CN108250326A - A kind of polymer containing hydroxy-functional side group and preparation method thereof and branched/network polymer - Google Patents
A kind of polymer containing hydroxy-functional side group and preparation method thereof and branched/network polymer Download PDFInfo
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- CN108250326A CN108250326A CN201611231870.5A CN201611231870A CN108250326A CN 108250326 A CN108250326 A CN 108250326A CN 201611231870 A CN201611231870 A CN 201611231870A CN 108250326 A CN108250326 A CN 108250326A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08J2315/00—Characterised by the use of rubber derivatives
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2323/32—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with phosphorus- or sulfur-containing compounds
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Abstract
The present invention provides a kind of polymer containing hydroxy-functional side group and preparation method thereof and branched/network polymer, and the method for producing polymer containing hydroxy-functional side group includes the following steps：(1) in the presence of the compound that can be generated free radicals under heat or light action, the polymer containing unsaturated double-bond with the organo-silicon compound of thiohydroxy-containing group is contacted and is reacted；(2) reaction is hydrolyzed in the reaction product that step (1) obtains, obtains the polymer containing hydroxy-functional side group；The structure of the organo-silicon compound of the thiohydroxy-containing group such as logical formula (II) HS X SiY3Y4Y5It is shown.The present invention can obtain branched polymer, the mixing uniformity of the polymer containing hydroxy-functional side group and filler is made to be greatly improved, while improve the performance of its blended vulcanizate by the hydrogen bond action between hydroxyl in functional group.
Description
Technical field
The present invention relates to functional polymer field, more particularly, to a kind of polymer containing hydroxy-functional side group
And preparation method thereof and branched/network polymer.
Background technology
Non-polar polymer is usually restricted due to its nonpolar feature in practical applications.To side group in polymer chain
Functionalization and modification is the important channel improved polymer performance and widen polymer application field.As one of three big synthetic materials
Synthetic rubber, available for manufacture tire, conveyor, petroleum pipeline, electric wire and cable jacket etc., need in use with it is inorganic
Filler or organic compound blending.Therefore, the difference of polarity causes the blended characteristic of polymer and filler relatively poor, such as butylbenzene
Rubber, butadiene rubber or isoprene rubber and the carbon black containing polar group on surface or the blended characteristic phase of White Carbon black inorganic filler
To poor, so as to influence end article quality and performance.For this reason, it may be necessary to develop the based polar functionalization of offside in polymer molecular chain
Polymer, typically prepared by the functionalization of pendant group.It is based polar functionalized using offside in strand
Polymer by Electronic interactions and similar compatibility principle, can improve itself and carbon black or the blended characteristic of White Carbon black,
Filler can play better strengthening action.
In addition, the topological structure of polymer molecular chain is also to influence one of an important factor for it is with filler blended characteristic.Branch
Fluidized polymer has excellent processing performance and mechanical property due to its special molecular chain structure and form.For example, macromolecule
It measures, the long chain branching polyisoprene of high cis- Isosorbide-5-Nitrae structural content, molecular chain degradation situation obtains very big in process
Improvement, rubber strain crystallization ability and tensile strength significantly improve, thermal stability, elongation at break, tearing strength, hardness and
The performance indicators such as anti-slippery significantly improve, even better than the correlated performance of natural rubber, referring to patent document
CN104231120B and CN100365030C.Branched polymer can also improve its mixing uniformity between inorganic filler, change
The physical mechanical property and dynamic mechanical of kind vulcanizate, referring to patent document CN201210332297.2,
CN201310251919.3, CN201310180858.6 and CN201310251852.3.Equally, star-branched butyl rubber and star
The branched butadiene-styrene rubber of shape can reach the unification for improving processing performance, physical mechanical property and dynamic mechanical, referring to：Zhao Jin
Wave, Beijing University of Chemical Technology's Master degree candidate's thesis, 2008；Liu Xiaojiao, Liu Jiwen, Zhao Shu high China Synthetic Rubber Industries,
2015,38(2):145-149。
Branched polymer is mainly the following synthetic method：Pick out Graft Method, access Graft Method (end of the chain coupling reaction),
Macromonomer method and molecule interchain coupling method.For branched butyl, branched butadiene-styrene rubber, branched polybutadiene rubber and
The preparation of branched polyisoprene, it is main to be synthesized using access Graft Method or intermolecular coupling reaction.Specifically, for the end of the chain
Coupling reaction adds in branching agent in the case where polymerization system does not terminate, makes the functional group of branching agent and linear molecule living chain
Coupling reaction is held, branching agent uses organohalogen compounds, the aminated compounds containing epoxy group, amino-containing aldehydes or thioaldehydes class
Conjunction object, the unsaturated natural oil of PART EPOXY or Anhydride functional, butter of tin, phenyl tin trichloride, silicon tetrachloride, function
Fluidized polymer etc., but these polyfunctional compounds usually require to add in the presence of polymerization activity chain, and reaction efficiency is opposite
It is low, and be more easy to participate in coupling reaction due to carrying the low molecular weight part of active end group in polymerization system, lead to short-chain branch product
It is relatively more, referring to patent document EP0863165A1, EP1026181A1, EP1099711A2 and EP1650227A2；For molecule
Between coupling method, bis- (more) functional compounds (such as S are added in the polybutadiene solution of linear structure2Cl2, double mercapto alkane classes
Compound) double bond addition reaction is carried out, branched structure is erected by-S-S- or-C-C- bondings, improves the resistance to cold flow of raw rubber
Can, promote vulcanized mechanical and dynamic mechanical, referring to patent document US5567784, TW201418298,
CN201210332297.2, CN 201310251919.3, CN201310180858.6 and CN201310251852.3.In order to change
Kind relationship between anti-slippery and rolling resistance, silane is introduced in the strand of diene polymer or alkadienes and styrene
Coupling agent structural unit, such as 3- mercaptopropyl trimethoxysilanes, referring to patent document CN201310512238,
CN201310512794、CN201310513369.Structural unit is to repeat the polymer that is formed by connecting by covalent bond, referring to Pan ancestral
Benevolence, polymer chemistry (second edition), Chemical Industry Press, 1997.
In conclusion functionalization or branched polymer in strand, can assign material more excellent processing performance
And mechanical property, but preparation method there is also some problems, the coupling efficiency such as active chain end coupling reaction is relatively low, short branch
Chain product is relatively more；- S-S- bondings controllable the difficulty of addition reaction is big, is easily locally crosslinking reaction, is causing to generate gel,
Rubber performance is influenced, and-S-S- keys are also easy to produce fracture when being kneaded.Particularly, there is presently no contain strand side simultaneously
Base hydroxy-functional, branched and network structure polymer.
Invention content
In order to solve the problems in the prior art, the purpose of the present invention is to provide a kind of polymerization containing hydroxy-functional side group
Object and preparation method thereof, branched/network polymer by the hydrogen bond action between hydroxyl in functional group, can obtain branched poly-
It closes object and improves the degree of branching of strand, obtain the mixing uniformity of the polymer containing hydroxy-functional side group and filler
To larger improvement, while improve the performance of its blended vulcanizate.
The present invention provides a kind of polymer containing hydroxy-functional side group, contains in the strand side group of the polymer
Logical formula (I)-S-X-SiY1Y2Functional group shown in OH, wherein, lead to X in formula (I) and be selected from C1-C15Linear chain or branch chain alkylene, Y1
And Y2It is identical or different, it is each independently selected from halogen, hydroxyl or C1-C20Linear or branched alkyl group.
According to polymer provided by the invention, the weight average molecular weight (M of the polymerw) it is preferably 1.0 × 104~1.5 ×
106, more preferably 5.0 × 104~1.2 × 106, further preferably 8.0 × 104~1.0 × 106；Hydroxyl in the logical formula (I)
Degree of functionality be preferably 0.008%~15%, more preferably 0.01%~10%, further preferably 0.03%~8%.
Preferably, the side group containing logical formula (I) is on the polymer molecule backbone into random distribution.
The present invention also provides a kind of preparation method of the polymer containing hydroxy-functional side group, this method includes following step
Suddenly：
(1) under heat or light action in the presence of the compound that can generate free radicals, by the polymer containing unsaturated double-bond with
The organo-silicon compound contact of thiohydroxy-containing group is reacted；
(2) reaction is hydrolyzed in the reaction product that step (1) obtains, obtained described poly- containing hydroxy-functional side group
Close object；
The structure of the organo-silicon compound of the thiohydroxy-containing group such as logical formula (II) HS-X-SiY3Y4Y5It is shown, wherein,
X is selected from C in logical formula (II)1-C15Linear chain or branch chain alkylene, be preferably selected from C1-C12Linear chain or branch chain alkylene, further
It is preferably selected from C1-C10Linear chain or branch chain alkylene；Y3、Y4And Y5It is identical or different, Y3Selected from C1-C20Linear chain or branch chain alkane
Oxygroup, Y4And Y5It is each independently selected from halogen, C1-C20Linear or branched alkyl group or C1-C20Linear chain or branch chain alcoxyl
Base is preferably selected from C1-C19Linear or branched alkyl group or C1-C19Straight or branched alkoxyl, further preferably selected from C1-
C18Linear or branched alkyl group or C1-C18Straight or branched alkoxyl.
According to preparation method provided by the invention, it is preferable that the polymer containing unsaturated double-bond is selected from conjugated diene
Hydrocarbon homopolymer and/or its copolymer are more preferably selected from polybutadiene, polyisoprene, butadiene/isoprene binary copolymerization
Object, phenylethylene/butadiene bipolymer, styrene/isoprene bipolymer, isobutene/isoprene binary copolymerization
At least one of object and butadiene/isoprene/styrene terpolymer.
According to preparation method provided by the invention, it is preferable that the organo-silicon compound of the thiohydroxy-containing group are selected from 2-
Mercapto ethyl-methyl methoxy-ethoxy-silane, 3- mercaptopropyl trimethoxysilanes, 3- mercaptopropyltriethoxysilanes, 3- mercapto propyl
Tripropoxy silane, three butoxy silane of 3- mercaptos propyl, 4- mercapto butyl triethoxysilane, 4- mercapto butyl tripropoxies silane,
6- mercapto hexyls triethoxysilane, 6- mercapto hexyl tripropoxies silane, 10- mercapto decyls triethoxysilane, 10- mercaptos decyl 3 third
Oxysilane, three amoxy silane of 3- mercaptos propyl, three octyloxy silane of 3- mercaptos propyl, three nonyl epoxide silane of 3- mercaptos propyl, 3- mercaptos
Propyl three (14 oxygroup) silane, 16 oxygroup of 3- mercaptos 14 oxygroup of propyl, 18 oxysilane, bis- mercapto butyl of 3,4-, three ethoxy
In base silane, thiopurine methyltransferase diethoxymethylsilane, 3- mercaptos propyltrichlorosilan and 3- mercapto dimethylamine oxygroup methyl-monosilanes
It is at least one.
According to preparation method provided by the invention, it is preferable that it may result from the compound by base under the heat or light action,
Selected from azo compound, organic peroxide class compound, benzoin class compound, benzil class compound, alkane (virtue) base
At least one of benzene ketone compounds, acyl group phosphorous oxides, benzophenone compound and thioxanthones compound.
The azo compound is selected from azodiisobutyronitrile, azo isobutyronitrile, azobisisoheptonitrile, azo dicyano penta
Acid, azo-bis-iso-dimethyl, diethyl azodiformate, diisopropyl azodiformate, azoformic acid dibenzyl ester, 2,
2 '-azo bis- (4- methoxyl group -2,4- methyl pentane nitriles), 4,4 '-azo two (4- cyano valeryl (p- dimethylamino) aniline),
2,2 '-azo bis- (N- methylols) at least one of -2- methyl-malonamics and azodicarbonamide；It is preferably selected from selected from even
In nitrogen bis-isobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, diisopropyl azodiformate and azodicarbonamide
At least one；Further preferably it is selected from azodiisobutyronitrile and/or azobisisoheptonitrile.
The organic peroxide class compound is selected from benzoyl peroxide, dibenzoyl peroxide, benzoyl peroxide
At least one of the tert-butyl ester, benzoyl peroxide ethyl ketone and dilauroyl peroxide；It is preferably selected from benzoyl peroxide, diphenyl peroxide
At least one of formyl, benzoyl peroxide ethyl ketone and dilauroyl peroxide；Further preferably selected from benzoyl peroxide, peroxidating two
At least one of benzoyl, benzoyl peroxide ethyl ketone and dilauroyl peroxide.
The benzoin class compound is selected from benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether and styrax fourth
At least one of ether is preferably selected from benzoin isopropyl ether and/or benzoin isobutyl ether；
The benzil class compound is selected from diphenylethan and/or α, and alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone is preferably selected
From diphenylethan；
Alkane (virtue) the base benzene ketone compounds are selected from α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone and α-amine alkyl
At least one of benzophenone is preferably selected from α, α-diethoxy acetophenone and/or alpha-hydroxyalkyl benzophenone；
The acyl group phosphorous oxides is selected from aroyl phosphine oxide and/or bis(benzoylphenyl) phosphine oxide, is preferably selected from
Aroyl phosphine oxide；
The benzophenone compound is selected from benzophenone, 2,4 dihydroxyl benzophenone and bis- (the diformazan ammonia of 4,4'-
At least one of base) hexichol (first) ketone, it is preferably selected from benzophenone and/or 2,4-DihydroxyBenzophenone；
The thioxanthones compound is selected from thio propoxyl group thioxanthone and/or isopropyl thioxanthone, preferably selects
From thio propoxyl group thioxanthone.
According to preparation method provided by the invention, it is preferable that the organo-silicon compound of the thiohydroxy-containing group with it is described
The molar ratio of double bond is 0.005~20 in polymer containing unsaturated double-bond：100, more preferably 0.01~10：100, further
Preferably 0.02~8：100.
Preferably, the molar ratio of the initiator and the organo-silicon compound of the thiohydroxy-containing group is 0.03~5.0：
100, more preferably 0.05~3.0：100, further preferably 0.07~1.6：100.
According to preparation method provided by the invention, in step (1), reaction carries out in an inert atmosphere, preferably nitrogen gas
Atmosphere；Reaction temperature is preferably 30~150 DEG C, more preferably 40~110 DEG C, further preferably 50~100 DEG C；Reaction time is excellent
It is selected as 1min~35h, more preferably 2min~30h, further preferably 5min~25h.Polymer containing unsaturated double-bond with
The organo-silicon compound of thiohydroxy-containing group can react in organic media.
According to preparation method provided by the invention, in step (2), polymer solution can be made to carry out water in an aqueous medium
Solution reaction.Preferably, reaction temperature is 20~100 DEG C, more preferably 30~100 DEG C, further preferably 40~100 DEG C；Instead
It is 1min~10h, further preferably more preferably 5min~10h, 10min~5h between seasonable.
According to preparation method provided by the invention, it is preferable that in step (2), the pH value of aqueous media is 6.5~10.0,
More preferably 6.5~9.5, further preferably 6.5~10.0.In general, selected aqueous media be tap water, it is used originally
The pH value of water is 6.55.
According to preparation method provided by the invention, it is preferable that in step (2), the volume ratio of polymer solution and water phase is
0.1~100:100；Further preferably 0.5~80:100；Still more preferably it is 1~50:100.
According to preparation method provided by the invention, in step (1) and step (2), the organic media is selected from C4~C8's
Alkane, C5~C8Cycloalkane, C6~C10Substituted or unsubstituted aromatic hydrocarbons, raffinate oil (C6~C8Alkane mixed solution) and halogen
For at least one of hydrocarbon；Be preferably selected from pentane, hexane, methyl cyclopentane, hexamethylene, heptane, octane, hexahydrotoluene, benzene,
Toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, dichloromethane, chloroform, dichloroethanes, trichloroethanes, chloropropane, chlorobutane, chlorine
It is one or more in pentane, chlorobenzene, dichloro-benzenes.
According to preparation method provided by the invention, in step (1) and step (2), the polymerization containing unsaturated double-bond
The factors such as concentration of the object in organic media and molecular weight, organic solvent, temperature, solution viscosity are related.It is provided according to the present invention
Preparation method, it is preferable that it is described containing unsaturated double-bond in the polymer containing unsaturated double-bond/organic media solution system
A concentration of 10g/L~250g/L of polymer, further preferably preferably 15g/L~220g/L, 20g/L~200g/L.
Polymer containing the unsaturated double-bond/organic media solution system can be by commercially available conjugated diene
Type of Collective object, which is dissolved in organic media, to be obtained, and can also be directly obtained by monomer polymerization, and polymerization includes radical polymerization
Conjunction, anionic polymerisation, cationic polymerization and coordination polymerization can be interval implementation or continuous implementation.
The present invention also provides a kind of polymer containing hydroxy-functional side group obtained using preparation method as described above.
The present invention also provides a kind of branched/network polymer, the branched/network polymer is made by the following method：
The polymer containing hydroxy-functional side group is subjected to curing process, obtains the branched/network polymer.
According to branched/network polymer provided by the invention, the curing process can will obtain after hydrolysis
Polymer solution containing hydroxy-functional side group carries out removing solvent processing, and the removing solvent processing is using this field
Conventional means can be realized.
It is described containing unsaturated double-bond under heat or light action in the presence of the compound that can generate free radicals in the present invention
Polymer and the organo-silicon compound of thiohydroxy-containing group efficiently click and are chemically reacted, by the organosilicon of thiohydroxy-containing group
Compound is accessed on conjugated diene polymer macromolecular chain, and reaction efficiency is up to 100%, then by being made after hydrolysis
The standby polymer containing hydroxy-functional side group, further carries out curing process, the polymerization containing hydroxy-functional side group to it
In object, by part of hydroxyl, hydrogen bond action erects tie point between macromolecular chain, forms the branched polymer of different degrees of branching,
When hydroxy-functional degree is high, macromolecular interchain hydrogen bond number increases, and forms degree of branching increase or even the shape of branched polymer
Into network polymer, insoluble in that in solvent, can improve and improve polymer and the mixing uniformity of filler, organic/nothing is improved
The performance of machine composite material.The crosslinked network polymer of physics is generated by hydrogen bond action if being formed, without chemical crosslinking, can be carried
High Material Physics mechanical performance.In process, temperature increases, and hydrogen bond action, which weakens, in branched or network polymer even solves
It opens, both improves processing performance, also can generate stronger interaction with inorganic filler, improve the mixing of polymer and inorganic filler
Effect.
The degree of branching of the branched polymer is represented using branching factor (g '), for line polymer, g '=
1.0；For branched polymer, g '<1.0, g ' value is smaller, and the degree of branching of polymer is higher.The network polymer of formation can lead to
Gel content is crossed to represent, gel content is higher, shows that network polymer content is higher.
Preferably, the degree of branching (g ') of branched polymer of the present invention is 0.45~0.99.
The advantageous effect that technical scheme of the present invention is brought is：(1) by polymer molecular chain to polarity side group
Hydroxy-functional modification and the hydrogen bond action of hydroxyl can pass through reversible non-covalent bond effect and generate branched chain structure
Or network structure, simple process, branched chain structure or network structure depend on hydroxy-functional degree；(2) it is of the invention to contain
The polymer of hydroxy-functional side group can improve inorganic nano-filler (such as：White carbon etc.) point of the particle in rubber matrix
It dissipates, reduces and even inhibit agglomeration of the inorganic nano-filler in rubber matrix, while it is close to improve the crosslinking of its blended vulcanizate
Degree improves cured properties, reduces rolling resistance, improves the rigidity of rubber.
Description of the drawings
Fig. 1 is the polymer containing hydroxy-functional side group described in embodiment 10 in the present invention and is equivalent to polymer quality
The phase contrast microscope photo of 10% white carbon blending.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although following examples illustrate the excellent of the present invention
Embodiment is selected, however, it is to be appreciated that may be realized in various forms the present invention without should be by embodiments set forth herein institute
Limitation.
The present invention calculates the microstructure of polymer by FTIR spectrum；By by multi-angle light diffusion detector
(MALLS) it is combined with routine SEC/RI and viscosity (Viscometer) detector system, the weight average molecular weight of test polymer
(Mw), number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) and branching factor (g '), wherein g ' is the branched poly- of identical molecular weight
Close the ratio between object and line polymer inherent viscosity.Using dispersity of phase contrast microscope (PCM) the characterization white carbon in rubber.
Gel content is tested using standard SH/T 1050-2014.Crosslink density is tested using low field nuclear-magnetism crosslink density method.
By taking polybutadiene rubber as an example, the formula of vulcanizate (with reference to standard GB/T/T8660-2008, does not add carbon black, behaviour
Make oil, zinc oxide and stearic acid)：100 mass parts of rubber, 1.5 mass parts of sulphur S, 0.9 mass parts of accelerator TBBS, hard charcoal
Black 10 mass parts, conditions of vulcanization are 145 DEG C × 30min.
Vulcanizate using TA-Q800DMA dynamic mechanical analyzers test vulcanizate dynamic mechanical, temperature range for-
130 DEG C~100 DEG C, heating rate is 10 DEG C/min.Vulcanizate can represent heat generation or the rolling of rubber in 60 DEG C of tan δ values
Dynamic resistance, value are the smaller the better；Storage modulus E ' represents the rigidity of material at 25 DEG C of room temperature, and value is bigger, and rigidity is higher, also table
The handling of bright tire when being used as tire material improves.
Embodiment 1
In a nitrogen atmosphere, linear high-cis polybutadiene (cis-content=98.3%) is dissolved in hexane (concentration
For 60g/L), after which is mixed with azodiisobutyronitrile, mercaptopropyltriethoxysilane, reacted at 103 DEG C
30 minutes, the molar ratio of wherein mercaptopropyltriethoxysilane and double bond in polymer was 0.04：100, azodiisobutyronitrile with
The molar ratio of mercaptopropyltriethoxysilane is 0.1：100.After reaction, polymer solution is hydrolyzed at 100 DEG C
Reaction 1 hour, the pH of water phase is 9.9, and after removing hexane, the polymer containing hydroxy-functional side group is made.It is described to contain hydroxyl
The polymer of base functionalization side group forms branched polybutadiene by molecule interchain hydrogen bond action, wherein：Cis- 1,4 structural content
It is 98.3%, weight average molecular weight (Mw) it is 3.4 × 105, molecular weight distributing index (Mw/Mn) it is 3.2, branching factor (g ') is
0.94。
Polybutadiene containing hydroxy-functional side group can reach with being equivalent to the silica of polymer quality 10%
Mix uniformly effect, this is less than common polybutadiene.
In the case where addition mass ratio is 10% white carbon, crosslink density test, crosslinking are carried out to its vulcanizate
Density is 21.0 × 10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are 0.084,25 at 60 DEG C
Storage modulus (E ') is 4.0MPa at DEG C.Compared with comparative example 1, crosslink density improves 408%；Tan δ values reduce at 60 DEG C
70%, heat reduces, and rolling resistance reduces；E ' improves 204%, illustrates rigid raising, also indicates that when being used as tire material
The handling of tire improves.
Embodiment 2
Experimental method is with embodiment 1, and the difference lies in mercaptopropyltriethoxysilane and the molar ratios of polymer double bond
It is 0.2：100, the molar ratio of azodiisobutyronitrile and mercaptopropyltriethoxysilane is 1.6：100, water phase in hydrolysis
PH value is 6.55.The polybutadiene containing hydroxy-functional side group and corresponding branched polybutadiene is made, wherein：Cis- 1,4 knot
Structure content is 98.3%, MwIt is 3.2 × 105, Mw/MnIt is 0.95 for 2.4, g '.
Polybutadiene containing hydroxy-functional side group can reach equal with being equivalent to the silica of polymer quality 10%
Even mixing, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, and crosslink density test, crosslink density 24.3 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are storage modulus at 0.12,25 DEG C at 60 DEG C
(E ') is 3.8MPa.Compared with comparative example 1, crosslink density improves 488%；Tan δ values reduce 57% at 60 DEG C, and heat reduces,
Rolling resistance reduces；Storage modulus (E ') improves 189%, and rigidity improves.
Embodiment 3
Experimental method is with embodiment 1, and the difference lies in mercaptopropyltriethoxysilane and the molar ratios of polymer double bond
It is 0.04：100, the molar ratio of azodiisobutyronitrile and mercaptopropyltriethoxysilane is 0.1：100, react 180 at 103 DEG C
Minute, hydrolysis time 3.5h.The polybutadiene containing hydroxy-functional side group and corresponding branched polybutadiene is made,
Wherein：Cis- Isosorbide-5-Nitrae structural content is 98.3%, MwIt is 3.8 × 105, Mw/MnIt is 0.95 for 2.1, g '.
Polybutadiene/hexane solution (4wt%) containing hydroxy-functional side group can be with being equivalent to polymer quality 10%
Silica reach uniform mixing, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, and crosslink density test, crosslink density 32.4 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are storage modulus at 0.16,25 DEG C at 60 DEG C
(E ') is 3.0MPa, and compared with comparative example 1, crosslink density improves 685%；Tan δ values reduce 42% at 60 DEG C, and heat reduces,
Rolling resistance reduces；Storage modulus (E ') improves 128%, shows rigid raising.
Embodiment 4
Experimental method is with embodiment 1, and the difference lies in polymer solution (98g/L) reacts 120 minutes at 103 DEG C.
The polybutadiene containing hydroxy-functional side group and corresponding branched polybutadiene is made, wherein：Cis- 1,4 structural content is
98.3%, MwIt is 3.9 × 105, Mw/MnIt is 0.95 for 2.8, g '.
Polybutadiene containing hydroxy-functional side group can reach equal with being equivalent to the silica of polymer quality 10%
Even mixing, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, and crosslink density test, crosslink density 21.5 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Crosslink density improves 421%；Tan δ values are at 60 DEG C
Storage modulus (E ') is 3.0MPa at 0.096,25 DEG C.Compared with comparative example 1, tan δ values reduce 65% at 60 DEG C, heat drop
Low, rolling resistance reduces；Storage modulus (E ') improves 126%, shows rigid raising.
Embodiment 5
Experimental method is with embodiment 1, and the difference lies in, a concentration of 77g/L of hexane solution of polybutadiene, mercapto propyl first
The molar ratio of base dimethoxysilane and polymer double bond is 0.02：100, azodiisobutyronitrile and mercapto hydroxypropyl methyl dimethoxy
The molar ratio of silane is 0.1：100, it is reacted 120 minutes at 103 DEG C.Be made the polybutadiene containing hydroxy-functional side group and
Corresponding branched polybutadiene, wherein：Cis- Isosorbide-5-Nitrae structural content is 98.3%, MwIt is 3.4 × 105, Mw/MnIt is for 2.1, g '
0.94。
Polybutadiene/hexane solution (6wt%) containing hydroxy-functional side group can be with being equivalent to polymer quality 10%
Nano silicon dioxide reach uniform mixing, this is less than common polybutadiene.
The white carbon that mass ratio is 10% is added, crosslink density test is carried out to its vulcanizate, crosslink density is
13.1×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are energy storage at 0.19,25 DEG C at 60 DEG C
Modulus (E ') is 2.3MPa.Compared with comparative example 1, crosslink density improves 217%；Tan δ values reduce 31% at 60 DEG C, heat
It reduces；Storage modulus (E ') improves 79%, shows rigid raising.
Embodiment 6
Experimental method is with embodiment 1, and the difference lies in by linear butyl rubber, (isoprene unit molar content is
1.7%) it is dissolved in hexane solution (a concentration of 50g/L), mercaptopropyltriethoxysilane and the molar ratio of polymer double bond are
3.5：100, the molar ratio of azodiisobutyronitrile and mercaptopropyltriethoxysilane is 0.1：100,40 points are reacted at 103 DEG C
Clock.The butyl rubber containing hydroxy-functional side group and corresponding branched butyl is made, wherein：MwIt is 4.4 × 105, Mw/
MnIt is 2.0, branching factor (g ') is 0.98.
Polymer/hexane solution (6wt%) containing hydroxy-functional side group can be with being equivalent to polymer quality 10%
Silica reaches uniform mixing, this is less than conventional butyl rubbers.
The white carbon that mass ratio is 10% is added, crosslink density test is carried out to its vulcanizate, crosslink density is
13.5×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are to be stored up at 0.025,25 DEG C at 60 DEG C
Energy modulus (E ') is 1.13MPa.Compared with comparative example 2, crosslink density improves 32%；Tan δ values reduce 40% at 60 DEG C, life
Heat drop is low；Storage modulus (E ') improves 28%, shows rigid raising.
Embodiment 7
The experimental method of step (1) is with embodiment 1, and the difference lies in by linear isoprene rubber, (cis--Isosorbide-5-Nitrae content is
96.4%) it is dissolved in hexane solution (a concentration of 50g/L), mercaptopropyltriethoxysilane and the molar ratio of polymer double bond are
0.16：100, the molar ratio of azodiisobutyronitrile and mercaptopropyltriethoxysilane is 0.1：100,40 points are reacted at 103 DEG C
Clock.The experimental method of step (2) is the same as embodiment 2.The isoprene rubber containing hydroxy-functional side group and corresponding branched different is made
Penta rubber, wherein：Cis--Isosorbide-5-Nitrae structural content of branched isoprene rubber is 96.4%, MwIt is 5.0 × 105, Mw/MnIt is 1.7, branch
It is 0.99 to change the factor (g ').
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, this is less than common isoprene rubber.
The white carbon that mass ratio is 10% is added, crosslink density test, crosslink density 8.5 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are energy storage mould at 0.082,25 DEG C at 60 DEG C
It is 1.59MPa to measure (E ').Compared with comparative example 3, crosslink density improves 12%；Tan δ values reduce 3%, and heat reduces；Energy storage
Modulus (E ') improves 43%, shows rigid raising.
Embodiment 8
Experimental method is with embodiment 1, and the difference lies in by linear butadiene-styrene rubber (styrene mass content is 7.8%)
It is dissolved in cyclohexane solution (a concentration of 50g/L), the molar ratio of mercaptopropyltriethoxysilane and polymer double bond is 2：
100, the molar ratio of azobisisoheptonitrile and mercaptopropyltriethoxysilane is 0.1：100.It is reacted 40 minutes at 103 DEG C.System
The butadiene-styrene rubber containing hydroxy-functional side group and corresponding branched butadiene-styrene rubber are obtained, wherein：MwIt is 7.6 × 105, Mw/MnFor
1.8, branching factor (g ') is 0.73.
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, this is less than common butadiene-styrene rubber.
The white carbon that mass ratio is 10% is added, crosslink density test, crosslink density 5.2 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are energy storage mould at 0.040,25 DEG C at 60 DEG C
It is 5.5MPa to measure (E ').Compared with comparative example 4, crosslink density improves 6%；Tan δ values reduce 5%, and heat reduces, and roll resistance
Power reduces；Storage modulus (E ') improves 111%, shows rigid raising.
Embodiment 9
Experimental method is with embodiment 1, and the difference lies in mercaptopropyl trimethoxysilane and the molar ratios of polymer double bond
It is 0.04：100, the molar ratio of azodiisobutyronitrile and mercaptopropyl trimethoxysilane is 0.1：100, react 120 at 103 DEG C
Minute, the pH value of water phase is 8.01 in hydrolysis, time 75min.The polybutadiene containing hydroxy-functional side group is made
And corresponding branched polybutadiene, wherein：Cis- Isosorbide-5-Nitrae structural content is 98.3%, MwIt is 5.0 × 105, Mw/MnIt is 2.2, it is branched
The factor (g ') is 0.65.
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, and crosslink density test, crosslink density 15.4 are carried out to its vulcanizate
×10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are storage modulus at 0.14,25 DEG C at 60 DEG C
(E ') is 6.0MPa.Compared with comparative example 1, crosslink density improves 273%；Tan δ values reduce 48% at 60 DEG C, and heat reduces；
Storage modulus (E ') improves 361%, shows rigid raising.
Embodiment 10
Experimental method is with embodiment 1, and the difference lies in mercaptopropyltriethoxysilane and the molar ratios of polymer double bond
It is 0.024：100, the molar ratio of azodiisobutyronitrile and mercaptopropyltriethoxysilane is 0.1：100, it is reacted at 103 DEG C
120 minutes, the polybutadiene containing hydroxy-functional side group and corresponding branched polybutadiene is made, wherein：Cis- 1,4 structure
Content is 98.3%, MwIt is 3.3 × 105, Mw/MnIt is 0.99 for 1.8, g '.
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, dispersion effect is as shown in Figure 1, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, carries out crosslink density test to its vulcanizate, crosslink density for 31 ×
10-5mol/cm3.Dynamic mechanical test is carried out to its vulcanizate：Tan δ values are storage modulus at 0.094,25 DEG C at 60 DEG C
(E ') is 3.7MPa.Compared with comparative example 1, crosslink density improves 651%；Tan δ values reduce 66%, and heat reduces, and roll resistance
Power reduces；Storage modulus (E ') improves 185%, shows rigid raising.
Embodiment 11
Experimental method is with embodiment 1, and the difference lies in mercapto hydroxypropyl methyl dimethoxysilane rubs with polymer double bond
You are than being 0.04：100, the molar ratio of azodiisobutyronitrile and mercapto hydroxypropyl methyl diethoxy silane is 0.1：100, in 103 DEG C
Lower reaction 120 minutes.After reaction, polymer solution is condensed removal solvent in 100 DEG C of water (PH=6.55),
Hydrolysis is carried out at the same time, the polybutadiene containing hydroxy-functional side group and corresponding branched poly- fourth was made in 30 minutes time
Diene, wherein：98.4%, MwIt is 4.0 × 105, Mw/MnIt is 0.93 for 2.3, g '.
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, this is less than common polybutadiene.
The white carbon that mass ratio is 10% is added, crosslink density test is carried out to its vulcanizate, crosslink density is
17.7×10-5mol/cm3.Its vulcanizate dynamic mechanical is tested, it is energy storage at 0.062,25 DEG C to obtain tan δ values at 60 DEG C
Modulus (E ') is 2.5MPa.Compared with comparative example 1, crosslink density improves 329%；Tan δ values reduce 78%.Thermogenesis performance carries
It rises, rolling resistance reduces；E ' improves 91%, shows rigid raising.
Embodiment 12
Experimental method with embodiment 11, the difference lies at 103 DEG C react 90 minutes by step (1)；In hydrolysis
The pH value of water phase is 9.9,20 minutes time.The polybutadiene containing hydroxy-functional side group and corresponding branched polybutadiene is made
Alkene, wherein：Cis- Isosorbide-5-Nitrae structural content is 98.4%, MwIt is 4.6 × 105, Mw/MnIt is 0.96 for 4.7, g '.
Polymer containing hydroxy-functional side group can reach uniform with being equivalent to the silica of polymer quality 10%
Mixing, this is less than common polybutadiene.
Addition mass ratio is 10% white carbon, carries out crosslink density test to its vulcanizate, crosslink density for 4.6 ×
10-5mol/cm3.Vulcanizate dynamic mechanical test is carried out to it, it is energy storage mould at 0.24,25 DEG C to obtain tan δ values at 60 DEG C
It is 1.8MPa to measure (E ').Compared with comparative example 1, crosslink density improves 11%；Tan δ values reduce by 11%, and thermogenesis performance improves, rolling
Dynamic resistance reduces；E ' improves 38%, shows rigid raising.
Embodiment 13
Polybutadiene raw material and experimental method are with embodiment 1, and the difference lies in mercaptopropyl trimethoxysilane is with polymerizeing
The molar ratio of object double bond is 0.4：100, the molar ratio of azodiisobutyronitrile and mercaptopropyl trimethoxysilane is 1：100, in 103
It is reacted 40 minutes at DEG C.After reaction, it is molten that polymer solution is condensed to removal in 100 DEG C of water (PH=6.55)
Agent is carried out at the same time hydrolysis, and the polymer containing hydroxy-functional side group was made in 60 minutes time.Pass through hydrogen bond action, shape
The network polybutadiene high into degree of branching, network polybutadiene content are 85.7%, form physical cross-linked network.
Addition mass ratio is 10% white carbon, and raw rubber dynamic mechanical test is carried out to it, obtains tan δ at 60 DEG C
Be worth is that storage modulus (E ') is 5.13MPa at 0.23,25 DEG C.Compared with comparative example 1, tan δ values reduce 17% at 60 DEG C.It is raw
Hot property improves, and E ' improves 292% at 25 DEG C, shows rigid raising.
Embodiment 14
Polybutadiene raw material and experimental method are with embodiment 1, and the difference lies in mercaptopropyl trimethoxysilane is with polymerizeing
The molar ratio of object double bond is 7.2：100, the molar ratio of azodiisobutyronitrile and mercaptopropyl trimethoxysilane is 0.056：100,
It is reacted 40 minutes at 103 DEG C.After reaction, polymer solution is hydrolyzed in 100 DEG C of water (PH=6.55) anti-
It should and agglomerate removal solvent, 60 minutes time.The polybutadiene containing hydroxy-functional side group and corresponding highly -branched journey is made
The network polybutadiene of degree, wherein：Undissolved network polybutadiene content is 99.5%, forms physical cross-linked network.
Addition mass ratio is 10% white carbon, and raw rubber dynamic mechanical test is carried out to it, obtains tan δ at 60 DEG C
Be worth is that storage modulus (E ') is 5.3MPa at 0.18,25 DEG C.Compared with comparative example 1, tan δ values reduce 36% at 60 DEG C, improve
Thermogenesis performance reduces rolling resistance；E ' improves 302% at 25 DEG C, shows rigid raising.
Comparative example 1
Linear high-cis polybutadiene (Mw=3.4 × 105), the content of cis- Isosorbide-5-Nitrae structure is 98.3%.It will the non-function
Fluidized polymer/hexane solution (a concentration of 60g/L) is mixed with being equivalent to the silica of polymer quality 10%, and silica goes out
Now apparent agglomeration, dispersion are uneven.Its vulcanizate is tested, crosslink density is 4.13 × 10-5Mol/mL, at 60 DEG C
Tan δ values are that storage modulus (E ') is 1.3MPa at 0.27,25 DEG C.
Comparative example 2
Linear butyl rubber solution described in embodiment 6 is mixed with being equivalent to the silica of polymer quality 10%
It closes, apparent agglomeration occurs in silica, and dispersion is uneven.Its vulcanizate is tested, crosslink density is 10.2 × 10- 5Mol/mL, tan δ values are that storage modulus (E ') is 0.88MPa at 0.042,25 DEG C at 60 DEG C.
Comparative example 3
Linear isoprene rubber solution described in embodiment 7 is mixed with being equivalent to the silica of polymer quality 10%
It closes, apparent agglomeration occurs in silica, and dispersion is uneven.Its vulcanizate is tested, crosslink density is 7.6 × 10- 5Mol/mL, tan δ values are that storage modulus (E ') is 1.11MPa at 0.084,25 DEG C at 60 DEG C.
Comparative example 4
Linear butadiene-styrene rubber solution described in embodiment 8 is mixed with being equivalent to the silica of polymer quality 10%
It closes, apparent agglomeration occurs in silica, and dispersion is uneven.Its vulcanizate is tested, crosslink density is 4.9 × 10- 5Mol/mL, tan δ values are that storage modulus (E ') is 2.62MPa at 0.042,25 DEG C at 60 DEG C.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
1. a kind of polymer containing hydroxy-functional side group, which is characterized in that contain general formula in the side group of the polymer
(I)-S-X-SiY1Y2Functional group shown in OH, wherein, lead to X in formula (I) and be selected from C1-C15Linear chain or branch chain alkylene, Y1And Y2
It is identical or different, it is each independently selected from halogen, hydroxyl or C1-C20Linear or branched alkyl group.
2. the polymer according to claim 1 containing hydroxy-functional side group, the weight average molecular weight of the polymer are
1.0×104~1.5 × 106, preferably 5.0 × 104~1.2 × 106, further preferably 8.0 × 104~1.0 × 106；General formula
(I) degree of functionality of hydroxyl is 0.008%~15% in, preferably 0.01%~10%, further preferably 0.03%~8%.
3. a kind of preparation method of the polymer containing hydroxy-functional side group, which is characterized in that this method comprises the following steps：
(1) in the presence of the compound that can be generated free radicals under heat or light action, by the polymer containing unsaturated double-bond with containing mercapto
The organo-silicon compound contact of base functional group is reacted；
(2) reaction is hydrolyzed in the reaction product that step (1) obtains, obtains the polymerization containing hydroxy-functional side group
Object；
The structure of the organo-silicon compound of the thiohydroxy-containing group such as logical formula (II) HS-X-SiY3Y4Y5It is shown, wherein, general formula
(II) X is selected from C in1-C15Linear chain or branch chain alkylene, Y3、Y4And Y5It is identical or different, Y3Selected from C1-C20Linear chain or branch chain
Alkoxy, Y4And Y5It is each independently selected from halogen, C1-C20Linear or branched alkyl group or C1-C20Linear chain or branch chain alcoxyl
Base.
4. preparation method according to claim 3, wherein, the polymer containing unsaturated double-bond is selected from conjugated diene
Homopolymer and/or its copolymer are preferably selected from polybutadiene, polyisoprene, butadiene/isoprene bipolymer, benzene
Ethylene/butadiene bipolymer, styrene/isoprene bipolymer, isobutene/isoprene bipolymer and fourth
At least one of diene/isoprene/styrene copolymer.
5. preparation method according to claim 3, wherein, the organo-silicon compound of the thiohydroxy-containing group are selected from 2- mercaptos
Ethyl-methyl methoxy-ethoxy-silane, 3- mercaptopropyl trimethoxysilanes, 3- mercaptopropyltriethoxysilanes, 3- mercaptos propyl three
Npropoxysilane, three butoxy silane of 3- mercaptos propyl, 4- mercapto butyl triethoxysilane, 4- mercapto butyl tripropoxies silane, 6-
Mercapto hexyl triethoxysilane, 6- mercapto hexyl tripropoxies silane, 10- mercapto decyls triethoxysilane, 3 third oxygen of 10- mercaptos decyl
Base silane, three amoxy silane of 3- mercaptos propyl, three octyloxy silane of 3- mercaptos propyl, three nonyl epoxide silane of 3- mercaptos propyl, 3- mercaptos third
Base three (14 oxygroup) silane, 16 oxygroup of 3- mercaptos 14 oxygroup of propyl, 18 oxysilane, bis- mercapto butyl triethoxies of 3,4-
In silane, thiopurine methyltransferase diethoxymethylsilane, 3- mercaptos propyltrichlorosilan and 3- mercapto dimethylamine oxygroup methyl-monosilanes extremely
Few one kind.
6. preparation method according to claim 3, wherein, the compound that can be generated free radicals under the heat or light action,
Selected from azo compound, organic peroxide class compound, benzoin class compound, benzil class compound, alkane (virtue) base
At least one of benzene ketone compounds, acyl group phosphorous oxides, benzophenone compound and thioxanthones compound；
The azo compound be selected from azodiisobutyronitrile, azo isobutyronitrile, azobisisoheptonitrile, azo dicyano valeric acid,
Azo-bis-iso-dimethyl, diethyl azodiformate, diisopropyl azodiformate, azoformic acid dibenzyl ester, 2,2 '-
Azo bis- (4- methoxyl group -2,4- methyl pentane nitriles), 4,4 '-azo two (4- cyano valeryl (p- dimethylamino) aniline), 2,
2 '-azo bis- (N- methylols) at least one of -2- methyl-malonamics and azodicarbonamide；It is preferably selected from selected from azo
In bis-isobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, diisopropyl azodiformate and azodicarbonamide
It is at least one；Further preferably it is selected from azodiisobutyronitrile and/or azobisisoheptonitrile；
The organic peroxide class compound is selected from benzoyl peroxide, dibenzoyl peroxide, the tertiary fourth of benzoyl peroxide
At least one of ester, benzoyl peroxide ethyl ketone and dilauroyl peroxide；It is preferably selected from benzoyl peroxide, diphenyl peroxide first
At least one of acyl, benzoyl peroxide ethyl ketone and dilauroyl peroxide；Further preferably selected from benzoyl peroxide, diphenyl peroxide
At least one of formyl, benzoyl peroxide ethyl ketone and dilauroyl peroxide；
The benzoin class compound is in benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether
At least one, be preferably selected from benzoin isopropyl ether and/or benzoin isobutyl ether；
The benzil class compound is selected from diphenylethan and/or α, and alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone is preferably selected from two
Phenyl ethyl ketone；
Alkane (virtue) the base benzene ketone compounds are selected from α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone and α-amine alkyl phenones
At least one of, it is preferably selected from α, α-diethoxy acetophenone and/or alpha-hydroxyalkyl benzophenone；
The acyl group phosphorous oxides is selected from aroyl phosphine oxide and/or bis(benzoylphenyl) phosphine oxide, is preferably selected from fragrant acyl
Base phosphine oxide；
The benzophenone compound is selected from benzophenone, 2,4 dihydroxyl benzophenone and 4,4'- bis- (dimethylaminos) two
At least one of benzene (first) ketone, is preferably selected from benzophenone and/or 2,4-DihydroxyBenzophenone；
The thioxanthones compound is selected from thio propoxyl group thioxanthone and/or isopropyl thioxanthone, is preferably selected from sulphur
For propoxyl group thioxanthone.
7. preparation method according to claim 3, wherein, the organo-silicon compound of the thiohydroxy-containing group contain with described
The molar ratio of double bond is 0.005~20 in the polymer of unsaturated double-bond：100, preferably 0.01~10：100, more preferably
0.02~8：100；The molar ratio of the initiator and the organo-silicon compound of the thiohydroxy-containing group is 0.03~5.0：
100, preferably 0.05~3.0：100, more preferably 0.07~1.6：100.
8. preparation method according to claim 3, wherein, in step (1), reaction temperature is 30~150 DEG C, the reaction time
For 1min~35h；In step (2), reaction temperature is 20~100 DEG C, and the reaction time is 1min~10h.
9. the polymerization containing hydroxy-functional side group obtained using the preparation method as described in any one in claim 3-8
Object.
10. a kind of branched/network polymer, which is characterized in that the branched/network polymer is made by the following method：It will
The polymer containing hydroxy-functional side group carries out curing process described in claim 9, obtains the branched/network polymer.
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| CN104231120A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Long-chain branched high-cis-polyisoprene and preparation method thereof |
| CN104231119A (en) * | 2013-06-24 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of long-chain branched cis-rich polybutadiene |
| CN104558329A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Functionalized dialkene polymer as well as preparation method and application thereof |
| CN106133014A (en) * | 2014-03-31 | 2016-11-16 | 埃克森美孚化学专利公司 | The free radical grafting of tire functionalized resins |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104231120A (en) * | 2013-06-24 | 2014-12-24 | 北京化工大学 | Long-chain branched high-cis-polyisoprene and preparation method thereof |
| CN104231119A (en) * | 2013-06-24 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of long-chain branched cis-rich polybutadiene |
| CN104558329A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Functionalized dialkene polymer as well as preparation method and application thereof |
| CN106133014A (en) * | 2014-03-31 | 2016-11-16 | 埃克森美孚化学专利公司 | The free radical grafting of tire functionalized resins |
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