl
Shown in object and unsaturated hydrogen containing siloxane silicon hydrogenation process such as formula (m), wherein containing the epoxidation of vinyl in reaction equation
Object is closed to show using allyl glycidyl ether as representative:
Wherein, m=100~300；B=1~10；B≤5.6a,
R1For at least one of vinyl or vinyl norbornene base, R2For at least one in methyl, ethyl, vinyl
Kind.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 2, the change containing isocyano
Close object be TDI, MDI and the hydrocarbon chain link that is made of C1~C10 composed by alkyl or aromatic radical or naphthene group Dan Yi
One of cyanate.As a further preference, the compound containing isocyano is the hydrocarbon chain link of C1~C10 composition
One of composed alkyl or the monoisocyanates of aromatic radical or naphthene group.As it is further preferably, it is described to contain
The compound of isocyano is one of cyclohexyl isocyanate, isopropyl isocyanate, n-butyl isocyanate.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 2, the organic solvent is toluene
Or one of dimethylbenzene, the toluene or dimethylbenzene are preceding first through Non-aqueous processing in use.In the actual operation process, by insatiable hunger
After being dissolved in the organic solvent that Non-aqueous processing is crossed with the epoxidation polysiloxanes of siliceous-hydrogen, azeotropic is first used at 115~-120 DEG C
Evaporation further removes moisture.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 2, the reaction time is 8-
10h.Remaining active silicon-hydrogen can be thoroughly converted into ammonia ester bond within the reaction time.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 1 and step 2, the indifferent gas
Body is nitrogen.
A kind of preparation method of present invention unsaturated ring oxidation polysiloxanes, in step 2, the epoxy of unsaturated siliceous-hydrogen
Shown in the reaction process such as formula (n) for changing polysiloxanes and isocyanate ester compound, wherein the isocyanates in reaction equation
Object is closed using isopropyl isocyanate as displaying is represented, the epoxidation polysiloxanes of unsaturated siliceous-hydrogen is with formula m products therefrom work
It is shown to represent:
Wherein, m=100~300；B=1~10；b≧5.6a.
R1For at least one of vinyl or vinyl norbornene base, R2For in methyl, ethyl, vinyl at least
It is a kind of.
The present invention also attempted other a large amount of substances for closing silicon hydrogen, but effect obtained is all not as good as of the invention
Isocyanates.
A kind of application of unsaturated ring oxidation polysiloxanes of the present invention, unsaturated ring oxidation polysiloxanes of the invention is used
After being coupled SSBR end active lithium, then using the meridian half steel tire tread vulcanizate produced of the SSBR after coupling and lead to
Low with the year-on-year dynamic heat build up of type SSBR, rolling resistance rate of descent reaches 28%.
Unsaturated ring oxidation polysiloxanes of the invention with anionic polymerisation system butadiene-styrene copolymer end
The coupling reaction of active lithium (BS-Li) is carried out by process conditions well known to lithium series of polymer, shown in reaction process such as formula (p),
Unsaturated ring is aoxidized polysiloxanes and is shown using formula n products therefrom as representative:
Wherein, m=100~300；B=1~10；b≧5.6a；B >=c,
R1For at least one of vinyl or vinyl norbornene base, R2For in methyl, ethyl, vinyl at least
It is a kind of.
The principle of the present invention and advantage:
The epoxidation polysiloxanes chain link of highly polarization is introduced to middle-end or the end of SSBR strand, this epoxidation is poly-
The tread rubber of radial made of the material matings such as silicone-modified multiple functionalized SSBR and White Carbon black meets
" Payne " principle, in modified SSBR highly polar relatively long chain polysiloxanes have with White Carbon black mixed refining process and point
Dissipate the features such as performance is good, and vulcanizate is low temperature resistant, the small rolling resistance of cyclic deformation dynamic loss is low.
However due to polysilane it is epoxidised during inevitable remaining si-h bond, and it is remaining in epoxy polysiloxane
Silicon-hydrogen bond have to the end active lithium of butadiene-styrene polymer and terminate effect, can seriously reduce polybutadiene-benzene
The sealing end or coupling efficiency of ethylene atactic copolymer such as solution polymerized butadiene styrene rubber (SSBR), molecule after causing active lithium polymer to terminate
The polysiloxanes chain link being connected in chain without chemical bond, is not achieved the purpose of chemical modification end active lighium polymer.
For these reasons, inventor is obtained using unsaturated hydrogen containing siloxane with the epoxide containing vinyl first
The epoxidation polysiloxanes of unsaturated siliceous-hydrogen is obtained, then finds the group easily with active hydrogen reaction, closing " is passivated " in other words
Remaining active silicon-hydrogen can be converted into ammonia ester bond using isocyanates completely, obtained entirely without work by silicon hydrogen, finally discovery
Property silicon hydrogen unsaturated ring aoxidize polysiloxanes, and slightly excessive isocyanates belong in system it is micro need not react it is molten
It is removed in liquid, the wet steam of micro isocyanates energy hydrolysis liquid during storage can also carry out active lithium polymer
Sealing end.
Inventor has surprisingly been found that, even if using unsaturated ring oxidation of the invention without silicon hydrogen polysiloxanes as activity
Dosage is excessive when the coupling reaction of SSBR, and excessive epoxidation polysiloxanes can be free in polymer raw rubber, is free on raw rubber
Middle unsaturated ring oxidation can participate in cross-linking reaction when rubber compound vulcanizes without the double bond in silicon hydrogen polysiloxanes, be not in move
It moves, " bloom " phenomenon, i.e., it is useful and harmless to vulcanizate without silicon hydrogen polysiloxanes containing a small amount of unsaturated ring oxidation in raw rubber.
Containing unsaturated double-bond and there are the more of greater activity in the unsaturated polysiloxane molecule containing epoxy group of the invention
A epoxy group, in the unsaturated polysiloxane molecule containing epoxy group micro remaining silicon-hydrogen and isocyanate ester compound into
The inertia group that is formed cannot participate in the termination reaction of the polymer of active lithium after row addition closing, can efficiently by epoxy group with
Styrene-butadiene copolymer end active lithium carries out coupling or end capping reaction, without other during coupling and end capping reaction
Side reaction, coupling efficiency or ending ratio are close to 100%.
Unsaturated ring of the invention is aoxidized without silicon hydrogen polysiloxanes, can be substantially reduced SSBR long-chain molecule inert terminal and be existed
" Payne " effect generated under effects of strain reduces dynamic heat build up, can reduce the rolling resistance of tire to large extent, meet
The developing direction of current tire industry, is the ideal material for manufacturing safe, comfortable, energy-efficient green tire.
Unsaturated ring oxidation of the invention is without silicon hydrogen polysiloxanes preparation method, whether silicon-addition reaction of hydrogen or residual
The ammonia esterification of remaining silicon-hydrogen and isocyanates, it is simple to belong to homogeneous reaction, preparation method, can use it is existing at
Ripe technique synthesizes, and reacts easily controllable, is easy to industrialize.
Detailed description of the invention:
Attached drawing 1 is the unsaturated epoxy dimethyl silicone polymer that isopropyl cyanate radical urethane prepared by embodiment 1 is crossed
Infrared spectrogram.
Upper figure is the unsaturated epoxy crossed of isopropyl cyanate radical urethane prepared by the embodiment of the present invention 1 in 1 in attached drawing
Change the infrared spectrogram of dimethyl silicone polymer；The following figure is the infrared spectrogram of polymethyl siloxane.In figure, 1130-
1000cm-1For Si-O-Si functional group absorption peak, 1275-1245cm-1And 865-750cm-1For Si-CH3Absorption peak, 3050cm-1
Place is the stretching vibration peak of epoxy group C-H, 2280-2080cm-1Locate the characteristic absorption peak of not Si-H, 910cm-1Locate no Si-
The bending vibration absorption peak of H shows that Si-H has disappeared when Si-H carries out addition.
Specific embodiment
The present invention is illustrated with following embodiment, does not constitute the limitation to the scope of the invention or implementation method.Using
Long Shi nitrogen device is determined the hydrogen content in silicon-hydrogen in the unsaturated polysiloxanes containing epoxy group of synthesis, former
Reason is the volume of hydrogen to be generated by Accurate Determining, by gas using generation hydrogen is reacted in Si -- H bond and the toluene solution of sodium grain
State equation can calculate hydrogen content.
The epoxy of the epoxy group in the unsaturated polysiloxanes containing epoxy group is measured using bromination quaternary amine direct titrimetric method
Value.
Using in the polysiloxane molecule after the unsaturated isocyanates closing containing epoxy group of infra-red sepectrometry (IR) characterization
Remaining Si -- H bond.
It is even using the polysiloxanes after the unsaturated isocyanates closing containing epoxy group of gel permeation chromatograph (GPC) measurement
Close the coupling degree and molecular mass of lithium system diene copolymer.
Using the dynamic heat build up and rolling resistance of POLYSAR company DUNLOP power loss instrument measurement vulcanizate.
Embodiment 1
The anhydrous end-vinyl poly dimethyl hydrogen-containing siloxane (viscosity of 100g is added in dried 500mL four-hole boiling flask
For 15000mPas, vinyl 0.56mol%, hydrogen content 0.02%), the dried dry toluene 100mL of molecular sieve,
It is passed through high pure nitrogen and reaction system is driven away and protected to air in bottle, 0.1wt% chloroplatinic acid toluene solution 2.5mL, control is added dropwise
Temperature is at 50 DEG C, then 2.9g allyl glycidyl ether is added in separatory funnel in 1h and is instilled in reaction solution, in the temperature
It is stirred to react 5.5h under degree, after reaction, after adding 100mL deionized water progress washed reaction solution 15min, then exists
Divide water phase, then vacuum removal low-boiling-point substance, solvent and unreacted allyl glycidyl ether at about 90 DEG C at room temperature, obtains shallow
Yellow transparent liquid measures remaining active hydrogen content 3.0mmol% in product.
Then, dried dry toluene then in equipped with the four-hole boiling flask in light yellow clear product liquid is added
100mL, using the moisture content in azeotropic dehydration removing product at 115 DEG C, when temperature is down to 75 DEG C, under nitrogen protection,
Isopropyl isocyanate 0.30g is added, after keeping reaction temperature to react 9h at 75 DEG C, then the solvent removed by vacuum at about 75 DEG C
With the isopropyl isocyanate of micro residue.Finally measure the unsaturated ring oxidation poly dimethyl of isopropyl cyanate radical addition
The viscosity of siloxanes is 15200mPas, vinyl 0.54mol%, epoxide number 0.015mol/100g.
Attached drawing 1 is that the unsaturated ring that isopropyl cyanate radical urethane prepared by embodiment 1 is crossed aoxidizes polydimethylsiloxanes
The infrared spectrogram of alkane.
Embodiment 2
The poly- methyl ethylene hydrogen-containing siloxane of the anhydrous end-vinyl of 100g is added in dried 500mL four-hole boiling flask
(viscosity 18000mPas, vinyl 0.98mol%, hydrogen content 0.04mol%), the dried no water beetle of molecular sieve
Benzene 100mL, about 50 DEG C of of control temperature are added dropwise 0.1wt% chloroplatinic acid toluene solution 4.4mL, are passed through high pure nitrogen for air in bottle
Reaction system is driven away and protected, temperature is controlled and is added in separatory funnel at 65 DEG C, then by 5.3g allyl glycidyl ether in 2h
In interior instillation reaction solution, it is stirred to react 8h at such a temperature, after reaction, adds 100mL deionized water and is washed
After reaction solution 15min, then divide water phase, then vacuum removal low-boiling-point substance, solvent and unreacted at about 120 DEG C at room temperature
Allyl glycidyl ether obtains light yellow clear liquid, measures remaining active hydrogen content 6mmol% in product.
Then, dried dry toluene then in equipped with the four-hole boiling flask in light yellow clear product liquid is added
100mL, using the moisture content in azeotropic dehydration removing product at 120 DEG C, when temperature is down to 80 DEG C, under nitrogen protection,
Thiacyclohexane based isocyanate 0.9g is added, keeps after reaction temperature reacts 8h at 80 DEG C, then vacuum removal is molten at about 85 DEG C
The cyclohexyl isocyanate of agent and micro residue.Finally measure the poly- first of unsaturated epoxy that thiacyclohexane based isocyanate urethane is crossed
The viscosity of base vinylsiloxane is 18560mPas, vinyl 0.97mol%, epoxide number 0.018mol/100g.
Embodiment 3
The poly- diethyl hydrogen-containing siloxane of 100g end-vinyl is separately added into dry 500mL four-hole boiling flask, and (its viscosity is
58000mPas, vinyl 0.85mol%, hydrogen content 0.08%), the dried dry toluene 100mL of molecular sieve, lead to
Enter high pure nitrogen and reaction system is driven away and protected to air in bottle, 0.1wt% chloroplatinic acid toluene solution 4.2mL, control temperature is added dropwise
Degree is at 85 DEG C, then 1, the 2- epoxy -4- vinyl thiacyclohexane of 11g is added in separatory funnel and instills reaction solution in 1.5h
In, it is stirred to react 5.5h at such a temperature, after reaction, adds 100mL deionized water and carries out washed reaction solution 15min
Afterwards, then divide water phase, then vacuum removal low-boiling-point substance, solvent and unreacted 1 at about 150 DEG C, 2- epoxy -4- second at room temperature
Alkenyl thiacyclohexane obtains light yellow clear liquid.As a result the remaining active hydrogen content obtained in light yellow clear product liquid is
12mmol%.
Then, dried dry toluene then in equipped with the four-hole boiling flask in light yellow clear product liquid is added
100mL, using the moisture in azeotropic dehydration removing product at 120 DEG C, when temperature is down to 85 DEG C, under nitrogen protection,
Isopropyl isocyanate 1.12g is added, after keeping reaction temperature to react 9h at 85 DEG C, then the solvent removed by vacuum at about 90 DEG C
With the isopropyl isocyanate of micro residue, finally measures the unsaturated ring that end-vinyl epoxidation urethane is crossed and aoxidize poly- diethyl
Radical siloxane viscosity is 58300mPas, vinyl 0.82mol%, epoxide number 0.29mol/100g.
Embodiment 4
Associated process conditions in embodiment 1 are constant, it is merely that siloxanes is selected as vinyl norbornene hydridization to contain
Hydrogen siloxane 100g (its viscosity is 33000mPas, vinyl 0.23mol%, hydrogen content 0.06%), 0.1wt% chlorine
Platinic acid toluene solution 4.0mL, the epoxide containing vinyl are chosen to be 1,2- epoxy -4- vinyl thiacyclohexane 9.3g.As a result
Obtaining the remaining active hydrogen content in light yellow clear product liquid is 7.8mmol%.
Then above-mentioned light yellow clear product liquid is subjected to isocyano addition reaction, is merely to be added containing isocyanic acid
The compound of root is selected as cyclohexyl isocyanate, and dosage is 1.16g, and correlated condition is same to apply example 1.Finally measure cyclohexyl isocyanide
The viscosity for the vinyl norbornene hydridization epoxidation polysiloxane oligomers that acid esters urethane is crossed is 33500mPas, ethylene
Base is 0.22mol%, epoxide number 0.167mol/100g.
Embodiment 5
Associated process conditions in embodiment 2 are constant, it is merely that siloxanes is selected as end-vinyl poly dimethyl is hydrogeneous
Siloxanes 100g (viscosity 40300mPas, vinyl 0.38mol%, hydrogen content 0.04%), vinyl epoxy
It closes object and is chosen to be 1,2- epoxy -4- vinyl thiacyclohexane 6.3g, the remnants as a result obtained in light yellow clear product liquid are active
Hydrogen content is 5.5mmol%.
Then above-mentioned light yellow clear product liquid is subjected to isocyano addition reaction, is merely to be added containing isocyanic acid
The compound of root is selected as isopropyl isocyanate, and dosage is 0.57g, and correlated condition is same to apply example 2.Finally measure isopropyl isocyanide
The viscosity for polysiloxane oligomers of the end-vinyl poly dimethyl containing epoxy group that acid esters urethane is crossed is 40400mPas, second
Alkenyl is 0.38mol%, epoxide number 0.114mol/100g.
Embodiment 6
Associated process conditions in embodiment 2 are constant, it is merely that siloxanes is selected as vinyl norbornene hydridization to contain
Hydrogen polysiloxanes 100g (its viscosity is 56000mPas, vinyl 0.0.35mol%, hydrogen content 0.02%), allyl
Base glycidol ether 2.8g, as a result obtaining the remaining active hydrogen content in light yellow clear product liquid is 2.94mmol%.
Then above-mentioned light yellow clear product liquid is subjected to isocyano addition reaction, is merely to be added containing isocyanic acid
The compound of root is selected as cyclohexyl cyanate, and dosage is 0.41g, and correlated condition is same to apply example 2.Finally measure cyclohexyl isocyanic acid
The viscosity for polysiloxane oligomers of the vinyl norbornene hydridization containing epoxy group that ester urethane is crossed is 56400mPas, second
Alkenyl is 0.33mol%, epoxide number 0.023mol/100g.
Embodiment 7
Associated process conditions in embodiment 2 are constant, and the siloxanes of selection is end-vinyl poly dimethyl Silicon Containing Hydrogen oxygen
Alkane 100g (viscosity 57000mPas, vinyl 0.91mol%, hydrogen content 0.087%), allyl glycidyl ether
10.4g, as a result obtaining the remaining active hydrogen content in light yellow clear product liquid is 12.18mmol%.
Then above-mentioned light yellow clear product liquid is subjected to isocyano addition reaction, the change of the isocyano of selection
It closes object and is selected as cyclohexyl cyanate, and dosage is 1.64g, correlated condition is same to apply example 2.Finally measure cyclohexyl isocyanate urethane
The viscosity for polysiloxane oligomers of the end-vinyl poly dimethyl containing epoxy group changed is 57200mPas, and vinyl is
0.86mol%, epoxide number 0.176mol/100g.
Comparative example 1
Equipped with the light yellow clear product liquid containing remaining active hydrogen content 6mmol% obtained in embodiment 2
In four-hole boiling flask in, dried dry toluene 100mL is added, at 120 DEG C using azeotropic dehydration removing product in
Moisture content under nitrogen protection, is added thiacyclohexane based isocyanate 0.9g, keeps reaction temperature 80 when temperature is down to 80 DEG C
At DEG C react 5h after, then at about 85 DEG C solvent removed by vacuum and micro residue cyclohexyl isocyanate.Finally measure ring
The viscosity for the unsaturated epoxy Polymethyl methacrylate that alkyl isocyanate urethane is crossed is 18350mPas, vinyl
For 0.97mol%, epoxide number 0.018mol/100g, density 1.07 measures still remaining active hydrogen 1.4mmol%.
Comparative example 2
Equipped with the light yellow clear product liquid containing remaining active hydrogen content 6mmol% obtained in embodiment 2
In four-hole boiling flask in, dried dry toluene 100mL is added, at 120 DEG C using azeotropic dehydration removing product in
Moisture content under nitrogen protection, is added thiacyclohexane based isocyanate 0.6g, keeps reaction temperature 80 when temperature is down to 80 DEG C
After reacting 8h at DEG C, then solvent removed by vacuum and low-boiling-point substance at about 85 DEG C.Finally measure part thiacyclohexane based isocyanate ammonia
The viscosity for the unsaturated epoxy Polymethyl methacrylate being esterified is 18260mPas, vinyl 0.97mol%, ring
Oxygen value is 0.018mol/100g, and density 1.07 measures still remaining active hydrogen 1.2mmol%.
Application Example 1
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
3500mL, after material is warming up to 50 DEG C with hot water, then by the fourth two of 100g styrene and 482mL mixed in monomer measuring tank
Alkene is pressed into polymeric kettle with nitrogen, and 1mL tetrahydrofurfuryl alcohol ethylether, hexamethylene then is added with syringe in charging visor
50mL and 0.5mol/L n-BuLi 8mL, and initiation polymerization is carried out in nitrogen indentation polymeric kettle, polymerization temperature is controlled about 65
DEG C, after maintaining reaction 40min, then the thiacyclohexane based isocyanate urethane prepared in embodiment 2 is sucked with syringe and is crossed not
It is saturated epoxy Polymethyl methacrylate oligomer (wherein epoxide number is 0.018mol/100g, density 1.08) 21mL and adds
Enter and carries out coupling reaction in polymeric kettle, the coupling reaction 40min at 65 DEG C.Finally polymer is removed and is added from polymeric kettle
Antioxidant 1076 1.2g and after mixing, glue water vapor accumulation is drying to obtain.Measure polymer Mn=36 × 104,
Molecular weight distributing index is 1.64, polybutadiene section 1.2- unit content 57.8%, crude rubber Mooney viscosity ML=91, coupling
The mass content of the polysiloxanes chain link combined in SSBR is 5.21% (wt).
Application Example 2
The cyclohexane solution for the normal hexane that mass fraction is 10% is added in 5 liters of polymeric kettles under nitrogen protection
3500mL, after material is warming up to 45 DEG C with hot water, then by the fourth two of 100g styrene and 482mL mixed in monomer measuring tank
Alkene is pressed into polymeric kettle with nitrogen, and 1mL tetrahydrofurfuryl alcohol ethylether, hexamethylene then is added with syringe in charging visor
50mL and 0.5mol/L n-BuLi 8mL, and initiation polymerization is carried out in nitrogen indentation polymeric kettle, polymerization temperature is controlled about 65
DEG C, after maintaining reaction 40min, then the ethylene crossed with the cyclohexyl isocyanate urethane prepared in syringe sucking embodiment 6
Polysiloxanes (its epoxide number be 0.023mol/100g, density 1.1) 17mL of the base norbornene hydridization containing epoxy group is simultaneously added poly-
It closes in kettle and carries out coupling reaction, the coupling reaction 40min at 65 DEG C.Polymer is removed from polymeric kettle finally and antioxygen is added
1076 1.2g of agent and after mixing, glue water vapor accumulation is drying to obtain.Measure polymer Mn=38 × 104, molecule
Measuring profile exponent is 1.62, polybutadiene section 1.2- unit content 61.10%, crude rubber Mooney viscosity ML=82, sealing end and coupling
SSBR in the mass content of polysiloxanes chain link that combines be 4.32% (wt).
Application Example 3
Associated process conditions in Application Example 1 are constant, it be merely the styrene that uses is 120g, butadiene is
358mL, tetrahydrofurfuryl alcohol ethylether 0.8mL, 0.5mol/L n-BuLi 7mL, the isopropyl cyanate radical prepared in embodiment 1 add
At unsaturated epoxy dimethyl silicone polymer (wherein epoxide number is 0.015mol/100g, the density 1.07) 21mL crossed.Finally
Measure polymer Mn=64 × 104, molecular weight distributing index 1.61, polybutadiene section 1.2- unit content 57.8%, raw rubber
The mass content of the polysiloxanes chain link combined in Mooney viscosity ML=117, the SSBR of coupling is 6.30% (wt).
Application Example 4
Associated process conditions in embodiment 1 are constant, it be merely the styrene that uses is 110g, butadiene 413mL,
The unsaturated epoxy Polymethyl methacrylate oligomer that the thiacyclohexane based isocyanate urethane prepared in embodiment 2 is crossed
(wherein epoxide number is 0.018mol/100g, density 1.07) 23mL.Finally measure polymer Mn=33 × 104, molecular weight point
Cloth index is 1.65, polybutadiene section 1.2- unit content 60.2%, crude rubber Mooney viscosity ML=62, and sealing end is coupled and dissociates
The mass content of polysiloxanes chain link in SSBR raw rubber containing ammonia ester bond is 6.39% (wt).
Note: molal quantity of the molal quantity of this example epoxy group greater than active lithium, epoxy group/active lithium=1.20 (mol),
SSBR mixed polymerization body in SSBR containing a small amount of coupling and most of end-sealed type.
Comparison study example 1
Associated process conditions in Application Example 1, remaining raw material is constant, it is merely to be prepared using in comparative example 1
(wherein remaining active hydrogen is the unsaturated epoxy Polymethyl methacrylate that thiacyclohexane based isocyanate urethane is crossed
1.4mmol%) 21mL.
Finally measure polymer raw rubber Mn=23 × 104, molecular weight distributing index 1.64, polybutadiene section 1.2- is mono-
First content 56.8%, the mass content of the polysiloxanes chain link combined in Mooney viscosity ML=53, the SSBR of coupling are 4.67%
(wt), the 17.52wt% that the single armed SSBR without coupling accounts for raw rubber total amount is terminated.
Comparison study example 2
Associated process conditions in Application Example 1, remaining raw material is constant, it is merely to be prepared using in comparative example 2
Unsaturated epoxy Polymethyl methacrylate (wherein, the epoxide number 0.018mol/ that thiacyclohexane based isocyanate urethane is crossed
100g, remaining active hydrogen 1.2mmol%) 21mL.
Finally measure polymer raw rubber Mn=29 × 104, molecular weight distributing index 1.64, polybutadiene section 1.2- is mono-
First content 58.9%, the mass content of the polysiloxanes chain link combined in Mooney viscosity ML=61, the SSBR of coupling are 4.94%
(wt), the 18.22wt% that the single armed SSBR without coupling accounts for raw rubber total amount is terminated.
Comparison study example 3
Associated process conditions in embodiment 1 are constant, it is merely the styrene 100g of addition, butadiene 482mL, tetrahydro
Furfuryl alcohol ethylether 1.2mL, 0.5mol/L n-BuLi 10mL, what the end-vinyl epoxidation urethane prepared in embodiment 3 was crossed
Polydiethylsiloxane (wherein, epoxide number 0.29mol/100g, density 1.07) 1.3 mL.
Finally measure polymer Mn=32 × 104, molecular weight distributing index 1.63, polybutadiene section 1.2- unit content
The mass content of the polysiloxanes chain link combined in 63.6%, crude rubber Mooney viscosity ML=68, the SSBR of coupling is 0.34%
(wt)。
Cured properties application examples 1
By the polysiloxane-modified SSBR of epoxy in Application Example 1~4 and comparative example 1~2 and universal SSBR
It is identical that (such as VSL5025-2 of Lanxess Corporation's production) and Asahi Kasei Corporation production HPR-850 press meridian car tread rubber
Formula and refining gluing method are kneaded and are vulcanized, wherein 40 parts of 125 parts of mutation glue SSBR, Nd-45, White Carbon black 175GR
112 parts, 7.5 parts of carbon black N330,8 parts of Si-69,3 parts of stearic acid, 4.5 parts of zinc oxide, 2.5 parts of antioxidant 4020, promotor
2.7 parts of CZ, 2.3 parts of diphenylguanidine, 2.3 parts of sulphur, 55 parts of TDAE oil (wherein VSL5025-2 oil-containing 27.3wt%, in formula
21 parts of the oil of isodose is only added).The physical property and rolling resistance improvement rate of vulcanizate after molding are shown in Table 1.
The physical property and rolling resistance improvement rate of the vulcanizate after molding of table 1
Illustrate: the rolling resistance improvement rate of all SSBR vulcanizates on the basis of universal SSBR (such as VSL5025-2) into
Row calculates.
Although the end-vinyl thiacyclohexane based isocyanate urethane in Application Example 4 containing micro free in SSBR
The unsaturated epoxy Polymethyl methacrylate oligomer crossed, but the comprehensive physical of vulcanizate still better performances；Explanation
The poly- methyl ethylene silicon oxygen of the micro free unsaturated epoxy that end-vinyl thiacyclohexane based isocyanate urethane is crossed in SSBR
Alkane oligomer is useful and harmless to vulcanizate cross-linking reaction.
The poly- diethyl silicon oxygen crossed used in Comparison study example 3 using end-vinyl epoxidation urethane of the invention
Alkane, epoxide number (wherein epoxide number is 0.29mol/100g) with higher, theoretical amount cannot be excessively high, causes its vulcanizate same
More little than rolling resistance reduced rate, dynamic heat build up is relatively higher on year-on-year basis.
The raw rubber of 17~18% end couplings or sealing end in Comparison study example 1~2 in raw rubber containing mass fraction, does not reach
To modified purpose, vulcanizate " Penn effect " is larger, and dynamic mechanical improves unobvious.
Claims (17)
1. a kind of unsaturated ring aoxidizes polysiloxanes, which is characterized in that its viscosity is 10000~60000mPas, and vinyl is
0.20~1.0mol%, epoxide number are 0.01~0.30mol/100g, have the structure of formula A:
Wherein, m=100~300, b=1~10；b≧5.6a；
R1For at least one of vinyl or vinyl norbornene base, R2For at least one of methyl, ethyl, vinyl；R3
For the group containing epoxy group, R4For the group containing imide, wherein the carbon in acyl group is connected with silicon, the content of silicon hydrogen in structure
It is 0.
2. a kind of unsaturated ring according to claim 1 aoxidizes polysiloxanes, which is characterized in that the substituent R3It is selected from
One of formula a or formula b:
3. a kind of unsaturated ring according to claim 1 aoxidizes polysiloxanes, which is characterized in that the substituent R4It is selected from
Formula c:
Wherein R5It is a kind of in alkyl composed by the hydrocarbon chain link that is made of C1~C10 or aromatic radical or naphthene group.
4. a kind of unsaturated ring according to claim 3 aoxidizes polysiloxanes, which is characterized in that the substituent R4Choosing
From one of formula d, formula e, formula f:
5. a kind of unsaturated ring according to claim 1 aoxidizes polysiloxanes, which is characterized in that unsaturated ring in the present invention
Aoxidize polysiloxanes, viscosity 15000-60000mPas, vinyl is 0.20~1.0mol%, epoxide number for 0.015~
0.25mol/100g。
6. a kind of method for preparing unsaturated ring oxidation polysiloxanes as described in claim 1, which is characterized in that including following
Step:
Step 1: the preparation of the epoxidation polysiloxanes of unsaturated siliceous-hydrogen
Unsaturated hydrogen containing siloxane is dissolved in organic solvent, platinum catalyst is added, under inert gas protection, controls temperature
50~90 DEG C, unsaturated epoxy compound is added dropwise, after having reacted, through washing, divides water phase, then distilation at room temperature, i.e.,
Obtain the epoxidation polysiloxanes of unsaturated siliceous-hydrogen；
Step 2: the preparation of unsaturated ring oxidation polysiloxanes
By the resulting unsaturation of step 1 it is siliceous-the epoxidation polysiloxanes of hydrogen is dissolved in organic solvent, in inert gas shielding
Under, controlled at 75~85 DEG C, the compound containing isocyano is added, after reacting 8h or more, distilation, i.e. acquisition insatiable hunger
With epoxidation polysiloxanes, the additional amount of the compound containing isocyano according to the molar ratio, insatiable hunger obtained in step 1
With active hydrogen remaining in the epoxidation polysiloxane molecule of siliceous-hydrogen: isocyano 1: 1.05~1.10.
7. according to right ask 6 described in a kind of unsaturated ring oxidation polysiloxanes preparation method, which is characterized in that step 1
In, the unsaturation hydrogen containing siloxane, viscosity is 10000~60000mPas, and vinyl is 0.20~1.0mol%, is contained
Hydrogen amount is 0.02~0.10mol%, is had following general formula (I):
Wherein m=100~300, n=1~10, R1For at least one of vinyl or vinyl norbornene base, R2For first
At least one of base, ethyl, vinyl.
8. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 7, which is characterized in that it is described not
It is saturated hydrogen containing siloxane, is selected from end-vinyl poly dimethyl hydrogen-containing siloxane, the poly- methyl ethylene Silicon Containing Hydrogen oxygen of end-vinyl
The poly- diethyl hydrogen-containing siloxane of alkane, end-vinyl, end-vinyl polyvinyl hydrogen-containing siloxane and vinyl norbornene hydridization
One of hydrogen-containing siloxane.
9. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step 1
In, the platinum catalyst is chloroplatinic acid, and the chloroplatinic acid additional amount is counted in mass ratio, chloroplatinic acid: unsaturated hydrogen containing siloxane
For 2~5:100000.
10. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step
In one, the unsaturated epoxy compound is the epoxide containing vinyl, and the epoxide containing vinyl adds
Enter amount according to the molar ratio, silicon-hydrogen in unsaturated hydrogen containing siloxane: the vinyl in the epoxide containing vinyl is 1:
1.10~1.25.
11. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 10, which is characterized in that described
Unsaturated epoxy compound is one of 1,2- epoxy -4- vinyl thiacyclohexane, allyl glycidyl ether.
12. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step
In one, the reaction temperature is 50-85 DEG C, and the reaction time is 5.5~8h.
13. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step
In two, the compound containing isocyano is alkyl or aromatic radical or cycloalkanes composed by the hydrocarbon chain link of C1~C10 composition
One of monoisocyanates of group.
14. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 13, which is characterized in that described
Compound containing isocyano is one of cyclohexyl isocyanate, isopropyl isocyanate, n-butyl isocyanate.
15. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step
In two, the organic solvent is one of toluene or dimethylbenzene, and the toluene or dimethylbenzene are preceding first through Non-aqueous processing in use.
16. a kind of preparation method of unsaturated ring oxidation polysiloxanes according to claim 6, which is characterized in that step
In two, the reaction time is 8-10h.
17. a kind of application of unsaturated ring oxidation polysiloxanes according to claim 1, any one by Claims 1 to 5
After unsaturated ring oxidation polysiloxanes described in is used to be coupled SSBR end active lithium, then the SSBR after coupling is used to produce
Meridian half steel tire tread vulcanizate is low with the year-on-year dynamic heat build up of universal SSBR, rolling resistance rate of descent reach 28% with
On.
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Application publication date: 20190226 |