CN110218272B - Preparation method of polyisobutylene and isobutylene copolymer - Google Patents
Preparation method of polyisobutylene and isobutylene copolymer Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention relates to a preparation method of polyisobutylene and isobutylene copolymer, which adopts a catalyst consisting of a heterocyclic condensed cyclopentadienyl rare earth compound with a heterocyclic condensed cyclopentadienyl ligand having a greater conjugation effect and organic boron salt to realize isobutylene homopolymerization and copolymerization of isobutylene and a second monomer in an organic solution. The catalyst formed by the heterocyclic condensed cyclopentadienyl rare earth compound and the organic boron salt has high polymerization activity and efficiency, can be used for preparing high-activity polyisobutene at higher temperature and preparing high-molecular-weight polyisobutene and isobutene copolymer at lower temperature, and the chelate ligand has simple synthesis and lower cost and can be industrially produced. The preparation method of the polyisobutylene and the isobutylene copolymer provided by the invention can regulate and control the molecular weight of the polymer by changing the ratio of the catalyst to the monomer, the polymerization temperature and other methods.
Description
Technical Field
The invention relates to the technical field of preparation of polyisobutylene and isobutylene copolymers, in particular to a preparation method of polyisobutylene and isobutylene copolymers, which realizes isobutylene homopolymerization and copolymerization of isobutylene and a second monomer in an organic solution by using a rare earth metal catalyst, and the molecular weight of the polymer can be regulated and controlled by changing the ratio of the catalyst to the monomer, the polymerization temperature and the like.
Background
England scientists discovered in 1996 a bis-metallocene aluminum methyl compound and an organoboron salt B (C)6F5)3The formed catalytic system can catalyze the copolymerization of isobutene and isoprene at-78 ℃ to-25 ℃ to prepare polyisobutylene with high molecular weight (Angew. chem. int. Ed.1996,35, 2226-2228). However, the polymerization activity of the catalytic system is closely related to the metalloaluminium chelating ligand, and when a dicyclopentadienyl aluminium compound is chelated with a cyclopentadienyl ligand having a large steric hindrance, the polymerization activity disappears. Later, it was discovered that bis-metallocene rare earth yttrium methyl compoundsThe compound and an organic boron salt [ Ph3C][B(C6F5)4]The catalyst system formed can also initiate the polymerization of isobutene at-78 deg.C to-50 deg.C to prepare polyisobutene having a weight-average molecular weight of over 100 ten thousand, but the activity and efficiency of the catalyst system are low (Organometallics,1998,17, 1004-1006). Canadian found the titanocene trimethyl compound Cp. TiMe3With organic boron salts [ P h3C][B(C6F5)4]And B (C)6F5)3The catalyst system is capable of catalyzing isobutylene homopolymerization and isobutylene copolymerization with isoprene (J.chem.Soc., chem.Commun.1995, 1065-1066). England researchers found that zirconocenes or hafnium dimethyl in organoboron salts [ Ph3C][B(C6F5)4]With the aid of (A), it is possible to prepare high molecular weight polyisobutenes and butyl rubbers (macromolecules, 1998,31, 2035-2040). Recently, researchers at university of Macro-Cochinery discovered that the monocyclopentadienyl compound reacted with [ Ph3C][B(C6F5)4]The catalyst system can catalyze the polymerization of isobutene to prepare the polyisobutene with medium and high molecular weight, and the maximum molar ratio of the monomer to the catalyst reaches 4000 times (CN201611201946. X). According to literature data, the transition metal chelating ligand, initiating group, polymerization solvent and the like have great influence on the polymerization performance of a catalytic system, and the catalytic activity of the catalyst and the molecular weight of the prepared polymer can be effectively regulated and controlled through the optimized combination of the chelating ligand.
Disclosure of Invention
The invention provides a preparation method of polyisobutylene and isobutylene copolymer, aiming at solving the technical problems of low polymerization temperature, high energy consumption and complex polymerization process of the traditional preparation method of butyl rubber and polyisobutylene in the prior art.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a preparation method of polyisobutylene and an isobutylene copolymer, which comprises the following steps:
under the anhydrous and oxygen-free conditions, a catalyst composition consisting of a heterocyclic condensed cyclopentadienyl rare earth compound and an organic boron compound is utilized to initiate isobutylene homopolymerization or isobutylene and a second monomer copolymerization to prepare polyisobutylene or an isobutylene copolymer; the polymerization reaction is solution polymerization, the reaction temperature is-80 ℃ to 50 ℃, and the time is 1/6 to 24 hours.
In the technical scheme, the structural formula of the heterocyclic condensed cyclopentadienyl rare earth compound is shown as a formula I:
in formula I:
R1is hydrogen or methyl;
R2is hydrogen, methyl or phenyl;
R3is hydrogen, methyl, trimethylsilyl, phenyl or benzyl;
R4is hydrogen or methyl;
R5is hydrogen, methyl, trimethylsilyl, phenyl or benzyl;
X1and X2Independently selected from alkyl, silyl, aryl, benzyl and derivatives thereof, allyl and derivatives thereof or borohydride;
w is tetrahydrofuran or dimethyl ethylene glycol ether;
n is the number of bits of W and is 0,1 or 2;
ln is a rare earth metal element selected from scandium, yttrium, lutetium, ytterbium, thulium, erbium, holmium, dysprosium, gadolinium, neodymium or lanthanum.
In the above-mentioned aspect, X is preferable1And X2Independently selected from methyl, trimethylsilylene, bis (trimethylsilylene) methine, allyl, 2-methylallyl, benzyl, p-methylbenzyl or boron tetrahydride; w is tetrahydrofuran; ln is scandium, yttrium, lutetium, neodymium or gadolinium.
In the above-mentioned aspect, X is more preferably X1And X2Independently selected from methyl, trimethylsilylene, allyl, 2-methylallyl, benzyl or p-methylbenzyl, and Ln is scandium or yttrium.
In the above technical solutions, the most important isPreferably X1And X2Independently selected from methyl, trimethylsilylene, benzyl or p-methylbenzyl.
In the above technical scheme, most preferably, the heterocyclic fused cyclopentadienyl rare earth compound is selected from any one of the following structures:
in the above scheme, the organoboron compound is selected from [ Ph3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3、[NEt3H][B(C6F5)4]Or [ NBu ]3H][B(C6F5)4]。
In the above technical scheme, the mole ratio of the heterocyclic condensed cyclopentadienyl rare earth compound to the organoboron compound is 1: (0.5-2.0).
In the above technical scheme, the molar ratio of the heterocyclic fused cyclopentadienyl rare earth compound to the isobutene and the second monomer is 1: (100000-5000): (3000-0).
In the above technical solution, the second monomer is isoprene, butadiene, β -myrcene, 2, 3-dimethyl-1, 3-butadiene, p-methylstyrene, p-alkoxystyrene, σ -methylstyrene, σ -methyl-p-alkoxystyrene, or vinyl alkyl ether monomer.
The invention has the beneficial effects that:
the invention provides a preparation method of polyisobutylene and isobutylene copolymer, which adopts a catalyst consisting of a heterocyclic condensed cyclopentadienyl rare earth compound with a heterocyclic condensed cyclopentadienyl ligand having a greater conjugation effect and organic boron salt to realize isobutylene homopolymerization and copolymerization of isobutylene and a second monomer in an organic solution. The catalyst formed by the heterocyclic condensed cyclopentadienyl rare earth compound and the organic boron salt has high polymerization activity and efficiency, can be used for preparing high-activity polyisobutene at higher temperature and preparing high-molecular-weight polyisobutene and isobutene copolymer at lower temperature, and the chelate ligand has simple synthesis and lower cost and can be industrially produced.
The preparation method of the polyisobutylene and the isobutylene copolymer provided by the invention can regulate and control the molecular weight of the polymer by changing the ratio of the catalyst to the monomer, the polymerization temperature and other methods.
Detailed Description
The invention provides a preparation method of polyisobutylene and an isobutylene copolymer, which comprises the following steps:
under the anhydrous and oxygen-free conditions, a heterocyclic condensed cyclopentadienyl rare earth compound and an organic boron compound are mixed in an organic solvent according to a certain proportion to form a catalyst composition, then an organic solution of the catalyst composition is added into a reaction device filled with a certain amount of isobutene organic solution (or containing a certain amount of copolymerization second monomer) to initiate polymerization reaction, the polymerization reaction is carried out at-80-50 ℃, after 1/6-24 hours of polymerization, the polymerization solution is poured into ethanol to settle polymers, and the polyisobutylene or the isobutylene copolymer is obtained after drying.
The catalyst composition is prepared from a heterocyclic fused cyclopentadienyl rare earth compound and an organoboron compound in an organic solvent.
The structural formula of the heterocyclic condensed cyclopentadienyl rare earth compound is shown as a formula I:
in the formula I, R1Is hydrogen or methyl; r2Is hydrogen, methyl or phenyl; r3Is hydrogen, methyl, trimethylsilyl, phenyl or benzyl; r4Is hydrogen or methyl; r5Is hydrogen, methyl, trimethylsilyl, phenyl or benzyl.
In the formula I, X1And X2Selected from alkyl, silyl, aryl, benzyl and derivatives thereof, allyl and derivatives thereof or borohydride; preferably: methyl, trimethylsilylene, bis (trimethylsilylene) methine, allyl, 2-methylallyl, benzyl, p-methylbenzyl or boron tetrahydride; re-optimizationSelecting as follows: methyl, trimethylsilylene, allyl, 2-methylallyl, benzyl or p-methylbenzyl; most preferred is methyl, trimethylsilylene, benzyl or p-methylbenzyl.
In the formula I, W is tetrahydrofuran or dimethyl ethylene diether; preferably tetrahydrofuran; n is the number of bits of W and is 0,1 and 2.
In the formula I, Ln is a rare earth metal element selected from scandium, yttrium, lutetium, ytterbium, thulium, erbium, holmium, dysprosium, gadolinium, neodymium or lanthanum; preferably scandium, yttrium, lutetium, neodymium or gadolinium; more preferably scandium or yttrium.
The organoboron compound is selected from [ Ph3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、[NEt3H][B(C6F5)4]、B(C6F5)3Or [ NBu ]3H][B(C6F5)4]Preferably [ Ph3C][B(C6F5)4]。
The mol ratio of the heterocyclic condensed cyclopentadienyl rare earth compound to the organic boron compound is 1: (0.5 to 2.0); preferably 1:1 or 1: 2.
The heterocyclic condensed cyclopentadienyl rare earth compound, isobutene and a second monomer are in a molar ratio of 1: (100000-5000): (3000-0).
Preferably, the second monomer is isoprene, butadiene, beta-myrcene, 2, 3-dimethyl-1, 3-butadiene, p-methylstyrene, 4-alkoxystyrene, sigma-methylstyrene, sigma-methyl-p-alkoxystyrene or a vinyl alkyl ether monomer. Further preferably isoprene, β -myrcene, 2, 3-dimethyl-1, 3-butadiene, 4-allyloxystyrene, 4-butene-1-propoxystyrene, 4-allyloxy- σ -methylstyrene, 4-butene-1-oxy- σ -methylstyrene, vinyl ethyl ether, vinyl t-butyl ether or vinyl methyl ether; most preferred is isoprene, beta-myrcene, 2, 3-dimethyl-1, 3-butadiene, 4-buten-1-oxy-sigma-methylstyrene or vinyl ethyl ether.
In the invention, the solvent in the organic solution of the catalyst is preferably one or more of alkane, aromatic hydrocarbon, halogenated aromatic hydrocarbon and cycloalkane, more preferably one or more of saturated alkane, saturated aromatic hydrocarbon, saturated halogenated aromatic hydrocarbon and saturated cycloalkane, and most preferably one or more of n-hexane, petroleum ether, cyclohexane, pentane, toluene, chlorobenzene, decalin and dichloromethane. The solvent in the catalyst solution is not particularly limited in the present invention, and may be commercially available.
The polymerization reaction is carried out in an organic solvent, wherein the organic solvent is preferably one or more of alkane, aromatic hydrocarbon, halogenated aromatic hydrocarbon and cycloalkane, more preferably one or more of saturated alkane, saturated aromatic hydrocarbon, saturated halogenated aromatic hydrocarbon and saturated cycloalkane, and most preferably one or more of n-hexane, petroleum ether, cyclohexane, pentane, toluene, chlorobenzene and dichloromethane. The present invention is not particularly limited with respect to the source of the polymerization solvent.
In the specific implementation process, the invention is preferably illustrated by the following heterocyclic condensed cyclopentadienyl rare earth compounds as examples for polymerization of isobutene and the second comonomer:
to further illustrate the present invention, the technique of isobutylene polymerization or copolymerization with a second monomer provided by the present invention is described in detail below with reference to examples.
EXAMPLE 1 homopolymerization of isobutylene
Under the protection of nitrogen, 9.4 g of 30 wt% isobutylene toluene solution is added into a 100 ml reaction kettle at-45 ℃, after a polymerization reaction device and a polymerization solution are cooled to a set temperature, 10 micromoles of rare earth compound 1 and 10 micromoles of organic boron salt [ Ph ] are added3C][B(C6F5)4]Polymerization was then initiated with a toluene solution (2 ml) of the composition. Stirring at-45 deg.C for 60 min, adding the polymerized solution into a container containing 100 ml of ethanol to terminate reaction, drying the settled polyisobutylene in a vacuum drying oven at 60 deg.C to constant weight, and converting the monomerThe ratio was 75%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝3.03×104，Mn/Mw＝2.39。
The following examples 2-23 polymerization conditions were the same as in example 1 except for the conditions described in the table:
| examples | Cat. | IB/Cat. | Temp.(℃) | Time(h) | Yield(％) | Mn(×104) | PDI |
| 2 | 2 | 7200 | -45 | 1 | 88 | 7.50 | 2.20 |
| 3 | 2 | 10000 | -45 | 1 | 86 | 8.24 | 2.05 |
| 4 | 2 | 5000 | -45 | 1 | 67 | 6.52 | 2.29 |
| 5 | 2 | 3000 | -45 | 1 | 78 | 9.44 | 1.90 |
| 6 | 2 | 15000 | -45 | 1.5 | 83 | 9.97 | 1.80 |
| 7 | 2 | 12000 | -45 | 4 | 61 | 8.09 | 1.80 |
| 8 | 2 | 10000 | -35 | 10 | 76 | 4.89 | 2.74 |
| 9 | 2 | 10000 | -60 | 24 | 70 | 4.82 | 1.53 |
| 10 | 2 | 5700 | -75 | 24 | 73 | 3.00 | 1.62 |
| 11 | 2 | 10000 | 20 | 1 | 75 | 1.11 | 1.73 |
| 12 | 2 | 10000 | 0 | 1 | 78 | 1.54 | 1.98 |
| 13 | 2 | 10000 | -15 | 1 | 80 | 4.30 | 1.99 |
| 14 | 2 | 10000 | -30 | 1 | 77 | 5.23 | 2.08 |
| 15 | 2 | 20000 | -45 | 2 | 89 | 16.4 | 2.06 |
| 16 | 2 | 30000 | -45 | 2.5 | 79 | 19.7 | 2.14 |
| 17 | 2 | 50000 | -45 | 5 | 86 | 24.1 | 2.25 |
| 18 | 2 | 70000 | -45 | 8 | 79 | 32.3 | 1.89 |
| 19 | 2 | 100000 | -45 | 12 | 87 | 67.8 | 2.19 |
| 20 | 1 | 10000 | -45 | 1 | 78 | 10.2 | 1.67 |
| 21 | 3 | 10000 | -45 | 1 | 85 | 9.6 | 2.11 |
| 22 | 4 | 10000 | -45 | 1 | 91 | 10.3 | 2.02 |
| 23 | 5 | 10000 | 50 | 1 | 81 | 0.52 | 2.34 |
Note: in the table IB represents isobutene, Cat represents a heterocyclic fused cyclopentadienyl rare earth dialkyl compound and h represents h. When the ratio of IB to Cat is more than 4000 times, the polymerization reaction apparatus is 300 ml.
EXAMPLE 24 copolymerization of isobutylene with a second monomer
Under the protection of nitrogen, 18.8 g of 30 wt% isobutylene toluene solution and 0.68 g of isoprene were added into a 100 ml reaction kettle at-45 ℃, and after the polymerization reaction device and the polymerization solution were cooled to a set temperature, 10. mu. mol of rare earth compound 6 and 20. mu. mol of organic boron salt [ Ph ] were added3C][B(C6F5)4]Polymerization was then initiated with a toluene solution (2 ml) of the composition. Stirring and reacting at-45 ℃ for 60 minutes, pouring the polymerization solution into a container filled with 100 ml of ethanol to terminate the reaction, drying the settled isobutylene copolymer in a vacuum drying oven at 60 ℃ to constant weight, wherein the monomer conversion rate is 65%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝2.19×104，Mn/Mw＝2.39。
Example 25
Under the protection of nitrogen, 37.6 g of 30 wt% isobutylene toluene solution and 2.04 g of isoprene were added into a 250 ml reaction kettle at-55 ℃, and after the polymerization reaction device and the polymerization solution were cooled to a set temperature, 10. mu. mol of rare earth compound 2 and 20. mu. mol of organic boron salt [ Ph ] were added3C][B(C6F5)4]Polymerization was then initiated with a toluene solution (2 ml) of the composition. Stirring and reacting for 120 minutes at the temperature of minus 55 ℃, pouring the polymerization solution into a container filled with 200 ml of ethanol to terminate the reaction, drying the settled isobutene copolymer in a vacuum drying oven at the temperature of 60 ℃ to constant weight, wherein the monomer conversion rate is 71%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝5.14×104，Mn/Mw＝1.87。
Example 26
Otherwise as in example 24, the second monomer was 0.82 g of 2, 3-dimethyl-1, 3-butadiene. The total monomer conversion was 73%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝3.19×104，Mn/Mw＝1.69。
Example 27
Otherwise conditions were the same as in example 24, the second monomer was 1.36 grams of beta-myrcene. The overall conversion of monomer was 71%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝5.13×104，Mn/Mw＝2.15。
Example 28
Otherwise as in example 24, the second monomer was 0.72 g of vinyl ethyl ether. The overall monomer conversion was 87%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝6.21×104，Mn/Mw＝2.01。
Example 29
Otherwise the conditions were the same as in example 24, and the second monomer was 1.74 g of 4-allyloxy-sigma-methylstyrene. The overall conversion of monomer was 69%. The number average molecular weight M of the polyisobutene obtained was determined by gel chromatographyn＝4.63×104，Mn/Mw＝1.63。
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A preparation method of polyisobutylene and isobutylene copolymer is characterized by comprising the following steps:
under the anhydrous and oxygen-free conditions, a catalyst composition consisting of a heterocyclic condensed cyclopentadienyl rare earth compound and an organic boron compound is utilized to initiate isobutylene homopolymerization or isobutylene and a second monomer copolymerization to prepare polyisobutylene or an isobutylene copolymer; the polymerization reaction is solution polymerization, the reaction temperature is-80-50 ℃, and the time is 1/6-24 hours;
the molar ratio of the isobutene to the heterocyclic condensed cyclopentadienyl rare earth compound is (10000-7200): 1;
the structural formula of the heterocyclic condensed cyclopentadienyl rare earth compound is shown as a formula I:
in formula I:
R1is hydrogen or methyl;
R2is hydrogen, methyl or phenyl;
R3is hydrogen, methyl, trimethylsilyl, phenyl or benzyl;
R4is hydrogen or methyl;
R5is hydrogen, methyl, trimethylsilyl, phenyl or benzyl;
X1and X2Independently selected from alkyl, silyl, aryl, benzyl and derivatives thereof, allyl and derivatives thereof or borohydride;
w is tetrahydrofuran or dimethyl ethylene glycol ether;
n is the number of bits of W and is 0,1 or 2;
ln is a rare earth metal element selected from scandium, yttrium, lutetium, ytterbium, thulium, erbium, holmium, dysprosium, gadolinium, neodymium or lanthanum.
2. The process for the preparation of polyisobutenes and isobutene copolymers as claimed in claim 1, wherein X is1And X2Independently selected from methyl, trimethylsilylene, bis (trimethylsilylene) methine, allyl, 2-methylallyl, benzyl, p-methylbenzyl or boron tetrahydride; w is tetrahydrofuran; ln is scandium, yttrium, lutetium, neodymium or gadolinium.
3. The process for the preparation of polyisobutenes and isobutene copolymers as claimed in claim 2, wherein X is1And X2Independently selected from methyl, trimethylsilylene, allyl, 2-methylallyl, benzyl or p-methylbenzyl, and Ln is scandium or yttrium.
4. Preparation of polyisobutenes and isobutene copolymers as claimed in claim 3A process for preparing the same, wherein X is1And X2Independently selected from methyl, trimethylsilylene, benzyl or p-methylbenzyl.
5. The method of claim 1, wherein the heterocyclic fused cyclopentadienyl rare earth compound is selected from any one of the following structures:
6. the process for producing polyisobutylene and isobutylene copolymer according to claim 1, wherein the organoboron compound is selected from [ Ph ™ ]3C][B(C6F5)4]、[PhNMe2H][B(C6F5)4]、B(C6F5)3、[NEt3H][B(C6F5)4]Or [ NBu ]3H][B(C6F5)4]。
7. The method for preparing polyisobutylene and isobutylene copolymer according to claim 1, wherein the molar ratio of the heterocyclic fused cyclopentadienyl rare earth compound to the organoboron compound is 1: (0.5-2.0).
8. The method of claim 1, wherein the second monomer is isoprene, butadiene, β -myrcene, 2, 3-dimethyl-1, 3-butadiene, p-methylstyrene, p-alkoxystyrene, or vinyl alkyl ether monomer.
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| CN106632768B (en) * | 2016-12-23 | 2019-08-20 | 大连理工大学 | Rare earth butyl rubber and preparation method thereof |
| CN106632767B (en) * | 2016-12-23 | 2019-08-20 | 大连理工大学 | The method of the rare earth catalyst and its catalysis in olefine polymerization of a kind of nitrogen-containing heterocycle carbenes |
| CN109593161B (en) * | 2018-12-18 | 2020-09-22 | 中国科学院长春应用化学研究所 | High-1, 2-regioselectivity poly (allene) and preparation method thereof |
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