CN103804601A - Dialkene polymers and preparation method thereof - Google Patents
Dialkene polymers and preparation method thereof Download PDFInfo
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- CN103804601A CN103804601A CN201210437777.5A CN201210437777A CN103804601A CN 103804601 A CN103804601 A CN 103804601A CN 201210437777 A CN201210437777 A CN 201210437777A CN 103804601 A CN103804601 A CN 103804601A
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Abstract
The invention provides dialkene polymers, a dialkene polymer preparation method and the dialkene polymers prepared by the preparation method. The dialkene polymers contain two polymers having structures represented by the formula (I), and have a three-peak molecular weight distribution, wherein R is C1-C8 alkyl, C3-C8 cycloalkyl, C6-C18 substituted or unsubstituted aryl or C7-C18 aralkyl, Y is halogen, Z is a polymer chain containing a monovinylarene structure unit and a conjugated dialkene structure unit, a is 0-3, b1 is 0-3, b2 is 1-4, moreover, and a+b1+b2=4; and the values of b2 of the two polymers having the structures represented by the formula (I) are different. Dialkenes have relatively good processing performance, and extremely have industrial application prospects. The formula (I) is R<a>SiY<b1>Z<b2>.
Description
Technical field
The diene polymer that the present invention relates to the preparation method of a kind of diene polymer, a kind of diene polymer and prepared by the method.
Background technology
The copolyreaction of existing monovinylarene and conjugated diene mainly adopts anionic solution polymerization method to carry out.Particularly, take lithium alkylide and/or rare earth as catalyzer, by the multipolymer of the synthetic monovinylarene of anionic solution polymerization method and conjugated diene.At present, the copolymerization product that is reacted gained by monovinylarene with conjugated diene mainly contains take vinylbenzene, divinyl, isoprene as monomer, hexanaphthene is solvent, styrene analog thermoplastic elastomer (as SBS, SEBS, K resin) and synthetic rubber (as SSBR, SIBR) etc. prepared by lithium alkylide initiator system.This more than 50% class synthetic rubber is as tire product.In recent years, tire product develops into radial from bias tyre, and then to high-performance meridian tire and green radial, performance has also been proposed to more and more higher requirement, both required low rolling resistance to be beneficial to energy-conservation, require again to have very high wet-sliding resistant performance to guarantee vehicle driving safety, also require have good wearability energy and other over-all propertieies simultaneously.For elastomeric specific performance requirement for tire, the coupling agents that adopt improve the method for tire coupling more at present.The general coupling agent using is the halogenide of stanniferous or Siliciumatom, adopts synthetic in this way polymkeric substance and is generally bimodal molecular weight distribution.
CN102344529A discloses a kind of preparation method of solution polymerized butadiene styrene rubber of wide molecular weight distribution, the method comprises the following steps: (1) will account for the vinylbenzene of monomer total amount 20-50 % by weight, accounting for the divinylic monomer of monomer total amount 50-80 % by weight and the mixture of varsol and polar activator adds in polymerization system, under the effect of composite initiator, carry out polymerization, composite initiator adopts the mode dripping to add at twice, twice joining day is spaced apart 1-5min, rate of addition is that per minute 5-10 drips, the amount of the initiator adding is for the first time the 45-70 % by weight of the initiator total amount that adds, temperature of reaction is 50-80 ℃, reaction pressure is 0.10-0.25MPa, reaction times is 30-100min, (2) add coupling agent, the consumption of coupling agent and the mol ratio of initiator are 0.1-1.0, coupling agent divides three times and adds polymerization system, the time at every turn adding is 5-15min, add and be spaced apart 5-10min, the amount of the coupling agent at every turn adding be total coupling agent consumption 1/3, coupling temperature is 60-100 ℃, coupling time is 40-80min, (3) after reacting completely, polymers soln is obtained to star-like solution polymerized butadiene styrene rubber with water treatment, doubly, wherein, described composite initiator is made up of organic single-lithium compound and silicon lithium initiator the 100-300 that the consumption of water is initiator amount.Research shows, the solution polymerized butadiene styrene rubber being prepared by the method has wider molecular weight distribution.But the easy inactivation of this composite initiator, is difficult to promote in actual applications.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of new diene polymer, a kind of diene polymer and the diene polymer being prepared by the method.
The invention provides a kind of diene polymer, wherein, described diene polymer contains two kinds of polymkeric substance with structure shown in formula (I), and described diene polymer has three peak molecular weight distribution;
R
asiY
b1z
b2formula (I),
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, Z is the polymer chain that contains monovinylarene structural unit and conjugated diene structural unit, a is 0-3, b
1for 0-3, b
2for 1-4 and a+b
1+ b
2=4; Described two kinds of b with the polymkeric substance of structure shown in formula I
2vary in size.
The present invention also provides a kind of preparation method of diene polymer, and wherein, the method comprises the following steps:
(1) under the existence of organic single-lithium initiator and under anionic polymerisation condition, make monovinylarene and conjugated diene in solvent, carry out polyreaction, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) obtains is reacted with two kinds of silane coupling agents with structure shown in formula II, and the consumption of described silane coupling agent and linked reaction condition make the diene polymer obtaining have three peak molecular weight distribution;
R
asiY
bformula II,
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, a is that 0-3, b are 1-4 and a+b=4; Described two kinds of b with the silane coupling agent of structure shown in formula II vary in size.
In addition, the present invention also provides the diene polymer being prepared by aforesaid method.
The present inventor's discovery, mechanical property, wet-sliding resistant performance and the rolling resistance performance of existing solution polymerized butadiene styrene rubber are all very excellent, but processing characteristics is undesirable.In order to improve its processing characteristics, the same coupling agents that adopt make styrene-butadiene rubber(SBR) carry out linked reaction to add wide molecular weight distribution more at present, thereby make molecular weight become bimodal wide distribution from unimodal narrow distribution.The present invention adopts two kinds of silane coupling agents to carry out linked reaction, can make the diene polymer obtaining have three peaks distributions, thereby make its processing characteristics more excellent.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the GPC spectrogram of the diene polymer that prepared by embodiment 1;
Fig. 2 is the GPC spectrogram of the diene polymer that prepared by embodiment 2;
Fig. 3 is the GPC spectrogram of the diene polymer that prepared by embodiment 3;
Fig. 4 is the GPC spectrogram of the diene polymer that prepared by comparative example 1;
Fig. 5 is the GPC spectrogram of the diene polymer that prepared by comparative example 2.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Diene polymer provided by the invention contains two kinds of polymkeric substance with structure shown in formula (I), and described diene polymer has three peak molecular weight distribution;
R
asiY
b1z
b2formula (I),
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, Z is the polymer chain that contains monovinylarene structural unit and conjugated diene structural unit, a is 0-3, b
1for 0-3, b
2for 1-4 and a+b
1+ b
2=4; ; Described two kinds of b with the polymkeric substance of structure shown in formula I
2vary in size.Preferably, R is C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl, Y is chlorine or bromine.
Wherein, a represents with respect to 1 mole of diene polymer, and the mole number of radicals R is 0-3; b
1represent with respect to 1 mole of diene polymer, the mole number of group Y, is 0-3; b
2represent with respect to 1 mole of diene polymer, the mole number of polymer chain Z, is 1-4.B
2individual Z can be identical, also can be different, a R can be identical, also can difference, b
1individual Y can be identical, also can be different.Wherein, b
2individual Z difference refers to b
2incomplete same or the b of contained structural unit kind in individual polymer chain Z
2in individual polymer chain Z, contained structural unit kind is identical but content is incomplete same or b
2the chain length of individual polymer chain Z is incomplete same.Only has the b of working as
2when in individual polymer chain Z, the chain length of the kind of contained structural unit and content and polymer chain Z is all just the same, b
2individual Z is just identical.
According to the present invention, described C
1-C
8the example of alkyl can include but not limited to: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, isohexyl, heptyl, different heptyl, octyl group and iso-octyl.Described C
3-C
8the example of cycloalkyl can include but not limited to: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.Described C
6-C
18the example of substituted or non-substituted aryl can include but not limited to: phenyl, tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl (comprise adjacent di-n-butyl phenyl, a di-n-butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (comprise adjacent two positive ethylphenyls, a two positive ethylphenyl and to two positive ethylphenyls).Described C
7-C
10the example of aralkyl can include but not limited to: indenyl, benzyl and phenylethyl.
The present invention is all not particularly limited described diene polymer and number-average molecular weight and the molecular weight distribution of the polymer chain that contains monovinylarene structural unit and conjugated diene structural unit, for example, the number-average molecular weight of described diene polymer can be that 15-40 ten thousand, molecular weight distribution can be 1.3-1.5; The number-average molecular weight of the described polymer chain that contains monovinylarene structural unit and conjugated diene structural unit can be 100,000-200,000, molecular weight distribution can be 1-1.1.In addition, the number-average molecular weight at three peaks of described diene polymer is respectively 400,000-800,000,200,000-400,000,100,000-200,000 according to retention time is ascending, and the peak area per-cent at three peaks is according to ascending 10%-20%, 20%-40%, the 40%-70% of being respectively of retention time.The gel permeation chromatograph (GPC) that it is ALLIANCE2690 that described number-average molecular weight and molecular weight distribution can adopt purchased from the model of WATERS company of the U.S. is measured, and wherein, take THF as moving phase, take Narrow distribution polystyrene as standard specimen, temperature is 25 ℃.
According to the present invention, monovinylarene structural unit in the described polymer chain that contains monovinylarene structural unit and conjugated diene structural unit and the content of conjugated diene structural unit can be selected and change in wider scope, and can be in preparation process according to actual needs the dosage by material control, for example, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit can be 0.3-0.5:1.
According to the present invention, described monovinylarene structural unit is the structural unit derived from monovinylarene, the structural unit being formed by monovinylarene polymerization.Described monovinylarene can be the various aromatic monomers with a vinyl substituted base on the conventional aromatic ring in this area, and as a rule, described monovinylarene can have the structure shown in formula III:
Wherein, R
5can be C
6-C
20replacement or unsubstituted aryl, be preferably phenyl or by one or more C
1-C
5alkyl replace phenyl.
In the present invention, described C
6-C
20replacement or the example of unsubstituted aryl can for but be not limited to: phenyl, tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl (comprise adjacent di-n-butyl phenyl, a di-n-butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (comprise adjacent two positive ethylphenyls, a two positive ethylphenyl and to two positive ethylphenyls).
In the present invention, described monovinylarene for example can be selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene.
According to the present invention, derived from the structural unit of conjugated diene described conjugated diene structural unit is, the structural unit being formed by conjugate diene polymerization.Described conjugated diene refers to the various unsaturated acyclic hydrocarbons that contain conjugated double bond (,-C=C-C=C-) in molecular structure.Described conjugated diene can be the conventional various conjugated dienes in this area, be not particularly limited, and can carry out choose reasonable according to the application scenario of the polarity diene polymer finally obtaining, for example, described conjugated diene can be selected from divinyl, isoprene, 1,3-pentadiene, 1,3-hexadiene and 2, one or more in 3-dimethylbutadiene, are preferably divinyl and/or isoprene.
The preparation method of diene polymer provided by the invention comprises the following steps:
(1) under the existence of organic single-lithium initiator and under anionic polymerisation condition, make monovinylarene and conjugated diene in solvent, carry out polyreaction, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) obtains is reacted with two kinds of silane coupling agents with structure shown in formula II, and the consumption of described silane coupling agent and linked reaction condition make the diene polymer obtaining have three peak molecular weight distribution;
R
asiY
bformula II,
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, a is that 0-3, b are 1-4 and a+b=4; Described two kinds of b with the silane coupling agent of structure shown in formula II vary in size.Preferably, R is C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl, Y is chlorine or bromine.
Wherein, a represents with respect to 1 mole of silane coupling agent, and the mole number of radicals R is 0-3; B represents with respect to 1 mole of silane coupling agent, and the mole number of group Y is 1-4.Described C
1-C
8the example of alkyl can include but not limited to: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, amyl group, isopentyl, hexyl, isohexyl, heptyl, different heptyl, octyl group and iso-octyl.Described C
3-C
8the example of cycloalkyl can include but not limited to: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.Described C
6-C
18the example of substituted or non-substituted aryl can include but not limited to: phenyl, tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl (comprise adjacent di-n-butyl phenyl, a di-n-butyl phenyl and to di-n-butyl phenyl), n-propyl phenyl and diethyl phenyl (comprise adjacent two positive ethylphenyls, a two positive ethylphenyl and to two positive ethylphenyls).Described C
7-C
10the example of aralkyl can include but not limited to: indenyl, benzyl and phenylethyl.
According to the present invention, two kinds of silane coupling agents can be all the existing various materials with structure shown in formula II, for example, can be selected from independently of one another one or more in silicon tetrachloride, dimethyl silicon dichloride, methyl trichlorosilicane, Silicon bromide, dimethyl dibromo SiClx and methyl tribromo SiClx.
According to the present invention, in step (1), the consumption of described monovinylarene and conjugated diene can be selected and adjust in wider scope, and for example, the weight ratio of described monovinylarene and conjugated diene can be 0.3-0.5:1.In addition, can first add monovinylarene to carry out polymerization, add conjugated diene to proceed polymerization again, also can first add conjugated diene to carry out polymerization, add monovinylarene to proceed polymerization again, monovinylarene and conjugated diene can also be added simultaneously in reaction system, carry out polyreaction, all can know these those skilled in the art, and can reasonably select according to practical situation, will repeat no more at this.
According to the present invention, described organic single-lithium initiator can be for example that molecular formula is R
6the organic single-lithium initiator of Li, wherein, R
6for alkyl, cycloalkyl or the aryl of straight or branched.Particularly, described organic single-lithium initiator can be selected from one or more in lithium ethide, propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium, is preferably n-Butyl Lithium and/or s-butyl lithium.The present invention is not particularly limited the consumption of described organic single-lithium initiator, and can reasonably select according to the size of the molecular weight of design.Those skilled in the art should hold intelligible, in the time need to preparing the larger olefin polymer of molecular weight, can reduce the consumption of organic single-lithium initiator, but now rate of polymerization also can correspondingly reduce; In the time need to preparing the olefin polymer of molecular weight, can increase the consumption of organic single-lithium initiator, but now rate of polymerization also can correspondingly increase.Therefore, consider rate of polymerization and the molecular size range of the olefin polymer that obtains, under preferable case, take the gross weight of 100g monovinylarene and conjugated diene as benchmark, the consumption of described initiator is 0.15-2.5mmol.
The present invention is not particularly limited described anionic polymerisation condition, can be that the routine of this area is selected.As a rule, described anionic polymerisation condition comprises temperature, pressure and time.Wherein, described temperature and pressure all can be selected and change in wider scope, in order to be more conducive to the carrying out of polyreaction, described temperature is preferably 10-160 ℃, 40-110 ℃ more preferably, and described pressure is preferably 0.05-0.5MPa, 0.1-0.3MPa more preferably.As a rule, the prolongation of described polymerization time is conducive to the raising of the transformation efficiency of reactant and the yield of reaction product, but the amplitude that the long transformation efficiency to reactant of polymerization time and reaction product yield improve is also not obvious, therefore, consider polymerization efficiency and effect, the described time is preferably 20-80 minute, 25-45 minute more preferably.
In the present invention, described pressure all refers to gauge pressure.
According to the present invention, described solvent can be the various organic substances that can serve as reaction media, for example, can be varsol and/or ether solvent.Described varsol can be C
5-C
7naphthenic hydrocarbon, aromatic hydrocarbons and isoparaffin in one or more.The specific examples of described varsol can include but not limited to: one or more in benzene, toluene, hexane, hexanaphthene, pentane, heptane, hexane and hexanaphthene.Described ether solvent can be C
4-C
15monoether and/or polyether.The specific examples of described ether solvent can include but not limited to: tert.-butoxy Ethoxyethane and/or tetrahydrofuran (THF).Wherein, these solvents can use separately, also can mix use.The consumption of described solvent can reasonably be selected according to the consumption of monomer, and for example, it is 1-30 % by weight that the consumption of described solvent can make the total concn of described monovinylarene and conjugated diene, is preferably 5-20 % by weight.
In addition, as well known to those skilled in the art, in described solvent, may there is micro-water.But the terminator of water belongs with yin ionic polymerization, it can pass through prototropy and terminating chain reaction of propagation, and therefore, for described anionic polymerisation can be carried out smoothly, the present invention preferably dewaters solvent.The described mode dewatering can be for to add water-removal agent in described solvent.The kind of described water-removal agent is known to the skilled person, for example, can be the 5A molecular sieve purchased from Dalian Kang Yu Chemical Co., Ltd..
According to the present invention, under preferable case, in the anionic polymerisation process of step (1), can also add structure regulator, can effectively control the microtexture of described polymerisate like this.Described structure regulator can be the material of existing various microtextures that can telomerized polymer, comprise containing one or more in oxygen, nitrogenous, sulfur-bearing and phosphorous compound, particularly, described structure regulator can be selected from one or more in ether, dibutyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, triethylamine, Tetramethyl Ethylene Diamine, HMPA, potassium tert.-butoxide, tertiary amyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate (ABS) potassium and sodium alkyl benzene sulfonate.As a rule, the mol ratio of described structure regulator and organic single-lithium initiator can be 1-100:1, is preferably 80-100:1.
According to the present invention, the kind of described methyl monovinylarene and conjugated diene can, according to carrying out choose reasonable above, will repeat no more at this.
The present invention is also not particularly limited the consumption of described silane coupling agent, and for example, in the halogen in described silane coupling agent and organic single-lithium initiator, the mol ratio of lithium can be 0.3-0.6:1, be preferably 0.3-0.5:1.In addition,, for three peaks of the diene polymer that balance obtains better distribute, under preferable case, the mol ratio of two kinds of silane coupling agents is 0.4-0.6:1.
According to the present invention, in step (2), described linked reaction condition can be also that the routine of this area is selected, and is not particularly limited.As a rule, described linked reaction comprises temperature, pressure and time.Described temperature for example can for 50-80 ℃, be preferably 60-80 ℃, described pressure for example can be for 0.1-0.3MPa, be preferably 0.1-0.2MPa, the described time for example can for 10-30 minute, be preferably 10-20 minute.
According to the present invention, after linked reaction completes, active centre may also still exist.Therefore, should in reaction system, add terminator so that active centre inactivation.The consumption of described terminator can reasonably be selected according to the consumption of organic single-lithium initiator, and as a rule, the mol ratio of described terminator and organic single-lithium initiator can be 0.1-1:1.Described terminator can be the existing various reagent that can make anion active center inactivation, for example, can be selected from one or more in water, methyl alcohol, ethanol and Virahol, is preferably water.
According to the present invention, under preferable case, after linked reaction completes, can also in the diene polymer obtaining, add various additives, to give described diene polymer various performances.Described additive can be for example anti-aging agent, so that the diene polymer obtaining has good ageing resistance.
The present invention is not particularly limited for the kind of described anti-aging agent, can be the selection of this area routine.For example, described anti-aging agent can be phenols and/or amines antioxidants.Particularly, described anti-aging agent can be anti-aging agent, the four [3-(3 of Irganox 1520 for being purchased from the trade mark of Switzerland's vapour Bagong department, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 2,6-ditertbutylparacresol, tert-butyl catechol and 2, one or more in 2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol).By four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester mix use time, the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight; By 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is while being used in combination, and the content of tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester is not preferably higher than 50 % by weight.
According to the present invention, the consumption of described anti-aging agent can be also the conventional amount used of this area.For example, take the weight of described diene polymer as benchmark, the consumption of described anti-aging agent can be for 0.005-2 % by weight, be preferably 0.1-0.5 % by weight.
According to the present invention, adding after anti-aging agent, described diene polymer can be precipitated out by methods such as purifying precipitation, centrifugation, filtration, decant, hot water cohesions from solution, also can adopt air lift method by the removal of solvents in reaction system, all can know these those skilled in the art, will repeat no more at this.
In addition, the present invention also provides the diene polymer being prepared by aforesaid method.
In the present invention, the diene polymer being prepared by aforesaid method refers to except the solid reaction product after desolventizing.Except the diene polymer shown in formula I, this solid reaction product generally also may comprise other a small amount of diene polymers.Can know these those skilled in the art, will repeat no more at this.
Below will describe the present invention by embodiment.
In following examples and comparative example:
(1) diene polymer and contain monovinylarene structural unit and the number-average molecular weight of the polymer chain of conjugated diene structural unit and molecular weight distribution adopt the gel permeation chromatograph (GPC) that is ALLIANCE2690 purchased from the model of WATERS company of the U.S. to measure, wherein, take THF as moving phase, take Narrow distribution polystyrene as standard specimen, temperature is 25 ℃;
(2) in diene polymer, the content of each structural unit calculates by feed ratio;
(3) in diene polymer, the mole number b of the polymer chain Z that contains monovinylarene structural unit and conjugated diene structural unit
2calculate by GPC result.Concrete testing method is, the GPC curve of described diene polymer is that three peaks distribute, and wherein, relatively little two peaks of retention time are corresponding to the part that linked reaction has occurred, and the peak area at these two peaks and corresponding number-average molecular weight are respectively A
1, Mn
1and A
2, Mn
2; And the relatively large peak of retention time is corresponding to the part that linked reaction does not occur, the number-average molecular weight that this peak is corresponding is Mn
3.B
2=(c × Mn
1÷ Mn
3+ d × Mn
2÷ Mn
3) ÷ (c+d), wherein, c=A
1÷ (A
1+ A
2), d=A
2÷ (A
1+ A
2);
In diene polymer, the mole number a of radicals R calculates according to silane coupling agent raw material, circular is as follows: the mole number of supposing two kinds of used silane coupling agents is respectively e and f, and in the molecular structure of these two kinds of silane coupling agents, the silane coupling agent corresponding with respect to 1mol, the mole number of radicals R is respectively g and h, a=(e × g+f × h) ÷ (e+f).The mole number b of group Y
1=4-a-b
2.Wherein, a, the b that calculate according to the method described above
1and b
2for mean value.
Embodiment 1
This embodiment is used for illustrating diene polymer provided by the invention and preparation method thereof.
Before polymerization, by 5A molecular sieve for the mixed solvent of hexanaphthene and normal hexane (weight ratio is 88:12) (
purchased from Dalian Kang Yu Chemical Co., Ltd., at 500 ℃, dry 5 hours in advance) soak 1 week.Under high pure nitrogen protection, in 10 liters of polymeric kettles, add the above-mentioned mixed solvent of 195kg, 7.83kg vinylbenzene successively, 672g conditioning agent tetrahydrofuran (THF), paradigmatic system is through high-purity N
2after displacement deoxygenation, add 21.17kg divinyl, stir after 10 minutes, add the hexane solution (concentration of n-Butyl Lithium is 0.6mol/L) of 450mL n-Butyl Lithium to carry out polyreaction.Polymerization kick off temperature is that 50 ℃, pressure are 0.1MPa, reacts and after 10 minutes, reaches 90 ℃ of peak temperature (top temperature, lower with), peak pressure (top pressure, lower with) 0.28MPa.Continue reaction after 5 minutes sampling to survey monomer conversion be 100%, the number-average molecular weight of polymerisate is 14.2 ten thousand, molecular weight distribution is 1.05.
Be that 65 ℃, pressure are under 0.15MPa in temperature, to adding 35mL silicon tetrachloride solution in reactor, (concentration is 0.2mol/L, solvent is above-mentioned mixed solvent) and 100mL dimethyldichlorosilane(DMCS) solution (concentration is 0.2mol/L, solvent is above-mentioned mixed solvent) carry out linked reaction, after linked reaction 15 minutes, in polymeric kettle, add 4.8g deionized water to carry out termination reaction, then stirring reaction adds 232g anti-aging agent 2 after 5 minutes, 6-ditertbutylparacresol, obtains glue.Glue obtains diene polymer after water vapor condenses, is dried.In described diene polymer, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.37:1, and a is 1.5, b1 is 0.3, b
2be 2.2.The number-average molecular weight of described diene polymer is 180,000, molecular weight distribution is 1.31, and its GPC spectrogram as shown in Figure 1.As can be seen from Figure 1, the molecular weight of described diene polymer is three peaks and distributes, the number-average molecular weight at three peaks is respectively 54.7 ten thousand, 30.1 ten thousand, 14.2 ten thousand according to retention time is ascending, the peak area per-cent at three peaks is respectively 16.5%, 28.6%, 54.9% according to retention time is ascending, can infer that thus this diene polymer has very excellent processing characteristics.
Embodiment 2
This embodiment is used for illustrating diene polymer provided by the invention and preparation method thereof.
Carry out the preparation of diene polymer according to the method for embodiment 1, different, the add-on of described silicon tetrachloride solution is 40mL, and the add-on of described dimethyldichlorosilane(DMCS) solution is 95mL.In described diene polymer, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.37:1, and a is 1.4, b
1be 0.3, b
2be 2.3.The number-average molecular weight of the diene polymer obtaining is 190,000, molecular weight distribution is 1.34, and its GPC spectrogram as shown in Figure 2.As can be seen from Figure 2, the molecular weight of described diene polymer is three peaks and distributes, the number-average molecular weight at three peaks is respectively 56.6 ten thousand, 34.8 ten thousand, 14.6 ten thousand according to retention time is ascending, the peak area per-cent at three peaks is respectively 17.2%, 27.3%, 55.5% according to retention time is ascending, can infer that thus this diene polymer has very excellent processing characteristics.
Embodiment 3
This embodiment is used for illustrating diene polymer provided by the invention and preparation method thereof.
Carry out the preparation of diene polymer according to the method for embodiment 1, different, the add-on of described silicon tetrachloride solution is 45mL, and the add-on of described dimethyldichlorosilane(DMCS) solution is 90mL.In described diene polymer, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.37:1, and a is 1.3, b
1be 0.4, b
2be 2.3.The number-average molecular weight of the diene polymer obtaining is 190,000, molecular weight distribution is 1.36, and its GPC spectrogram as shown in Figure 3.As can be seen from Figure 3, the molecular weight of described diene polymer is three peaks and distributes, the number-average molecular weight at three peaks is respectively 58.0 ten thousand, 32.4 ten thousand, 14.8 ten thousand according to retention time is ascending, the peak area per-cent at three peaks is respectively 18.3%, 26.5%, 55.2% according to retention time is ascending, can infer that thus this diene polymer has very excellent processing characteristics.
Comparative example 1
This comparative example is used for illustrating reference diene polymer and preparation method thereof.
Carry out the preparation of diene polymer according to the method for embodiment 1, different, described dimethyldichlorosilane(DMCS) solution substitutes by the identical silicon tetrachloride solution of the concentration of identical weight part.In described diene polymer, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.37:1, and the number-average molecular weight of the diene polymer obtaining is 190,000, and its GPC spectrogram as shown in Figure 4.As can be seen from Figure 4, the molecular weight of described diene polymer is bimodal distribution.
Comparative example 2
This comparative example is used for illustrating reference diene polymer and preparation method thereof.
Carry out the preparation of diene polymer according to the method for embodiment 1, different, described dimethyldichlorosilane(DMCS) solution substitutes with the identical tin tetrachloride solution of the concentration of identical weight part.In described diene polymer, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.37:1, and the number-average molecular weight of the diene polymer obtaining is 190,000, and its GPC spectrogram as shown in Figure 5.As can be seen from Figure 5, the molecular weight of described diene polymer is bimodal distribution.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (12)
1. a diene polymer, is characterized in that, described diene polymer contains two kinds of polymkeric substance with structure shown in formula (I), and described diene polymer has three peak molecular weight distribution;
R
asiY
b1z
b2formula (I),
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, Z is the polymer chain that contains monovinylarene structural unit and conjugated diene structural unit, a is 0-3, b
1for 0-3, b
2for 1-4 and a+b
1+ b
2=4; Described two kinds of b with the polymkeric substance of structure shown in formula I
2vary in size.
2. diene polymer according to claim 1, wherein, R is C
1-C
6alkyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, tolyl, benzyl or styroyl, Y is chlorine or bromine.
3. diene polymer according to claim 1 and 2, wherein, the number-average molecular weight of described diene polymer is that 15-40 ten thousand, molecular weight distribution are 1.3-1.5; The number-average molecular weight of the described polymer chain that contains monovinylarene structural unit and conjugated diene structural unit is 100,000-200,000, molecular weight distribution 1-1.1.
4. diene polymer according to claim 3, wherein, the number-average molecular weight at three peaks of described diene polymer is according to the ascending difference 400,000-800,000 of retention time, 200,000-400,000,100,000-200,000, and the peak area per-cent at three peaks is according to ascending 10%-20%, 20%-40%, the 40%-70% of being respectively of retention time.
5. diene polymer according to claim 1 and 2, wherein, in the described polymer chain that contains monovinylarene structural unit and conjugated diene structural unit, the weight ratio of described monovinylarene structural unit and conjugated diene structural unit is 0.3-0.5:1; Preferably, described monovinylarene structural unit is the structural unit derived from monovinylarene, described monovinylarene is selected from vinylbenzene, Vinyl toluene, alpha-methyl styrene, 4-t-butyl styrene, 4-vinyl toluene, 3,5-diethylbenzene ethene, 3, one or more in 5-di-n-butyl vinylbenzene, 4-n-propylbenzene ethene and 4-dodecyl vinylbenzene; Preferably, described conjugated diene structural unit is the structural unit derived from conjugated diene, and described conjugated diene is selected from divinyl, isoprene, 1,3-pentadiene, 1, one or more in 3-hexadiene and 2,3-dimethylbutadiene.
6. a preparation method for diene polymer, wherein, the method comprises the following steps:
(1) under the existence of organic single-lithium initiator and under anionic polymerisation condition, make monovinylarene and conjugated diene in solvent, carry out polyreaction, obtain polymerisate;
(2) under linked reaction condition, the polymerisate that step (1) obtains is reacted with two kinds of silane coupling agents with structure shown in formula II, and the consumption of described silane coupling agent and linked reaction condition make the diene polymer obtaining have three peak molecular weight distribution;
R
asiY
bformula II,
Wherein, R is C
1-C
8alkyl, C
3-C
8cycloalkyl, C
6-C
18substituted or non-substituted aryl or C
7-C
18aralkyl, Y is halogen, a is that 0-3, b are 1-4 and a+b=4; Described two kinds of b with the silane coupling agent of structure shown in formula II vary in size.
7. preparation method according to claim 6, wherein, in the halogen in described silane coupling agent and organic single-lithium initiator, the mol ratio of lithium is 0.3-0.6:1, is preferably 0.3-0.5:1.
8. according to the preparation method described in claim 6 or 7, wherein, the mol ratio of two kinds of silane coupling agents is 0.4-0.6:1; Preferably, two kinds of silane coupling agents are selected from one or more in silicon tetrachloride, dimethyl silicon dichloride, methyl trichlorosilicane, Silicon bromide, dimethyl dibromo SiClx and methyl tribromo SiClx separately.
9. according to the preparation method described in claim 6 or 7, wherein, in step (1), the weight ratio of described monovinylarene and conjugated diene is 0.3-0.5:1.
10. according to the preparation method described in claim 6 or 7, wherein, in step (1), described anionic polymerisation condition comprises that temperature is that 10-160 ℃, pressure are that 0.05-0.5MPa, time are 20-80 minute; Preferably, described temperature is that 40-110 ℃, pressure are that 0.1-0.3MPa, time are 25-45 minute.
11. according to the preparation method described in claim 6 or 7, and wherein, in step (2), described linked reaction condition comprises that temperature is that 50-80 ℃, pressure are that 0.1-0.3MPa, time are 10-30 minute; Preferably, described temperature is that 60-80 ℃, pressure are that 0.1-0.2MPa, time are 10-20 minute.
12. diene polymers that prepared by the method described in any one in claim 6-11.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146734A (en) * | 2015-03-31 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of coupling agent and application and atactic butadiene styrene copolymer and preparation method thereof |
| CN107540890A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application |
| CN109575189A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene polymer and its preparation method and application |
| CN110461893A (en) * | 2017-03-31 | 2019-11-15 | 住友化学株式会社 | The manufacturing method of conjugated diene polymer and conjugated diene polymer |
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| CN1392166A (en) * | 2002-05-21 | 2003-01-22 | 巴陵石化岳阳石油化工总厂 | Process for preparing thermoplastic phenylethylene elastomer |
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| CN1392166A (en) * | 2002-05-21 | 2003-01-22 | 巴陵石化岳阳石油化工总厂 | Process for preparing thermoplastic phenylethylene elastomer |
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| CN106146734A (en) * | 2015-03-31 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of coupling agent and application and atactic butadiene styrene copolymer and preparation method thereof |
| CN106146734B (en) * | 2015-03-31 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of coupling agent and its application and atactic butadiene styrene copolymer and preparation method thereof |
| CN107540890A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | Coupling agent and the conjugated diene polymer of star line blending and its preparation method and application |
| CN110461893A (en) * | 2017-03-31 | 2019-11-15 | 住友化学株式会社 | The manufacturing method of conjugated diene polymer and conjugated diene polymer |
| CN110461893B (en) * | 2017-03-31 | 2023-10-27 | 住友化学株式会社 | Conjugated diene polymer and method for producing conjugated diene polymer |
| CN109575189A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene polymer and its preparation method and application |
| CN109575189B (en) * | 2017-09-29 | 2021-04-09 | 中国石油化工股份有限公司 | Monovinylarene-conjugated diene polymer and preparation method and application thereof |
| CN114316139A (en) * | 2020-09-30 | 2022-04-12 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
| CN114316139B (en) * | 2020-09-30 | 2024-03-01 | 中国石油天然气股份有限公司 | Solution polymerized styrene-butadiene rubber and preparation method and application thereof |
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