CN105440187A - Functional highly-syndiotactic polystyrene and preparation method thereof - Google Patents
Functional highly-syndiotactic polystyrene and preparation method thereof Download PDFInfo
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Abstract
The present invention provides functional highly-syndiotactic polystyrene comprising repeating units having the structure of formula I, in the formula I, R is an alkoxy having 1-20 carbon atoms, an aryloxy having 6-20 carbon atoms, an alkylthio group having 1-20 carbon atoms or an aryl group having 6-20 carbon atoms; the R can substitute arbitrary position on a benzene ring; m represents the number of substituent groups R, and the m is greater than or equal to 1 and less than or equal to 5. The present invention provides a preparation method of the functional highly-syndiotactic polystyrene comprising the repeating units having the structure of the formula I, the method comprises polymerization of functionalized styrene to obtain the functional highly-syndiotactic polystyrene under the role of a catalyst, the functionalized styrene has a structure of formula II, and the catalyst comprises a rare earth complexe, an organic boron compound and an organic aluminum compound. The functional highly-syndiotactic polystyrene has high syndiotactic selectivity.
Description
Technical field
The present invention relates to technical field of polymer, high syndiotactic polystyrene particularly relating to a kind of functionalization and preparation method thereof.
Background technology
High syndiotactic polystyrene (sPS) was realized by using cyclopentadienyl titanium metal catalyst to be polymerized by Japanese IdemitsuKosan company first in 1986.SPS, owing to having the characteristics such as high-melting-point, high crystalline, high elastic coefficient, low-k, low loss factors and excellent heat-resisting solvent resistant, industrially becomes a kind of material had a great attraction.But the fragility of sPS is comparatively large, and lacks polar group in polymkeric substance and make the polarity of sPS poor, and then cause the adhesive property of sPS, dyeing behavior and poor with the compatibility performance of other polar polymers, limit the application of sPS.Therefore, improve the fragility of sPS, improve its polarity, the sPS of complex functionality is the problem that numerous scientific workers endeavour to solve always.
It is most effective means that styrene monomer containing functionalization group is obtained the high syndiotactic polystyrene of functionalization by coordination polymerization catalysts.In prior art, T.C.Chung professor utilized cyclopentadienyl titanium catalyst to synthesize the high syndiotactic polystyrene (Macromolecules2000 of contraposition functional amido in 2000,33,5803-5809), however professor T.C.Chung the polarity of this functional polystyrene is not characterized.Titanium catalyst is utilized only to obtain the polymkeric substance (Macromolecules1989,22,104-108) of random structure to methoxy styrene; Utilize anionoid polymerization can obtain the random polystyrene (application number is the Chinese patent of 201180005819.1) of the alkoxyl group functionalization of lower molecular weight narrow molecular weight distributions, the polystyrene of the alkoxyl group functionalization that technique scheme prepares does not have stereoselectivity, is random structure.
Summary of the invention
In view of this, high syndiotactic polystyrene that the object of the present invention is to provide a kind of functionalization and preparation method thereof, the high syndiotactic polystyrene of functionalization provided by the invention has higher syndiotactic selective.
The invention provides a kind of high syndiotactic polystyrene of functionalization, comprise the repeating unit with structure shown in formula I:
In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces;
M represents the number of substituent R, 1≤m≤5.
Preferably, the number-average molecular weight of the high syndiotactic polystyrene of described functionalization is 1 × 10
4~ 300 × 10
4;
Normality >=90% between the high syndiotactic polystyrene of described functionalization.
Preferably, in described formula I, 1≤m≤3.
Preferably, in described formula I R to be carbonatoms be 2 ~ 10 alkoxyl group, the carbonatoms aryloxy that is 7 ~ 10, the carbonatoms alkylthio that is 2 ~ 10, carbonatoms be 7 ~ 10 arylthio or carbonatoms be the aryl of 7 ~ 10.
The invention provides the preparation method of the high syndiotactic polystyrene of functionalization described in a kind of technique scheme, comprising:
Under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization;
Described functionalization vinylbenzene has the structure shown in formula II:
In formula II, T to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of T on phenyl ring replaces;
N represents the number of substituting group T, 1≤n≤5;
Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.
Preferably, described rare earth compounding is for having the structural compounds shown in formula III or having the compound of structure shown in formula IV:
In formula III, R
1for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof;
R
2for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10;
Ln
1for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
L
1for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene;
P is L
1number, 0≤p≤2;
In formula IV, R
3for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof;
R
4for methylene radical, ethyl or dimethyl are silica-based;
R
5, R
6and R
7be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl independently;
R
8for hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl;
R
9for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10;
Ln
2for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
L
2for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene;
Q is L
2number, 0≤q≤2.
Preferably, described organoboron compound comprises [Ph
3c] [B (C
6f
5)
4], [PhNMe
2h] [BPh
4], [NEt
3h] [BPh
4], [PhNMe
2h] [B (C
6f
5)
4] or B (C
6f
5)
3.
Preferably, the mol ratio of described organoboron compound and rare earth compounding is (0.5 ~ 2.0): 1;
The mol ratio of described organo-aluminium compound and rare earth compounding is (0.5 ~ 3000): 1.
Preferably, the mol ratio of described functionalization vinylbenzene and rare earth compounding is (50 ~ 10000): 1.
Preferably, the temperature of described polyreaction is-60 DEG C ~ 80 DEG C.
The time of described polyreaction is 0.1 hour ~ 48 hours.
The invention provides a kind of high syndiotactic polystyrene of functionalization, comprise the repeating unit with structure shown in formula I; In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces; M represents the number of substituent R, 1≤m≤5.The syndiotactic selective of the high syndiotactic polystyrene of functionalization provided by the invention is higher.Experimental result shows, syndiotactic selective >=90% of the high syndiotactic polystyrene of functionalization provided by the invention.In addition, the functionalization group containing sulphur, oxygen element in the high syndiotactic polystyrene of functionalization provided by the invention, the high syndiotactic polystyrene of this functionalization has good polarity.Experimental result shows, the contact angle of the high syndiotactic polystyrene of functionalization provided by the invention is within the scope of 82 ° ~ 85 °.
The invention provides a kind of preparation method comprising the high syndiotactic polystyrene of the functionalization with structural repeat unit shown in formula I, comprising: under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization; Described functionalization vinylbenzene has the structure shown in formula II; Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.The present invention utilizes the method for polycoordination to prepare the high syndiotactic polystyrene of functionalization having synthesized and had sulphur, oxygen element functionalization group, and the high syndiotactic polystyrene of the functionalization that this method provided by the invention prepares has higher syndiotactic selective.In addition, the high syndiotactic polystyrene of functionalization that this method provided by the invention prepares has good polarity; And preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization provided by the invention is higher.Experimental result shows, preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization provided by the invention can reach 100%.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the carbon-13 nmr spectra figure of the high syndiotactic polystyrene of the functionalization that the embodiment of the present invention 42 prepares;
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the high syndiotactic polystyrene of the functionalization that the embodiment of the present invention 62 prepares.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of high syndiotactic polystyrene of functionalization, comprise the repeating unit with structure shown in formula I:
In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces;
M represents the number of substituent R, 1≤m≤5.
The high syndiotactic polystyrene of functionalization provided by the invention has higher syndiotactic selective.In addition, the functionalization group containing sulphur, oxygen element in the high syndiotactic polystyrene of functionalization provided by the invention, the high syndiotactic polystyrene of this functionalization has good polarity.
The high syndiotactic polystyrene of functionalization provided by the invention comprises the repeating unit with structure shown in formula I.In the present invention, the R in described formula I to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; Be preferably carbonatoms be 2 ~ 10 alkoxyl group, the carbonatoms aryloxy that is 7 ~ 10, the carbonatoms alkylthio that is 2 ~ 10, carbonatoms be 7 ~ 10 arylthio or carbonatoms be the aryl of 7 ~ 10; Be more preferably carbonatoms be 3 ~ 8 alkoxyl group, the carbonatoms aryloxy that is 8 ~ 9, the carbonatoms alkylthio that is 3 ~ 8, carbonatoms be 8 ~ 9 arylthio or carbonatoms be the aryl of 8 ~ 9; Most preferably be carbonatoms be 4 ~ 6 alkoxyl group, the carbonatoms aryloxy that is 8, the carbonatoms alkylthio that is 4 ~ 6, carbonatoms be 8 arylthio or carbonatoms be the aryl of 8.In the present invention, the R in described formula I is the most preferably-O-CH
3,-O-CH
2cH
3,-O-CH
2cH
2cH
3,-O-CH
2-Ph ,-O-Ph ,-S-Ph ,-S-CH
2-Ph ,-C
6h
5or-S-CH
3.In the present invention, the optional position of the R in formula I on phenyl ring replaces.
In the present invention, the m in described formula I represents the number of substituent R, 1≤m≤5.In the present invention, described m is 1,2,3,4 or 5.In the present invention, when m >=2, the R in described formula I on same phenyl ring can be identical substituting group, also can be different substituting groups.
The high syndiotactic polystyrene of functionalization provided by the invention preferably includes the one had in structural repeat unit shown in formula i ~ formula xxi:
In the present invention, the end group do not provided in described formula i ~ formula xxi is methyl.
The number-average molecular weight of the high syndiotactic polystyrene of functionalization provided by the invention is preferably 1 × 10
4~ 300 × 10
4, be more preferably 2 × 10
4~ 150 × 10
4, most preferably be 10 × 10
4~ 100 × 10
4, be the most preferably 110 × 10
4~ 50 × 10
4.
The preparation method of the high syndiotactic polystyrene of functionalization provided by the invention, comprising:
Under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization;
Described functionalization vinylbenzene has the structure shown in formula II:
In formula II, T to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of T on phenyl ring replaces;
N represents the number of substituting group T, 1≤n≤5;
Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.
The present invention utilizes the method for polycoordination to prepare the high syndiotactic polystyrene of functionalization having synthesized and had sulphur, oxygen element functionalization group, and the high syndiotactic polystyrene of the functionalization that this method provided by the invention prepares has higher syndiotactic selective.In addition, the high syndiotactic polystyrene of functionalization provided by the invention has good polarity, and preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization provided by the invention is higher.
Functionalization vinylbenzene, under the effect of catalyzer, is polymerized by the present invention, obtains the high syndiotactic polystyrene of functionalization.In the present invention, described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.In the present invention, described rare earth compounding preferably has the compound of structure shown in formula III or has the compound of structure shown in formula IV:
In the present invention, the R in described formula III
1for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof; Be preferably cyclopentadienyl, indenyl or fluorenyl.
In the present invention, the R in described formula III
2for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10; Be preferably carbonatoms be 2 ~ 8 alkyl, the carbonatoms silylation that is 2 ~ 8, the carbonatoms amido aryl that is 7 ~ 9, carbonatoms be 2 ~ 8 silicon amido, carbonatoms be 2 ~ 8 alkylamino radical or carbonatoms be the allyl group of 4 ~ 8; Be more preferably carbonatoms be 3 ~ 6 alkyl, the carbonatoms silylation that is 3 ~ 6, the carbonatoms amido aryl that is 8, carbonatoms be 3 ~ 6 silicon amido, carbonatoms be 3 ~ 6 alkylamino radical or carbonatoms be the allyl group of 5 ~ 6; Most preferably be carbonatoms be 4 ~ 5 alkyl, the carbonatoms silylation that is 4 ~ 5, the carbonatoms silicon amido that is 4 ~ 5, carbonatoms be 4 ~ 5 alkylamino radical or carbonatoms be the allyl group of 5.
In the present invention, the R in described formula III
2the most be preferably-CH
3,-CH
2siMe
3,-CH (SiMe
3)
2,-O-NMe
2-CH
2c
6h
4,-N (SiMe
3)
2,-NH (SiMe
3) ,-1,3-C
3h
5or-BH
4.
In the present invention, the Ln in described formula III
1for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; Be preferably Y, Sc, La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Gd or Lu, be more preferably Y, La, Pr, Gd, Nd, Sm, Ho, Tb, Er or Lu, most preferably be Y, Sc, Ho, Gd, La, Nd or Lu.
In the present invention, the L in described formula III
1for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene; Described L
1be preferably tetrahydrofuran (THF), ether or toluene, be more preferably tetrahydrofuran (THF) or toluene, most preferably be tetrahydrofuran (THF).
In the present invention, the p in described formula III is L
1number, 0≤p≤2.In the present invention, described p is 0,1 or 2.In the present invention, when described p is 0, in described formula III, ligand L is not had
1.
In the present invention, the compound described in structure shown in formula III preferably has the one in structural compounds shown in formula 1 ~ formula 16:
In the present invention, the end group do not provided in described formula 1 ~ formula 16 is methyl.
The present invention does not have special restriction to the described source with structural compounds shown in formula III, and the preparation method that can have a structural compounds shown in formula III according to preparation well known to those skilled in the art prepares.As the compound with structure shown in formula 1, formula 5 and formula 8 can be prepared according to the method disclosed in document (J.AM.CHEM.SOC., 2009,131,13870-13882); The compound with structure shown in formula 10 is prepared according to the method disclosed in document (Chem.Eur.J., 2009,846-850); The compound with structure shown in formula 11 is prepared according to the method disclosed in document (Organometalics, 2013,32,1445-1458); The compound with structure shown in formula 12 is prepared according to the described disclosed method of document (Angew.Chem.Int.Ed.2013,52,4418-4421); The compound with structure shown in formula 13 and formula 16 is prepared according to the method disclosed in document (Organometalics, 2011,30,3270-3274); The compound with structure shown in formula 14 is prepared according to the described disclosed method of document (Chem.Commun., 2009,3380-3382); The compound with structure shown in formula 15 is prepared according to the described disclosed method of document (Chem.AsianJ.2008,3,1406-1414).
In the present invention, the R in described formula IV
3for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof, be preferably cyclopentadienyl, indenyl or fluorenyl.
In the present invention, the R in described formula IV
4for methylene radical, ethyl or dimethyl are silica-based, be preferably methylene radical or ethyl.In the present invention, the R in described formula IV
5, R
6and R
7be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl independently; Be preferably hydrogen, methyl or ethyl.
In the present invention, the R in described formula IV
8for hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Be preferably hydrogen, methyl, ethyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl; Be more preferably hydrogen, methyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl or 2,4,6-triisopropyl phenyl.
In the present invention, the R in described formula IV
9for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10; Be preferably carbonatoms be 2 ~ 8 alkyl, the carbonatoms silylation that is 2 ~ 8, the carbonatoms amido aryl that is 7 ~ 9, carbonatoms be 2 ~ 8 silicon amido, carbonatoms be 2 ~ 8 alkylamino radical or carbonatoms be the allyl group of 4 ~ 8; Be more preferably carbonatoms be 3 ~ 6 alkyl, the carbonatoms silylation that is 3 ~ 6, the carbonatoms amido aryl that is 8, carbonatoms be 3 ~ 6 silicon amido, carbonatoms be 3 ~ 6 alkylamino radical or carbonatoms be the allyl group of 4 ~ 6; Most preferably be carbonatoms be 4 ~ 5 alkyl, the carbonatoms silylation that is 4 ~ 5, the carbonatoms silicon amido that is 4 ~ 5, carbonatoms be 4 ~ 5 alkylamino radical or carbonatoms be the allyl group of 5.In the present invention, the R in described formula IV
9the most be preferably-CH
3,-CH
2siMe
3,-CH (SiMe
3)
2,-O-NMe
2-CH
2c
6h
4,-N (SiMe
3)
2,-NH (SiMe
3) ,-1,3-C
3h
5or-BH
4.
In the present invention, the Ln in described formula IV
2for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; Be preferably Y, Sc, La, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Gd or Lu, be more preferably Y, La, Pr, Gd, Nd, Sm, Ho, Tb, Er or Lu, most preferably be Y, Er, Gd, La or Lu.
In the present invention, the L in described formula IV
2for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene; Described L
2be preferably tetrahydrofuran (THF), ether or toluene, be more preferably tetrahydrofuran (THF) or toluene, most preferably be tetrahydrofuran (THF).
In the present invention, the q in described formula IV is L
2number, 0≤q≤2.In the present invention, described q is 0,1 or 2.In the present invention, when described q is 0, in described formula IV, ligand L is not had
2.
In the present invention, there is described in formula IV and show that the compound of structure preferably has the one in structural compounds shown in formula 17 ~ formula 28:
In the present invention, the end group do not provided in described formula 17 ~ formula 28 is methyl.
The present invention does not have special restriction to the described source with structural compounds shown in formula IV, and the preparation method that can have a structural compounds shown in formula IV according to preparation well known to those skilled in the art prepares.As can according to document (Macromolecules, 2012,45,1248-1253) disclosed in method, and application number is the method disclosed in the Chinese patent of 201210020478.1 and 201310750870.6, prepares the compound with structure shown in formula 17 ~ formula 28.
In the present invention, described organoboron compound is preferably [Ph
3c] [B (C
6f
5)
4], [PhNMe
2h] [BPh
4], [NEt
3h] [BPh
4], [PhNMe
2h] [B (C
6f
5)
4] or B (C
6f
5)
3, be more preferably [Ph
3c] [B (C
6f
5)
4] or [PhNMe
2h] [B (C
6f
5)
4].The source of the present invention to described organic boride does not have special restriction, adopts the organic boride of mentioned kind well known to those skilled in the art, can be bought obtain by market.
In the present invention, described organo-aluminium compound is preferably aluminum alkyls, alkyl aluminium hydride, one or more in haloalkyl aluminium and aluminium alkoxide compound, are more preferably trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium, diethylbenzyl aluminium, dimethyl hydrogenated aluminium, ADEH, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl aluminum hydride, dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-n-butyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium, ethyl p-methylphenyl aluminum chloride, methylaluminoxane, ethylaluminoxane, one or more in n-propyl aikyiaiurnirsoxan beta and normal-butyl aikyiaiurnirsoxan beta, most preferably be one or more in triisobutyl aluminium, triethyl aluminum, trimethyl aluminium, methylaluminoxane and diisobutylaluminium hydride.
The source of the present invention to described organo-aluminium compound does not have special restriction, adopts the organo-aluminium compound of mentioned kind well known to those skilled in the art, can be bought obtain by market.
In the present invention, the mol ratio of described organoboron compound and rare earth compounding is preferably (0.5 ~ 2.0): 1, is more preferably (0.8 ~ 1.5): 1, most preferably is (0.9 ~ 1.1): 1.In the present invention, the mol ratio of described organo-aluminium compound and rare earth compounding is preferably (0.5 ~ 3000): 1, be more preferably (1 ~ 1000): 1, most preferably be (2 ~ 500): 1, be the most preferably (5 ~ 200): 1.
In the present invention, the preparation method of described catalyzer is preferably:
Rare earth compounding, organoboron compound and organo-aluminium compound are mixed, obtains catalyzer.
In the present invention, the temperature of described mixing is preferably-60 DEG C ~ 80 DEG C, is more preferably-20 DEG C ~ 60 DEG C, most preferably is 0 DEG C ~ 60 DEG C, is the most preferably 25 DEG C ~ 40 DEG C.In the present invention, the time of described mixing is preferably 1 minute ~ 4 minutes, is more preferably 2 minutes ~ 3 minutes.The present invention preferably mixes under the condition of protective gas.In the present invention, described protective gas is preferably nitrogen or rare gas element, is more preferably nitrogen or argon gas.In the present invention, the kind of the kind of described rare earth compounding, organoboron compound and organo-aluminium compound and source and the rare earth compounding described in technique scheme, organoboron compound and organo-aluminium compound and originate consistent, does not repeat them here.In the present invention, described organoboron compound is consistent with the mol ratio of rare earth compounding with organoboron compound described in technique scheme with the mol ratio of rare earth compounding, does not repeat them here.In the present invention, described organo-aluminium compound is consistent with the mol ratio of organo-aluminium compound described in technique scheme and rare earth compounding with the mol ratio of rare earth compounding, does not repeat them here.
In the present invention, described catalyzer is preferably catalyst solution.In the present invention, solvent in described catalyst solution is preferably one or more in alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon and naphthenic hydrocarbon, be more preferably one or more in saturated alkane, saturated aromatic hydrocarbons, saturated halogenated aryl hydrocarbon and saturated rings alkane, most preferably be one or more in normal hexane, normal heptane, hexanaphthene, benzene,toluene,xylene, chlorobenzene, dichlorobenzene and trichlorobenzene.The present invention does not have special restriction to the source of solvent in described catalyst solution, can be bought obtain by market.In the present invention, the volumetric molar concentration of described catalyst solution middle-weight rare earths title complex is preferably 0.1mmol/L ~ 500mmol/L, is more preferably 0.2mmol/L ~ 50mmol/L, most preferably is 0.3mmol/L ~ 5mmol/L.
In the present invention, the preparation method of described catalyst solution is preferably:
By catalyzer dispersion in a solvent, catalyst solution is obtained.
The present invention, more preferably under the condition of protective gas, by catalyzer dispersion in organic solvent, obtains catalyst solution.In the present invention, described protective gas is preferably nitrogen or rare gas element, is more preferably nitrogen or argon gas.The method of the present invention to described dispersion does not have special restriction, adopts dispersion technology scheme well known to those skilled in the art.
In the present invention, described catalyzer is consistent with the catalyzer described in technique scheme, does not repeat them here.In the present invention, described solvent is consistent with the solvent in the catalyst solution described in technique scheme, does not repeat them here.In the present invention, the consumption of described solvent preferably makes the volumetric molar concentration of catalyst solution middle-weight rare earths title complex reach the volumetric molar concentration of rare earth compounding described in technique scheme in catalyst solution.
In the present invention, described functionalization vinylbenzene has the structure shown in formula II:
In the present invention, the T in described formula II to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; Be preferably carbonatoms be 2 ~ 10 alkoxyl group, the carbonatoms aryloxy that is 7 ~ 10, the carbonatoms alkylthio that is 2 ~ 10, carbonatoms be 7 ~ 10 arylthio or carbonatoms be the aryl of 7 ~ 10; Be more preferably carbonatoms be 3 ~ 8 alkoxyl group, the carbonatoms aryloxy that is 8 ~ 9, the carbonatoms alkylthio that is 3 ~ 8, carbonatoms be 8 ~ 9 arylthio or carbonatoms be the aryl of 8 ~ 9; Most preferably be carbonatoms be 4 ~ 6 alkoxyl group, the carbonatoms aryloxy that is 8, the carbonatoms alkylthio that is 4 ~ 6, carbonatoms be 8 arylthio or carbonatoms be the aryl of 8.In the present invention, the T in described formula II is the most preferably-O-CH
3,-O-CH
2cH
3,-O-CH
2cH
2cH
3,-O-CH
2-Ph ,-O-Ph ,-S-Ph ,-S-CH
2-Ph ,-C
6h
5or-S-CH
3.In the present invention, the optional position of the T in formula II on phenyl ring replaces.
In the present invention, the n in described formula II represents the number of substituting group T, 1≤n≤5.In the present invention, described n is 1,2,3,4 or 5.In the present invention, when n >=2, the T in described formula II on phenyl ring can be identical substituting group, also can be different substituting groups.
In the present invention, described functionalization vinylbenzene preferably has the one in structural compounds shown in formula A ~ formula X:
The present invention does not have special restriction to the cinnamic source of described functionalization, adopts the functionalization vinylbenzene of mentioned kind well known to those skilled in the art, can be bought obtain by market.
In the present invention, the mol ratio of described functionalization vinylbenzene and Rare Earths in Catalyst title complex is preferably (50 ~ 10000): 1, be more preferably (100 ~ 9000): 1, most preferably be (200 ~ 8000): 1, be the most preferably (500 ~ 5000): 1.
Functionalization vinylbenzene, under the effect of catalyzer, is carried out polyreaction by the present invention, obtains the high syndiotactic polystyrene of functionalization; Preferably functionalization vinylbenzene is joined in catalyzer and carry out polyreaction, obtain functionalization height syndiotactic polystyrene.The present invention preferably carries out described polyreaction under the condition of anhydrous, anaerobic.In the present invention, the temperature of described polyreaction is preferably-60 DEG C ~ 80 DEG C, is more preferably-30 DEG C ~ 60 DEG C, most preferably is 0 DEG C ~ 50 DEG C, is the most preferably 20 DEG C ~ 40 DEG C.In the present invention, the time of described polyreaction is preferably 0.1 hour ~ 48 hours, is more preferably 0.2 hour ~ 35 hours, most preferably is 0.3 hour ~ 24 hours, is the most preferably 0.4 hour ~ 12 hours.
In the present invention, described polyreaction both can carry out solution polymerization under the condition having solvent, also can carry out mass polymerization in the absence of a solvent.In the present invention, when described polyreaction is carried out under the condition having solvent, the solvent of described polyreaction is preferably one or more in alkane, aromatic hydrocarbons, halogenated aryl hydrocarbon and naphthenic hydrocarbon, be more preferably one or more in saturated alkane, saturated aromatic hydrocarbons, saturated halogenated aryl hydrocarbon and saturated rings alkane, most preferably be one or more in normal hexane, normal heptane, hexanaphthene, benzene,toluene,xylene, chlorobenzene, dichlorobenzene and trichlorobenzene.The source of the present invention to described polymerization solvent does not have special restriction, can be bought obtain by market.
In the present invention, when described polyreaction is polymerized under the condition having solvent, the consumption of solvent preferably makes the cinnamic mass concentration of described functionalization be 1g/100mL ~ 60g/100mL, be more preferably 2g/100mL ~ 50g/100mL, most preferably be 3g/100mL ~ 35g/100mL, be the most preferably 5g/100mL ~ 20g/100mL.
After described polyreaction completes, the present invention preferably adopts ethanol solution hydrochloride to stop described polyreaction; The reaction soln obtained is carried out sedimentation, drying, obtains the high syndiotactic polystyrene of functionalization.In the present invention, the volumetric concentration of described ethanol solution hydrochloride is preferably 5% ~ 15%, is more preferably 8% ~ 12%, most preferably is 10%.In the present invention, described in sedimentation, the reagent of reaction soln is preferably methyl alcohol.In the present invention, the method for described drying is preferably vacuum-drying.In the present invention, the time of described drying is preferably 40 hours ~ 60 hours, is more preferably 45 hours ~ 55 hours, most preferably is 50 hours.
The high syndiotactic polystyrene of functionalization provided by the invention is carried out carbon-13 nmr spectra detection, and detected result is, the high syndiotactic polystyrene of functionalization provided by the invention comprises the repeating unit with structure shown in formula I.The high syndiotactic polystyrene of functionalization provided by the invention is carried out hydrogen nuclear magnetic resonance spectrum analysis and carbon-13 nmr spectra analysis, detect the content of the high syndiotactic polystyrene middle rule structural unit of described functionalization, detected result is, syndiotactic selective >=90% of the high syndiotactic polystyrene of functionalization provided by the invention.Adopt gel permeation chromatography to test number-average molecular weight and the molecular weight distribution of the high syndiotactic polystyrene of functionalization provided by the invention, test result is, the number-average molecular weight of the high syndiotactic polystyrene of functionalization provided by the invention is 1 × 10
4~ 300 × 10
4, molecular weight distribution is 1.18 ~ 2.17.Tested the fusing point of the high syndiotactic polystyrene of functionalization provided by the invention by differential scanning calorimeter, detected result is, the fusing point of the high syndiotactic polystyrene of functionalization provided by the invention is 175 DEG C ~ 320 DEG C.Adopt contact angle measurement to test the contact angle of the high syndiotactic polystyrene of functionalization provided by the invention, test result is, the contact angle of the high syndiotactic polystyrene of functionalization provided by the invention is within the scope of 82 ° ~ 85 °.
By testing the quality of the high syndiotactic polystyrene of the functionalization prepared, calculate the transformation efficiency of the preparation method of the high syndiotactic polystyrene of functionalization provided by the invention, calculation result is, the transformation efficiency of the preparation method of the high syndiotactic polystyrene of functionalization provided by the invention is 100%.
The invention provides a kind of high syndiotactic polystyrene of functionalization, comprise the repeating unit with structure shown in formula I; In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces; M represents the number of substituent R, 1≤m≤5.The high syndiotactic polystyrene of functionalization provided by the invention has higher syndiotactic selective.In addition, the functionalization group containing sulphur, oxygen element in the high syndiotactic polystyrene of functionalization provided by the invention, the high syndiotactic polystyrene of this functionalization has good polarity.
The invention provides a kind of preparation method comprising the high syndiotactic polystyrene of the functionalization with structural repeat unit shown in formula I, comprising: under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization; Described functionalization vinylbenzene has the structure shown in formula II; Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.The present invention utilizes the method for polycoordination to prepare the high syndiotactic polystyrene of functionalization having synthesized and had sulphur, oxygen element functionalization group, and the high syndiotactic polystyrene of the functionalization that this method provided by the invention prepares has higher syndiotactic selective.In addition, the high syndiotactic polystyrene of functionalization that this method provided by the invention prepares has good polarity; And preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization provided by the invention is higher.
Embodiment 1
At 25 DEG C, in the aggregation container of anhydrous, anaerobic process, add rare earth compounding, the 10 μm of ol [Ph that 10 μm of ol have structure shown in formula 1 to 25mL
3c] [B (C
6f
5)
4], 100 μm of ol triisobutyl aluminiums and toluene solvant mix 2 minutes, the volumetric molar concentration obtaining rare earth compounding is 2.0mmolL
– 1catalyst solution.
Embodiment 2 ~ embodiment 41
According to the method described in embodiment 1, adopt the condition in table 1, prepare catalyst solution respectively; Table 1 is the condition of embodiment 2 ~ embodiment 41 Kaolinite Preparation of Catalyst solution.In the present invention, the consumption of embodiment 2 ~ embodiment 41 middle-weight rare earths title complex is 10 μm of ol.
The condition of table 1 embodiment 2 ~ embodiment 41 Kaolinite Preparation of Catalyst solution
Embodiment 42
The catalyst solution that 5mL embodiment 1 prepares is placed in the polymerization bottle of anhydrous, anaerobic process, in described polymerization bottle, adds the functionalization vinylbenzene that 5.0mmol has structure shown in formula A, at 25 DEG C, carry out the polyreaction of 0.4 hour; It is that 10% ethanol solution hydrochloride stops polyreaction that described polyreaction terminates to add 2mL volumetric concentration in backward described polymerization bottle, the reaction soln obtained is poured in the methyl alcohol of 100mL and carry out sedimentation, by the sedimentation products that obtains in vacuum drying oven dry 48 hours, obtain the high syndiotactic polystyrene of the functionalization of 0.67g.
The high syndiotactic polystyrene of the functionalization embodiment of the present invention 42 prepared carries out carbon-13 nmr spectra detection, and as shown in Figure 1, Fig. 1 is the carbon-13 nmr spectra figure of the high syndiotactic polystyrene of the functionalization that the embodiment of the present invention 42 prepares to detected result.As shown in Figure 1, the high syndiotactic polystyrene of functionalization that the embodiment of the present invention 42 prepares comprises the repeating unit with structure shown in formula 29:
The transformation efficiency of the high syndiotactic polystyrene preparation method of functionalization provided according to the method test embodiment of the present invention 42 described in technique scheme, and the syndiotactic selective of the high syndiotactic polystyrene of functionalization for preparing of the embodiment of the present invention 42, number-average molecular weight, molecular weight distribution, fusing point and contact angle; Test result is as shown in table 2, the performance test results of the high syndiotactic polystyrene of the functionalization that the transformation efficiency of the high syndiotactic polystyrene preparation method of the functionalization that table 2 provides for the embodiment of the present invention 42 ~ embodiment 101 and the embodiment of the present invention 42 ~ embodiment 101 prepare.
The performance test results of the high syndiotactic polystyrene of the functionalization that the transformation efficiency of the high syndiotactic polystyrene preparation method of the functionalization that table 2 embodiment of the present invention 42 ~ embodiment 101 provides and the embodiment of the present invention 42 ~ embodiment 101 prepare
As shown in Table 2, preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization of providing of the embodiment of the present invention is higher; And the syndiotactic selective of the high syndiotactic polystyrene of functionalization that the embodiment of the present invention prepares is higher; Simultaneously the contact angle of the high syndiotactic polystyrene of functionalization for preparing of the embodiment of the present invention is less, and polarity is better.
Embodiment 43 ~ embodiment 101
According to the method described in embodiment 42, adopt the condition in table 3, prepare the high syndiotactic polystyrene of functionalization respectively; Table 3 is the condition that embodiment 43 ~ embodiment 101 prepares the high syndiotactic polystyrene of functionalization.
The transformation efficiency of the high syndiotactic polystyrene preparation method of functionalization provided according to the method test embodiment of the present invention 43 ~ 101 described in technique scheme, and the syndiotactic selective of the high syndiotactic polystyrene of functionalization for preparing of the embodiment of the present invention 43 ~ 101, number-average molecular weight, molecular weight distribution, fusing point and contact angle; Test result is as shown in table 2.
The high syndiotactic polystyrene of the functionalization embodiment of the present invention 62 prepared carries out proton nmr spectra detection, detected result as shown in Figure 2, Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the functionalization height syndiotactic polystyrene that the embodiment of the present invention 62 prepares, as shown in Figure 2, the high syndiotactic polystyrene of functionalization that the embodiment of the present invention 62 prepares has the structure shown in formula 30:
Table 3 embodiment 43 ~ embodiment 101 prepares the condition of the high syndiotactic polystyrene of functionalization
As seen from the above embodiment, the invention provides a kind of high syndiotactic polystyrene of functionalization, comprise the repeating unit with structure shown in formula I; In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces; M represents the number of substituent R, 1≤m≤5.The high syndiotactic polystyrene of functionalization provided by the invention has higher syndiotactic selective.In addition, the functionalization group containing sulphur, oxygen element in the high syndiotactic polystyrene of functionalization provided by the invention, the high syndiotactic polystyrene of this functionalization has good polarity.
The invention provides a kind of preparation method comprising the high syndiotactic polystyrene of the functionalization with structural repeat unit shown in formula I, comprising: under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization; Described functionalization vinylbenzene has the structure shown in formula II; Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.The present invention utilizes the method for polycoordination to prepare the high syndiotactic polystyrene of functionalization having synthesized and had sulphur, oxygen element functionalization group, and the high syndiotactic polystyrene of the functionalization that this method provided by the invention prepares has higher syndiotactic selective.In addition, the high syndiotactic polystyrene of functionalization that method provided by the invention prepares has good polarity; And preparation method's transformation efficiency of the high syndiotactic polystyrene of functionalization provided by the invention is higher.
Claims (10)
1. a high syndiotactic polystyrene for functionalization, comprises the repeating unit with structure shown in formula I:
In formula I, R to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of R on phenyl ring replaces;
M represents the number of substituent R, 1≤m≤5.
2. the high syndiotactic polystyrene of functionalization according to claim 1, is characterized in that, the number-average molecular weight of the high syndiotactic polystyrene of described functionalization is 1 × 10
4~ 300 × 10
4;
Normality >=90% between the high syndiotactic polystyrene of described functionalization.
3. the high syndiotactic polystyrene of functionalization according to claim 1, is characterized in that, in described formula I, and 1≤m≤3.
4. the high syndiotactic polystyrene of functionalization according to claim 1, it is characterized in that, in described formula I R to be carbonatoms be 2 ~ 10 alkoxyl group, the carbonatoms aryloxy that is 7 ~ 10, the carbonatoms alkylthio that is 2 ~ 10, carbonatoms be 7 ~ 10 arylthio or carbonatoms be the aryl of 7 ~ 10.
5. a preparation method for the high syndiotactic polystyrene of the functionalization described in Claims 1 to 4 any one, comprising:
Under the effect of catalyzer, functionalization vinylbenzene is carried out polyreaction, obtain the high syndiotactic polystyrene of functionalization;
Described functionalization vinylbenzene has the structure shown in formula II:
In formula II, T to be carbonatoms be 1 ~ 20 alkoxyl group, the carbonatoms aryloxy that is 6 ~ 20, the carbonatoms alkylthio that is 1 ~ 20, carbonatoms be 6 ~ 20 arylthio or carbonatoms be the aryl of 6 ~ 20; The optional position of T on phenyl ring replaces;
N represents the number of substituting group T, 1≤n≤5;
Described catalyzer comprises rare earth compounding, organoboron compound and organo-aluminium compound.
6. method according to claim 5, is characterized in that, described rare earth compounding is for having the compound of structure shown in formula III or having the compound of structure shown in formula IV:
In formula III, R
1for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof;
R
2for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10;
Ln
1for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
L
1for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene;
P is L
1number, 0≤p≤2;
In formula IV, R
3for cyclopentadienyl and derivative, indenyl and derivative thereof or fluorenyl and derivative thereof;
R
4for methylene radical, ethyl or dimethyl are silica-based;
R
5, R
6and R
7be hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl independently of one another;
R
8for hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl, 2,6-3,5-dimethylphenyls, 4-aminomethyl phenyl, mesitylene base, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl or 2,6-di-tert-butyl-phenyl;
R
9for allyl group or borine radical that carbonatoms be 1 ~ 10 alkyl, the carbonatoms silylation that is 1 ~ 10, the carbonatoms amido aryl that is 6 ~ 10, the carbonatoms silicon amido that is 1 ~ 10, the carbonatoms alkylamino radical that is 1 ~ 10, carbonatoms are 3 ~ 10;
Ln
2for Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu;
L
2for part, comprise tetrahydrofuran (THF), ether, glycol dimethyl ether or toluene;
Q is L
2number, 0≤q≤2.
7. method according to claim 5, is characterized in that, described organoboron compound comprises [Ph
3c] [B (C
6f
5)
4], [PhNMe
2h] [BPh
4], [NEt
3h] [BPh
4], [PhNMe
2h] [B (C
6f
5)
4] or B (C
6f
5)
3.
8. method according to claim 5, is characterized in that, the mol ratio of described organoboron compound and rare earth compounding is (0.5 ~ 2.0): 1;
The mol ratio of described organo-aluminium compound and rare earth compounding is (0.5 ~ 3000): 1.
9. method according to claim 5, is characterized in that, the mol ratio of described functionalization vinylbenzene and rare earth compounding is (50 ~ 10000): 1.
10. method according to claim 5, is characterized in that, the temperature of described polyreaction is-60 DEG C ~ 80 DEG C;
The time of described polyreaction is 0.1 hour ~ 48 hours.
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| US15/501,737 US10246536B2 (en) | 2014-08-14 | 2015-08-13 | Functionalized highly syndiotactic polystyrene and preparation method thereof |
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