CN102775539A - Preparation method of polybutadiene - Google Patents
Preparation method of polybutadiene Download PDFInfo
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- CN102775539A CN102775539A CN201210299125XA CN201210299125A CN102775539A CN 102775539 A CN102775539 A CN 102775539A CN 201210299125X A CN201210299125X A CN 201210299125XA CN 201210299125 A CN201210299125 A CN 201210299125A CN 102775539 A CN102775539 A CN 102775539A
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- 0 CC[C@@](C)(CC=C)N=C(CCl)C1=CCC(C(C2=N)Cl)*2=N1 Chemical compound CC[C@@](C)(CC=C)N=C(CCl)C1=CCC(C(C2=N)Cl)*2=N1 0.000 description 3
- VWIOMFMPIVMLIR-UHFFFAOYSA-N COC(c1nc(C(O)=O)ccc1)=O Chemical compound COC(c1nc(C(O)=O)ccc1)=O VWIOMFMPIVMLIR-UHFFFAOYSA-N 0.000 description 1
- HRNWHYCHEQWELE-UHFFFAOYSA-N Cc(cc(cc1C)Cl)c1NC(c1cc(C(Nc(c(C)c2)c(C)cc2Cl)=O)ccc1)=O Chemical compound Cc(cc(cc1C)Cl)c1NC(c1cc(C(Nc(c(C)c2)c(C)cc2Cl)=O)ccc1)=O HRNWHYCHEQWELE-UHFFFAOYSA-N 0.000 description 1
- GWHOGODUVLQCEB-UHFFFAOYSA-N O=C(c1nc(C(Cl)=O)ccc1)Cl Chemical compound O=C(c1nc(C(Cl)=O)ccc1)Cl GWHOGODUVLQCEB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a preparation method of a polybutadiene, which comprises the following steps: under the actions of a cocatalyst and a cobalt complex disclosed as Formula (I), carrying out polymerization reaction on butadiene in an organic solvent to obtain polybutadiene. In the polybutadiene preparation process, the cobalt complex disclosed as Formula (I) and the cocatalyst are used as the catalyst, the electrophilic chlorine atoms introduced into the ligand structure of the cobalt complex increase the electropositivity of the active center cobalt atom, thereby endowing the butadiene monomer with larger coordination space; and thus, the cobalt complex has higher catalytic activity, so the polybutadiene has higher yield. The experiment proves that the yield of polybutadiene is 72-97% in the butadiene catalytic polymerization process of the cobalt complex.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to a kind of preparation method of polyhutadiene.
Background technology
Viton is a kind of very important synthetic materials, in fields such as automobile, building, medical treatment, all has extremely widely to use.Along with the development of China Synthetic Rubber Industry, polybutadiene rubber has obtained using widely in the production of rubber items such as tire, adhesive tape, sebific duct and rubber overshoes owing to have advantages such as good springiness, strong, the living heat of wear resistance is low, hysteresis loss is little.Polybutadiene rubber is to be a kind of general purpose synthetic rubber that monomer polymerization obtains with the 1,3-butadiene.
Up to now, the catalystsystem that the catalysis polymerizing butadiene is commonly used in the prior art has LiR, TiCl
4/ I
2/ Al
iBu
3, Co (OCOR)
2/ H
2O/AlEt
2Cl, Ni (OCOR)
2/ BF
3OEt
2/ AlEt
3, Nd (OCOR)
3/ Et
3Al
2Cl
3/ Al
iBu
2H, above-mentioned five catalyst systems have successfully been realized the industriallization of polymerizing butadiene.Wherein, cobalt series catalyst is as one of industrialized five big catalyzer, and its catalysis polymerizing butadiene has distinct stereoselective, at different parts with under the situation of electronics, can obtain cis-1,4-and 1, two kinds of polymeric chain structures of 2-.For example, cobalt salt directly under the alkylaluminium cpd effect catalysis obtain high-cis-1; And when in polymerization system, introducing electron donor such as triphenylphosphine or dithiocarbonic anhydride, help obtaining 1, the polyhutadiene of 2-structure.Can obtain the polybutadiene of different structure in view of cobalt series catalyst adopts different co-catalysts, often adopt cobalt series catalyst catalysis polymerizing butadiene in the commercial production.
The cobalt series catalyst of Schiff bases part becomes the focus of research, and this type of catalyzer has single active site, and the catalysis polymerizing butadiene also has good selectivity.For example, pyridine list imines alcohols NNO three denticles system, catalysis polymerizing butadienes such as salicylic alidehyde imine NO bidentate system have active preferably, can access the polyhutadiene of high-cis.But during the cobalt series catalyst catalysis divinyl alkene polymerization of existing Schiff bases part, catalytic activity is still lower, thereby makes the yield of polyhutadiene lower.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of preparation method with polyhutadiene of higher yields.
In view of this, the invention provides a kind of preparation method of polyhutadiene, comprising:
Under the effect of promotor and cobalt complex with formula I structure, divinyl is carried out polyreaction in organic solvent, obtain polyhutadiene;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
Preferably, the mol ratio of said cobalt complex and said divinyl is 1: (1000 ~ 5000).
Preferably, the temperature of said polyreaction is 0 ~ 100 ℃.
Preferably, said promotor is diethylammonium sesquialter aluminium, triisobutyl aluminium, triethyl aluminum or methyl alcoxyl aluminium.
Preferably, the time of said polyreaction is 0.05h ~ 4h.
Preferably, said R
1And R
2Independently be selected from hydrogen, methyl, ethyl or sec.-propyl separately.
Preferably, said R
3Be hydrogen, chlorine, bromine, methyl, ethyl or sec.-propyl.
Preferably, the preparation method of said cobalt complex is specially:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and cobalt is carried out the reaction second time, the cobalt complex that obtains having the formula I structure in second organic solvent;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
Preferably, said two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is 1: (1.5 ~ 2.5).
Preferably, the time of said first set reaction is 3 ~ 5h, and the time of the said reaction second time is 3 ~ 7h.
The invention provides a kind of preparation method of polyhutadiene, under the effect of promotor and cobalt complex, divinyl is carried out polyreaction in organic solvent, obtain polyhutadiene with formula I structure.The present invention has adopted cobalt complex with formula I structure and promotor as catalyzer, owing in the ligand structure of cobalt complex, having introduced electrophilic chlorine atom in the process of preparation polyhutadiene; Then increased the positive polarity of active site cobalt atom; Make the angle of two phenyl ring become big, thereby reduced the steric hindrance around the cobalt of active site, given divinylic monomer bigger coordination space; Make catalyzer have advantages of high catalytic activity, so polyhutadiene have higher yield.Experiment showed, cobalt complex in the process of catalysis polymerizing butadiene, the yield of polyhutadiene is 72% ~ 97%.
Description of drawings
Fig. 1 is the crystalline structure figure that the X-single crystal diffraction of the title complex 5 of the embodiment of the invention 1 preparation characterizes;
Fig. 2 is the crystalline structure figure that the X-single crystal diffraction of the title complex 9 of the embodiment of the invention 2 preparations characterizes;
The crystalline structure figure that the X-single crystal diffraction of the title complex 10 of Fig. 3 embodiment of the invention 3 preparations characterizes;
Fig. 4 is the active comparative graph of title complex 5 and title complex 31 catalysis polymerizing butadienes.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of polyhutadiene, be specially:
Under the effect of promotor and cobalt complex with formula I structure, divinyl is carried out polyreaction in organic solvent, obtain polyhutadiene;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
In above-mentioned polymerization process, the independent catalysis polymerizing butadiene of said cobalt complex has catalytic activity, but after adding promotor, the common catalysis polymerizing butadiene of cobalt complex and promotor, then catalyzer has higher catalytic activity.Said promotor is preferably diethylammonium sesquialter aluminium, triisobutyl aluminium, triethyl aluminum or methyl alcoxyl aluminium, more preferably diethylammonium sesquialter aluminium.The mol ratio of cobalt is preferably 50 ~ 100 in aluminium in the said promotor and the said cobalt complex.
In the above-mentioned cobalt complex, said R
1And R
2Be the substituting group on the aniline, independently be preferably hydrogen, methyl, ethyl or sec.-propyl separately, more preferably hydrogen, methyl or sec.-propyl.Said R
3Be similarly the substituting group on the aniline, be preferably hydrogen, halogen, methyl, ethyl or sec.-propyl, more preferably hydrogen, chlorine, bromine or methyl.In the above-mentioned late transition metal complex, R
3During for halogen, R
3Same kind of halogen can be with X, also different halogens can be, as, R
3During for Cl, X can be Br.Cobalt is a kind of rear transition metal, and it is as the active site atom of title complex, and said rear transition metal and early transition metal are how much distinguishing according to d orbital electron number.Well known to those skilled in the art, said early transition metal is that d layer electronic number is no more than 5 transition metal, like Sc, V, Ti or Cr etc.; Said rear transition metal is that d layer electronic number surpasses 5 transition metal.
According to the present invention, said cobalt complex with formula I structure is specially title complex 1 ~ title complex 30, and is as shown in table 1, and table 1 is the concrete title complex table with late transition metal complex of formula I structure,
Table 1 is the concrete title complex table with late transition metal complex of formula I structure
According to the present invention, said preparation method, specifically preparation as follows with cobalt complex of formula II structure:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and cobalt is carried out the reaction second time, the cobalt complex that obtains having the formula I structure in second organic solvent;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
Said preparation process with part of formula II structure is specially:
Under nitrogen protection, with two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride are added in the methylene dichloride, and back flow reaction obtains mix products, with mix products extraction, recrystallization, the part that promptly obtains having the formula II structure.
Said two (substituted aniline)-2, the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is preferably 1:1.5 ~ 2.5,1:2 more preferably, the time of said back flow reaction is preferably 3 ~ 5h, more preferably 3.5 ~ 4.5h.
After obtaining said part, the halogenide of said part and cobalt is carried out the reaction second time, the cobalt complex that obtains having the formula I structure in second organic solvent.Said second organic solvent is preferably THF.The time of said reaction is preferably 3 ~ 7h, more preferably 4 ~ 6h.
According to the present invention, the halogenide of said part, said cobalt and the said second organic solvent blended be not restriction in proper order, can the halogenide of said part, said cobalt and said second organic solvent be added simultaneously to react.Equally also can said part be dissolved in second organic solvent, the halogenide of said cobalt is dissolved in second organic solvent, the halide solution that will be dissolved in the cobalt of second organic solvent then drops in the ligand solution that is dissolved in second organic solvent, reacts.Thorough for the halide reaction that makes said part and said cobalt, the present invention preferably adopts the back to plant hybrid mode.
After will having the cobalt complex preparation completion of formula I structure, the present invention will have the cobalt complex of formula I structure as catalyzer, and divinyl is carried out polyreaction in organic solvent.In the process of carrying out polyreaction, said divinyl and said cobalt complex blended be not restriction in proper order, can said divinyl, organic solvent, promotor and cobalt complex be added simultaneously and carry out polyreaction.Equally also can respectively divinyl be dissolved in the organic solvent, obtain first solution, promotor is dissolved in the organic solvent, obtain second solution, the title complex of cobalt is dissolved in the organic solvent, obtain the 3rd solution; Three kinds of solution that will obtain then mix, and carry out polyreaction.For said divinyl, promotor and cobalt complex are fully dissolved, the present invention preferably adopts the back to plant the adding mode.Simultaneously, for polyreaction is abundant, in the process of said polyreaction, guarantee that preferably ethene constantly supplies with.The temperature of said polyreaction is preferably 0 ~ 80 ℃, more preferably 20 ~ 60 ℃.The time that said polyreaction is is preferably 0.05h ~ 4h, and more preferably 0.1 ~ 2h most preferably is 0.3 ~ 1h.
Organic solvent is preferably toluene described in the present invention.Said volume of organic solvent is 15 ~ 20mL.The mol ratio of said cobalt complex and said divinyl is preferably 1: (1000 ~ 5000), more preferably 1: (2000 ~ 4000) most preferably are 1:3000.Test shows that the cobalt complex with formula I structure is in the process of catalysis polymerizing butadiene, and the yield of the polyhutadiene that obtains is 72 ~ 97%.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of polyhutadiene provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Reagent in the embodiment of the invention is the commercially available prod.
Embodiment 1
Take by weighing 5g (30mmol) pyridine-2, the 6-dioctyl phthalate adds the 30mL sulfur oxychloride to the 50mL round-bottomed flask, and backflow 24h is to forming homogeneous phase, and the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take by weighing 8.11g (60mmol) 2 and 8.36g (60mmol) triethylamine is dissolved in 50ml CH
2Cl
2In, take by weighing 6.1g (30mmol) pyridine dimethyl chloride and be dissolved in 20mL CH
2Cl
2In, pyridine dimethyl chloride/CH
2Cl
2Solution is toward substituted aniline/CH
2Cl
2The middle dropping refluxed after 4 hours, used 100ml water and 100ml1.5M Na respectively
2CO
3Solution washing obtains the CH of lower floor with separating funnel
2Cl
2Solution adds MgSO
4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (5b), and productive rate is 91%.(5b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm): 9.02 (s, 2H, NH), 8.51 (d, 2H, Pyr-H
m), 8.14 (t, 1H, Pyr-H
p), 6.95 (s, 4H, Ar-H), 2.30 (s, 6H, Ar-C
pH
3), 2.26 (s, 12H, Ar-C
oH
3);
13C NMR (100MHz, CDCl
3, δ, ppm): 161.6,148.8,139.3,137.1,134.8,130.5,128.9,125.5,20.9,18.4.Hence one can see that, and product (5b) can prepare.
Take by weighing 5g (12.46mmol) (5b) with 5.19g (24.92mmol) PCl
5In the 100mL round-bottomed flask, add the 100mL methylene dichloride afterwards, reflux after three hours, drain, with hot heptane extraction, get lurid n-heptane solution, decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (5c), and productive rate is 44.6%.(5c) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm): 8.49 (d, 2H, Pyr-H
m), 8.01 (t, 1H, Pyr-H
o), 6.94 (s, 4H, Ar-H), 2.32 (s, 6H, Ar-C
pH
3), 2.10 (s, 12H, Ar-C
oH
3);
13C NMR (100MHz, CDCl
3, δ, ppm): 151.2,145.2,143.4,137.6,134.0,128.6,125.8,125.6,20.8,17.8.IR（KBr，cm
-1）：1658（v
C=N）。Hence one can see that, and part (5c) can prepare.Above-mentioned reaction process is as follows:
Take by weighing 0.13g (1mmol) CoCl
2Be dissolved in and obtain blue suspension liquid among the 3mL THF, take by weighing 0.44g (1mmol) part (5c) and be dissolved among the 5mL THF, part/THF solution is toward CoCl
2Drip in/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get required title complex.Dry 0.4g, the productive rate 70.2% of getting.IR（KBr，cm
-1）：1626（v
C=N）。Above-mentioned reaction process is as follows:
Embodiment 2
Take by weighing 5g (30mmol) dinicotinic acid to the 50mL round-bottomed flask, add the 30mL sulfur oxychloride, backflow 24h is to forming homogeneous phase, and the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take by weighing 9.3g (60mmol) 4-chloro-2,6-xylidine and 8.36ml (60mmol) triethylamine is dissolved in 50mL CH
2Cl
2In, take by weighing 6.1g (30mmol) pyridine dimethyl chloride and be dissolved in 20mLCH
2Cl
2In, pyridine dimethyl chloride/CH
2Cl
2Solution is toward substituted aniline/CH
2Cl
2The middle dropping refluxed after 4 hours, used 100mL water and 100mL1.5M Na respectively
2CO
3Solution washing obtains the CH of lower floor with separating funnel
2Cl
2Solution adds MgSO
4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (9b).Productive rate 83.5%.(9b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm): 9.02 (s, 2H ,-NH), 8.54 (d, 2H, Pyr-H
m), 8.19 (t, 1H, Pyr-H
o), 7.16 (s, 4H, Ar-H), 2.28 (s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：161.5，148.6，139.5，137.1，132.8，131.8，128.1，125.8，18.4。Hence one can see that, and product (9b) can prepare.
Take by weighing (9b) 5.51g (12.46mmol) and PCl
55.19g (24.92mmol) in the 100mL round-bottomed flask, add the 100mL methylene dichloride afterwards, reflux after three hours; Drain,, get lurid n-heptane solution with hot heptane extraction; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (9c), productive rate 63%.(9c) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm): 8.50 (d, 2H, Pyr-H
m), 8.03 (t, 1H, Pyr-H
o), 7.11 (s, 4H, Ar-H), 2.11 (s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：150.8，145.2，144.1，137.6，129.4，127.8，127.7，125.6，17.6。IR（KBr，cm
-1）：1656（v
C=N）。Hence one can see that, and part (9c) can prepare.Above-mentioned reaction process is as follows:
Take by weighing 0.13g (1mmol) CoCl
2Be dissolved in and obtain blue suspension liquid among the 3mL THF, take by weighing 0.48g (1mmol) part (9c) and be dissolved among the 5mL THF, part/THF solution is toward CoCl
2Drip in/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get required title complex.Dry 0.53g, the productive rate 86.9% of getting.IR（KBr，cm
-1）：1625（v
C=N）。Above-mentioned reaction process is as follows:
Take by weighing 5g (30mmol) dinicotinic acid to the 50mL round-bottomed flask, add the 30mL sulfur oxychloride, backflow 24h is to forming homogeneous phase, and the sulfur oxychloride that decompressing and extracting is unnecessary obtains the pyridine dimethyl chloride of pale pink, directly as next step reaction.
Take by weighing 11.94g (60mmol) 4-bromo-2,6-xylidine and 8.36mL (60mmol) triethylamine is dissolved in 50mL CH
2Cl
2In, take by weighing 6.1g (30mmol) pyridine dimethyl chloride and be dissolved in 20mL CH
2Cl
2In, pyridine dimethyl chloride/CH
2Cl
2Solution is toward substituted aniline/CH
2Cl
2The middle dropping refluxed after 4 hours, used 100mL water and 100mL1.5M Na respectively
2CO
3Solution washing obtains the CH of lower floor with separating funnel
2Cl
2Solution adds MgSO
4Dried overnight is filtered and is drained, and carries out recrystallization with toluene then, and filtration drying promptly gets product (10b).Productive rate 86.4%.(10b) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm), 8.98 (s, 2H ,-NH-), 8.55 (d, 2H, Pyr-H
m), 8.19 (t, 1H, Pyr-H
o), 7.33 (s, 4H, Ar-H), 2.30 (s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：161.5，148.6，139.5，137.4，131.0，128.2，125.8，120.9，18.2。Hence one can see that, and product (10b) can prepare.
Take by weighing (10b) 6.62g (12.46mmol) and PCl
55.19g (24.92mmol) in the 100mL round-bottomed flask, add the 100mL methylene dichloride afterwards, reflux after three hours; Drain,, get lurid n-heptane solution with hot heptane extraction; Decompression is evacuated to saturated back recrystallization, promptly gets yellow powder product (10c), productive rate 44.6%.(10c) carries out nuclear magnetic resonance spectroscopy to product, and characterization result is following:
1H NMR (400MHz, CDCl
3, δ, ppm): 8.49 (d, 2H, Pyr-H
m), 8.03 (t, 1H, Pyr-H
o), 7.25 (s, 4H, Ar-H), 2.10 (s, 12H ,-CH
3).
13C?NMR（100MHz，CDCl
3，δ，ppm）：150.8，146.0，144.7，137.6，130.5，128.1，125.6，117.3，17.5。IR（KBr，cm
-1）：1655（v
C=N）。Hence one can see that, and part (10c) can prepare.Above-mentioned reaction process is as follows:
Take by weighing 0.13g (1mmol) CoCl
2Be dissolved in and obtain blue suspension liquid among the 3mL THF, take by weighing 0.57g (1mmol) part (10c) and be dissolved among the 5mL THF, part/THF solution is toward CoCl
2Drip in/THF the solution, stir 2h, obtain green suspension, cross and filter green powder, promptly get required title complex.Dry 0.61g, the productive rate 87.1% of getting.IR（KBr，cm
-1）：1624（v
C=N）。Above-mentioned reaction process is as follows:
Embodiment 4
Basic identical with the preparation method of embodiment 1, difference is: 60mmol aniline and 60mmol triethylamine are dissolved in 50mLCH
2Cl
2In, all the other operation stepss are identical, promptly obtain having the title complex 1 of formula III structure.
Embodiment 5
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.006g title complex 1, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 71.8%, and molecular weight is 17.54 * 10
4, MWD is 2.77, cis-1,4 content are 96%.
Embodiment 6
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.0075g title complex 9, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 93.6%, and molecular weight is 6.48 * 10
4MWD is 4.82, and cis-1, the content of 4-are 94.4%.
Embodiment 7
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 1mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization, behind the 3min, in polymerization bottle, add and contain 2; The ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out glue and uses a large amount of washing with alcohol, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 74%, and molecular weight is 7.03 * 10
4, MWD is 1.62, cis-1, the content of 4-are 97.7%.
Embodiment 8
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 1mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization, behind the 8min, in polymerization bottle, add and contain 2; The ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out glue and uses a large amount of washing with alcohol, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 76.2%, and molecular weight is 7.05 * 10
4, MWD is 3.46, cis-1, the content of 4-are 93%.
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 0 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 74.7%, and molecular weight is 18.0 * 10
4, MWD is 1.81, cis-1, the content of 4-are 98.5%.
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 80 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 70%, and molecular weight is 2.14 * 10
4, MWD is 7.53, cis-1, the content of 4-are 76.8%.
Embodiment 11
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add the 0.05mL MAO, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization, behind the 4h, in polymerization bottle, add and contain 2; The ethanolic soln of 6-di-tert-butyl-4-methy phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) stops polyreaction, separates out glue and uses a large amount of washing with alcohol, and 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 73.5%, and molecular weight is 0.81 * 10
4MWD is 3.72, and cis-1, the content of 4-are 94.9.
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 97%, and molecular weight is 5.32 * 10
4, MWD is 5.19, cis-1, the content of 4-are 93.1%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, and the ■ curve is the polymerization activity curve of polymkeric substance 5 among the figure.
Embodiment 13
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing 0.007g title complex 5, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization; Behind the 8min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 76.2%, and molecular weight is 7.0 * 10
4, MWD is 3.46, cis-1, the content of 4-are 93.0.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, and the ■ curve is the polymerization activity curve of polymkeric substance 5 among the figure.Can know that by Fig. 4 polymkeric substance 5 has advantages of high catalytic activity.
Comparative Examples 1
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.In previously baked ampoule after filling nitrogen, take by weighing the title complex 31 that 0.0065g has the formula IV structure, add 20mL divinyl toluene solution then; Shake up, add 0.5mL diethylammonium sesquialter aluminium, become homogeneous phase solution with syringe; Put into pre-prepd 20 ℃ water bath with thermostatic control initiated polymerization; Behind the 20min, in polymerization bottle, add the ethanolic soln that contains 2,6 di tert butyl 4 methyl phenol (1wt/v-%) and small amount of hydrochloric acid (2v/v-%) and stop polyreaction; Separate out glue and use a large amount of washing with alcohol, 40 ℃ of freeze-day with constant temperature are to constant weight.The yield of polyhutadiene is 92%, and molecular weight is 5.32 * 10
4, MWD is 5.21, cis-1, the content of 4-are 93.1%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, among the figure ● curve is the polymerization activity curve of polymkeric substance 31.
Comparative Examples 2
Divinylic monomer is fed in the toluene solution, according to the divinyl toluene solution of mass method configuration 0.1g/mL.After a pre-baking nitrogen ampoule bottled in 31 complexes weighed 0.0065g, then adding a toluene solution of butadiene 20mL, shake, 0.5mL syringe diethyl aluminum sesqui, a homogeneous solution, put 20 ℃ prepared in advance into a constant temperature water bath to initiate the polymerization, 8min after the polymerization flask containing 2,6 - di-tert-butyl-4 - methylphenol (1wt/v-%) and a small amount of hydrochloric acid (2v / v -%) in ethanol to terminate the polymerization, with plenty of ethanol precipitated gel, 40 ℃ temperature drying to constant weight.The yield of polyhutadiene is 32.3%, and molecular weight is 10.4 * 10
4, MWD is 2.1, cis-1, the content of 4-are 95.9%.Fig. 4 is title complex 5 and the polymerization activity graphic representation of title complex 31 under different time, among the figure ● curve is the polymerization activity curve of polymkeric substance 31.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a polyhutadiene is characterized in that, comprising:
Under the effect of promotor and cobalt complex with formula I structure, divinyl is carried out polyreaction in organic solvent, obtain polyhutadiene;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
2. preparation method according to claim 1 is characterized in that, the mol ratio of said cobalt complex and said divinyl is 1: (1000 ~ 5000).
3. preparation method according to claim 1 is characterized in that, the temperature of said polyreaction is 0 ~ 100 ℃.
4. preparation method according to claim 1 is characterized in that, said promotor is diethylammonium sesquialter aluminium, triisobutyl aluminium, triethyl aluminum or methyl alcoxyl aluminium.
5. preparation method according to claim 1 is characterized in that, the time of said polyreaction is 0.05h ~ 4h.
6. preparation method according to claim 1 is characterized in that, said R1 and R2 independently are selected from hydrogen, methyl, ethyl or sec.-propyl separately.
7. preparation method according to claim 1 is characterized in that, said R3 is hydrogen, chlorine, bromine, methyl, ethyl or sec.-propyl.
8. preparation method according to claim 1 is characterized in that, the preparation method of said cobalt complex is specially:
With two (substituted aniline)-2,6-pyridine diformamide and phosphorus pentachloride carry out first set reaction, the part that obtains having the formula II structure in first organic solvent;
The halogenide of said part and cobalt is carried out the reaction second time, the cobalt complex that obtains having the formula I structure in second organic solvent;
Wherein, R
1And R
2Independently be selected from the alkyl of hydrogen or C1 ~ C10 separately;
R
3Alkyl for hydrogen, halogen or C1 ~ C10;
X is a halogen.
9. according to Claim 8 preparation method is characterized in that, said two (substituted aniline)-2, and the mol ratio of 6-pyridine diformamide and said phosphorus pentachloride is 1: (1.5 ~ 2.5).
10. preparation method according to claim 8 is characterized in that, the time of said first set reaction is 3 ~ 5h, and the time of the said reaction second time is 3 ~ 7h.
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|---|---|---|---|---|
| CN104837877A (en) * | 2012-12-20 | 2015-08-12 | 维尔萨利斯股份公司 | Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt |
| CN114058376A (en) * | 2021-11-10 | 2022-02-18 | 崔怡 | Recoverable soil restoration agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119662A1 (en) * | 1999-08-06 | 2003-06-26 | The Goodyear Tire & Rubber Company | Transition metal catalysts for diene polymerizations |
| CN1980873A (en) * | 2004-07-13 | 2007-06-13 | 国际壳牌研究有限公司 | Process for preparing linear alpha olefins |
| CN101277981A (en) * | 2005-08-02 | 2008-10-01 | 英尼奥斯欧洲有限公司 | Diene polymerisation |
-
2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030119662A1 (en) * | 1999-08-06 | 2003-06-26 | The Goodyear Tire & Rubber Company | Transition metal catalysts for diene polymerizations |
| CN1980873A (en) * | 2004-07-13 | 2007-06-13 | 国际壳牌研究有限公司 | Process for preparing linear alpha olefins |
| CN101277981A (en) * | 2005-08-02 | 2008-10-01 | 英尼奥斯欧洲有限公司 | Diene polymerisation |
Non-Patent Citations (1)
| Title |
|---|
| THEO M.SMIT ET AL: "The effect of imine-carbon substituents in bis(imino）pyridine-based ethylene polymerisation catalysts across the transition series", 《CATALYSIS SCIENCE & TECHNOLOGY》, no. 2, 19 December 2011 (2011-12-19), pages 643 - 655 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104837877A (en) * | 2012-12-20 | 2015-08-12 | 维尔萨利斯股份公司 | Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt |
| TWI602836B (en) * | 2012-12-20 | 2017-10-21 | 維薩里公司 | Process for the preparation of (co) polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt |
| CN104837877B (en) * | 2012-12-20 | 2017-11-10 | 维尔萨利斯股份公司 | For the technique for the (co) polymer that conjugated diene is prepared in the presence of the catalyst system and catalyzing of the oxo nitridation complex compound comprising cobalt |
| CN114058376A (en) * | 2021-11-10 | 2022-02-18 | 崔怡 | Recoverable soil restoration agent and preparation method thereof |
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