Method for preparing polyisobutene and segmented copolymer thereof through Fe-based coinitiator

Abstract

The invention provides a method for preparing polyisobutene and a segmented copolymer thereof through a Fe-based co-initiator, and particularly relates to a method for polymerizing isobutene in the presence of a main initiator and a co-initiator, and then terminating and quenching to obtain high-activity polyisobutene of which the terminal external olefin double bond is close to 100%. And adding the third component, and then preparing the segmented copolymer from the third component, vinyl ether monomers, styrene and derivatives thereof, and bio-based monomers.

Description

Technical Field

[0001] The present invention relates to a method for preparing highly active polyisobutylene and copolymerization thereof with vinyl ether monomers, styrene and its derivatives, and bio-based monomers, and particularly to FeCl 3 and FeCl 3 ·xH 2 O is aged and complexed with a complexing agent to obtain a co-initiator, isobutylene is polymerized in the presence of a main initiator and a co-initiator, and then terminated and quenched to obtain a highly active polyisobutylene with nearly 100% terminal external olefin double bonds, and a method for preparing a block copolymer with vinyl ether monomers, styrene and its derivatives, and bio-based monomers after adding a third component. Background Art

[0002] Cationic polymerization of isobutylene (IB) has attracted wide attention due to its potential value in industrial applications. Highly reactive polyisobutylene (HRPIB) is a special type of polyisobutylene with extremely high reactivity. Its molecular weight is usually between 500 and 5000, and the content of exoolefin functional groups at the chain end exceeds 60%. HRPIB has the characteristics of acid and alkali resistance, excellent dispersibility, excellent low temperature resistance and excellent thermal stability. Due to the presence of α-exoolefin, its performance is better than that of ordinary polyisobutylene. In addition to being used as a macromolecular material blended into elastomers to improve the low temperature resistance and viscosity of elastomers, HRPIB can also be used for building seals. It can also change its physical and chemical properties by reacting with other substances to form block polymers, thereby broadening its application areas, such as polyisobutylene phenol, polyisobutylene phosphate and polyisobutylene amine, cyclohexyl vinyl ether-isobutylene-cyclohexyl vinyl ether triblock copolymer, poly-tert-butyl vinyl ether-b-isobutylene-b-tert-butyl vinyl ether triblock copolymer, etc.

[0003] HRPIB with different terminal structures includes the following structures: A is an α-exoolefin structure; B and C are β-exoolefin structures; D is a trisubstituted terminal structure; E and F are coupled double bond structures.

[0004]

[0005] In the highly active polyisobutylene polymerization process, AlCl 3 SnCl 4 、TiCl 4 and BCl 3 etc. as co-initiators, but the reaction system is severely isomerized and the exo-olefin content is difficult to further increase. The reaction needs to be carried out under low temperature conditions, and the reaction cost is high. In addition, the product contains a large amount of heavy metal residues, which increases the cumbersome post-processing process.

[0006] The existing technology uses boron trifluoride to form a complex catalyst with alkyl ethers and alcohols to prepare highly active polyisobutylene at a relatively high temperature. However, this type of polymerization method requires multiple polymerization stages, complex processes, strict requirements on raw material purity, and boron trifluoride is highly toxic and corrosive, making it difficult to post-process. Summary of the invention

[0007] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a method for preparing a highly active polyisobutylene having nearly 100% terminal external olefin double bonds by quenching after Fe-based co-initiation, and adding a third component to the method to prepare a block copolymer with vinyl ether monomers, styrene and its derivatives, and bio-based monomers. The method simplifies the process steps on the basis of suppressing the chain transfer phenomenon that is easy to occur in cationic polymerization, making industrial production feasible, environmentally friendly, and can bring higher economic benefits.

[0008] The technical solution of the present invention is as follows:

[0009] A composition for catalyzing isobutylene to prepare polyisobutylene, comprising: a main initiator, a co-initiator, a terminator and a quencher;

[0010] Wherein, the main initiator is selected from at least one of water, 2-chloro-2,4,4-trimethylpentane, cumyl chloride, tert-butyl chloride, 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, 5-tert-butyl-1,3-di(2-isopropyl chloride)benzene, and 5-tert-butyl-1,3-dimethylbenzene;

[0011] The co-initiator is a substance formed by aging and complexing of an Fe-based compound and a complexing agent;

[0012] The Fe-based compound includes FeCl 3 and FeCl 3 ·xH 2 O, where x=1, 3, 4 or 6;

[0013] The complexing agent is at least one of an ether compound (preferably ethyl ether, butyl ether, isopropyl ether), an alcohol compound (preferably isopropanol, tert-butyl alcohol, dicumyl alcohol, dipentaerythritol, tripentaerythritol), a thiol compound (preferably dithiothreitol, dithiothreitol, methyl mercaptan, dimercaptopropanol, dodecanethiol), and an amino acid compound (preferably alanine, lysine, etc.);

[0014] The quencher is at least one of a pyrrole compound (preferably 2,5-dimethylpyrrole, 1,2,2,6,6-pentylmethylpyrrole), a pyridine compound (preferably 2-tert-butylpyridine), and an ether compound (preferably ethyl ether, isopropyl ether, cyclopentyl methyl ether).

[0015] The terminator is at least one of water, alcohol (preferably methanol, ethanol, n-butanol, isopropanol), ammonia compound (preferably ammonia water), and alkali metal hydroxide (preferably sodium hydroxide aqueous solution).

[0016] According to an embodiment of the present invention, ferric chloride or FeCl 3 ·xH 2 The molar ratio of O and the coinitiator formed by the complex is (0.1-1):1; for example (0.2-0.8):1; if the coinitiator is FeCl 3 ·i-PrOH.

[0017] According to an embodiment of the present invention, the co-initiator system needs to be prepared in advance and aged.

[0018] According to an embodiment of the present invention, the co-initiator is prepared in the following manner: an Fe-based compound is added to a halogenated alkane solvent to dissolve, and then a complexing agent is added and stirred for more than 0.5 hours, for example, 0.5 to 12 hours.

[0019] According to an embodiment of the present invention, the molar ratio of the main initiator to the co-initiator is 1:(2-100), for example 1:(5-50), such as 1:(10-20).

[0020] According to an embodiment of the present invention, the mass molar ratio of the main initiator to the quencher is 1:(1-50), for example, 1:(2-10), such as 1:(4-8).

[0021] The present invention also provides a method for preparing polyisobutylene by catalyzing isobutylene with the above-mentioned composition, comprising the following steps:

[0022] Isobutylene is polymerized in the presence of a primary initiator and a co-initiator, and then a quencher is used to quench the reaction, and a terminator is used to terminate the polymerization reaction.

[0023] According to an embodiment of the present invention, the mass of the isobutylene monomer accounts for 10 wt % to 55 wt %, such as 15 wt % to 50 wt %, of the total mass of the isobutylene monomer, the composition and the solvent.

[0024] According to an embodiment of the present invention, the molar ratio of the isobutylene monomer to the primary initiator in the composition is (100-1000):1, for example (200-500):1, such as (220-400):1.

[0025] According to an embodiment of the present invention, the reaction is carried out in an inert gas atmosphere, such as nitrogen.

[0026] According to an embodiment of the present invention, the polymerization reaction temperature is below -10°C, for example, the polymerization reaction temperature is -90 to -30°C.

[0027] According to an embodiment of the present invention, the polymerization reaction time is 5 min to 240 min, for example, 10 min to 120 min.

[0028] According to an embodiment of the present invention, the solvent for the polymerization reaction is a polar solvent and / or a non-polar solvent;

[0029] The polar solvent is a chlorinated alkane compound, and at least one of monochloromethane and dichloromethane is selected.

[0030] The non-polar solvent is selected from at least one of n-hexane compounds, methylcyclohexane compounds and cyclohexane compounds.

[0031] According to an embodiment of the present invention, the volume ratio of the polar solvent to the non-polar solvent is (0-5):(5-10).

[0032] According to an embodiment of the present invention, the method comprises the following steps: at -90 to -30°C, in an inert gas atmosphere, isobutylene monomer is polymerized in the presence of a main initiator and a co-initiator, a quencher is added after the reaction for 5 to 240 minutes to quench the reaction, and a terminator is used to terminate the polymerization.

[0033] According to an embodiment of the present invention, the method comprises the following steps: adding isobutylene monomer to a solvent by continuous dropwise addition in an inert gas atmosphere at -90 to -30°C, and then adding a main initiator and a co-initiator to carry out a polymerization reaction, adding a quencher to quench the reaction after reacting for 5 to 240 minutes, and using a terminator to terminate the polymerization.

[0034] According to an embodiment of the present invention, the conversion rate of isobutylene monomer in the method is 80% or more, such as 85% or more, such as 90% or more.

[0035] According to an embodiment of the present invention, the method further comprises a step of washing with an acid after the reaction is completed; the acid used for washing can be a relatively weak acid such as formic acid, acetic acid, propionic acid, hydrosulfuric acid, hypochlorous acid, phosphoric acid, etc.

[0036] According to an embodiment of the present invention, the product may be washed with an acid after the reaction is terminated using a terminator.

[0037] According to an embodiment of the present invention, the product obtained after termination with a terminator can be centrifuged to remove iron-containing precipitates.

[0038] The present invention also provides polyisobutylene prepared by the above method, wherein the α-terminal double bond content is 1 The H nuclear magnetic resonance measurement is 80% or more, for example 85% or more, such as 90% or more.

[0039] According to an embodiment of the present invention, the Mn of the polyisobutylene is 2000 to 20000 g / mol, for example 8000 to 16000 g / mol.

[0040] According to an embodiment of the present invention, the molecular weight distribution of the polyisobutylene is 1.0 to 2.0, for example, 1.1 to 1.5.

[0041] The present invention also provides a method for preparing a block copolymer containing polyisobutylene by catalyzing isobutylene, comprising:

[0042] Isobutylene is polymerized in the presence of a main initiator and a co-initiator, and after a period of reaction, a third component and a second monomer are added to carry out polymerization, and then a terminator is used to terminate the polymerization;

[0043] The main initiator, co-initiator and terminator have the definitions and stoichiometric relationships as described above;

[0044] The second monomer is selected from at least one of vinyl ether monomers, styrene and its derivatives, and bio-based monomers.

[0045] According to an embodiment of the present invention, when the second monomer is a vinyl ether monomer (eg, isobutyl vinyl ether), the third component may be a styrene compound (preferably 1,1-stilbene, bromotriphenylethylene, 2-methylstilbene, 4-bromostilbene).

[0046] According to an embodiment of the present invention, when the second monomer is styrene and its derivatives, the third component may be an ester compound (preferably dimethylaminoethyl methacrylate, 2-carboxyethyl methacrylate, ethylene glycol dimethacrylate).

[0047] According to an embodiment of the present invention, when the second monomer is a bio-based monomer, the bio-based monomer is β-pinene, β-myrcene, limonene, myrcene, ocimene, etc.; the third component can be a pyridine compound (2-vinylpyridine or 2,5-dimethylpyridine), an ester compound (for example, dimethylaminoethyl methacrylate, 2-carboxyethyl methacrylate, ethylene glycol dimethacrylate).

[0048] According to an embodiment of the present invention, the method further comprises a step of washing with an acid after the reaction is completed; the acid used for washing can be a relatively weak acid such as formic acid, acetic acid, propionic acid, hydrosulfuric acid, hypochlorous acid, phosphoric acid, etc.

[0049] According to an embodiment of the present invention, the second monomer may be added multiple times to generate a polymer of two blocks, three blocks or more.

[0050] The present invention also provides a block copolymer containing polyisobutylene prepared by the above method, wherein the block ratio of the second monomer is above 50%, such as 55-75%, such as 60-70%.

[0051] According to an embodiment of the present invention, the Mn of the block copolymer is 2000-50000 g / mol, such as 10000-30000 g / mol; and the molecular weight distribution thereof is 1.1-2.5, such as 1.3-2.0.

[0052] Beneficial Effects

[0053] The composition provided by the present invention can catalyze isobutylene to prepare highly active polyisobutylene. Specifically, the beneficial effects achieved by the scheme of the present invention include:

[0054] 1. In the method for preparing highly active polyisobutylene by catalysis using the composition of the present invention, due to the presence of a quencher in the composition, polyisobutylene having an α-terminal double bond content of nearly 100% and a molecular weight distribution of <2.0 can be obtained.

[0055] 2. In the method for catalytically preparing block copolymers containing polyisobutylene of the present invention, the obtained block polymer Mn ranges from 2000 to 50000 g / mol, the block rate of the second stage monomer is more than 50%. The obtained block copolymer is a diblock or triblock copolymer, and its molecular weight distribution is 1.1 to 2.5.

[0056] 3. The method of the present invention can quickly remove the residual metal ions in the polymer by simply using the dissolution-acid washing method during the polymer post-treatment process.

[0057] 4. The Fe-based co-initiator in the composition used in the present invention is low-toxic, does not contain heavy metals, is inexpensive, and is easy to purchase, and the economic benefits are greatly improved compared with previous polymerizations.

[0058] In summary, the composition of the present invention can stably catalyze the production of highly active polyisobutylene with an α-terminal double bond content of up to 98%, simplifying the process steps, making industrial production feasible, being environmentally friendly, and bringing higher economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 Schematic diagram of the molecular structure of the highly active polyisobutylene of the present invention;

[0060] Figure 2 is the chlorine-terminated polyisobutylene in Example 1 1 H NMR spectrum;

[0061] Figure 3 is the exoolefin polyisobutylene in Example 2 1 H NMR spectrum;

[0062] Figure 4 is the PIB-b-PIBVE in Example 11 1 H NMR spectrum; DETAILED DESCRIPTION

[0063] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The components of the embodiments of the present invention generally described in the drawings here can be arranged and designed in various different configurations.

[0064] In the following examples, the number average molecular weight and molecular weight distribution of the polymers were measured by multi-angle laser scattering, and the α-terminal double bond content was measured by 1 Determined by H NMR.

[0065] The FeCl used in the following examples 3 The i-PrOH complex was aged as follows: 0.00216 mol of FeCl 3 Add 0.128 mol CH 2 Cl 2 Dissolve in , add 0.0026 mol of isopropanol with stirring, and let stand for 2 hours.

[0066] Example 1

[0067] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 0.0185 mol of i-PrOH complex was used to initiate polymerization. After 120 min of reaction, anhydrous ethanol was added to terminate the polymerization. After washing with acetic acid, iron-containing residues were precipitated with water. The organic phase and the aqueous phase were separated and washed three times, and then dried to constant weight to obtain chlorine-terminated polyisobutylene. Figure 2 Chlorine-terminated polyisobutylene 1 H NMR spectrum.

[0068] Example 2

[0069] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and after 120 min of reaction, diisopropyl ether (i-Pr 2 O) 0.0002 mol was used for quenching, and finally the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight, recorded as HRPIB, with a molecular weight of 4800 g / mol, and its structure is as follows Figure 1 As shown, the conversion rate is 90.52%, the molecular weight distribution is 1.396, and the α-terminal double bond is 91.57%.

[0070] Figure 3 For highly active polyisobutylene 1 H NMR spectrum, δ = 4.85 ppm at g and δ = 4.63 ppm at f are -CH 2 -C(CH 3 )=CH 2 The characteristic peak of the end group, δ = 5.14 ppm at h, is -CH=C(CH 3 ) 2 The characteristic peak of the end group is due to the fact that tertiary carbon cations easily form external and internal double bonds during chain growth. δ = 4.82 ppm at i is the characteristic peak in structure 3, due to the formation of internal unsaturated bonds through isomerization of carbon cations. Therefore, 1 The HNMR spectrum shows that PIB has three isomerized end groups, among which the content of structure 1 is as high as 91.57%.

[0071] Example 3

[0072] A low-temperature polymerization reactor was used, which was baked, vacuumed, and filled with nitrogen and then cooled to -50°C. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and diisopropyl ether (i-Pr 2 O) 0.0004 mol was used for quenching, and finally anhydrous ethanol was used to terminate the polymerization. After adding acetic acid for washing, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0073] Example 4

[0074] A low-temperature polymerization reactor was used, which was refrigerated to -40°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and after 120 min of reaction, diisopropyl ether (i-Pr 2 O) 0.0006 mol was used for quenching, and finally anhydrous ethanol was used to terminate the polymerization. After adding acetic acid for washing, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0075] Example 5

[0076] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and after 120 min of reaction, diisopropyl ether (i-Pr 2 O) 0.0008 mol was used for quenching, and finally the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0077] Example 6

[0078] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and after 120 min of reaction, diisopropyl ether (i-Pr 2 O) 0.0010 mol was used for quenching, and finally anhydrous ethanol was used to terminate the polymerization. After adding acetic acid for washing, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0079] Example 7

[0080] A low-temperature polymerization reactor was used, which was refrigerated to -40°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and diisopropyl ether (i-Pr 2 O) 0.0008 mol was used for quenching, and finally the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0081] Example 8

[0082] A low-temperature polymerization reactor was used, which was baked, vacuumed, and filled with nitrogen and then cooled to -50°C. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and diisopropyl ether (i-Pr 2 O) 0.0008 mol was used for quenching, and finally the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0083] Example 9

[0084] A low-temperature polymerization reactor was used, which was baked, vacuumed, and filled with nitrogen and then cooled to -70°C. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and diisopropyl ether (i-Pr 2 O) 0.0002 mol was used for quenching, and finally anhydrous ethanol was used to terminate the polymerization. After adding acetic acid for washing, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0085] Example 10

[0086] A low-temperature polymerization reactor was used, which was baked, vacuumized, and filled with nitrogen and then cooled to -80°C. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · i-PrOH complex 0.0185 mol initiated polymerization, and diisopropyl ether (i-Pr 2 O) 0.0002 mol was used for quenching, and finally anhydrous ethanol was used to terminate the polymerization. After adding acetic acid for washing, the iron-containing residue was precipitated with water, and the organic phase and the aqueous phase were separated, washed three times, and then dried to constant weight.

[0087] Embodiment 11

[0088] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · 0.0185 mol of i-PrOH complex was used to initiate polymerization. After 120 min of reaction, 0.0015 mol of 1,1-diphenylethylene was added. After 4 to 5 min, 0.13 mol of isobutyl vinyl ether (IBVE) was added to react for 20 min. Finally, the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water. The organic phase and the aqueous phase were separated and washed three times, and then dried to constant weight.

[0089] Example 12

[0090] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · 0.0185 mol of i-PrOH complex was used to initiate polymerization. After 120 min of reaction, 0.0015 mol of ethylene glycol dimethacrylate was added. After 4-5 min, 0.13 mol of styrene (St) was added to react for 20 min. Finally, the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water. The organic phase and the aqueous phase were separated and washed three times, and then dried to constant weight.

[0091] Embodiment 13

[0092] A low-temperature polymerization reactor was used, which was refrigerated to -60°C after baking, vacuuming, and nitrogen filling. 100 ml of a mixed solvent of hexane / monochloromethane (v / v = 6:4) was added, 0.26 mol of isobutylene raw material, 0.00113 mol of 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, and FeCl 3 · 0.0185 mol of i-PrOH complex was used to initiate polymerization. After 120 min of reaction, 0.0015 mol of 2,5-dimethylpyridine was added. After 4-5 min, 0.13 mol of β-pinene was added to react for 20 min. Finally, the polymerization was terminated with anhydrous ethanol. After washing with acetic acid, the iron-containing residue was precipitated with water. The organic phase and the aqueous phase were separated and washed three times, and then dried to constant weight.

[0093] Table 1 Reaction temperature, molecular weight, molecular weight distribution and conversion rate data table of the embodiment

[0094]

[0095]

[0096] In Table 1, “-” means that the structure is not contained.

[0097] The total isobutylene conversion α% in Table 1 is calculated as follows: Calculated by weight method. 1 Represents the mass of the monomer, m 2 Indicates the mass of the polymer.

[0098] α=m 2 / m 1 ×100%.

[0099] Table 2 Molecular weight, molecular weight distribution and conversion rate data of the block products of the embodiment

[0100] Example Block monomer Mn(g / mol) Mw / Mn Block rate % 11 IBVE 15760 1.613 61.74 12 St 22510 1.596 63.51 13 β-pinene 14700 1.470 56.14

[0101] The “blocking rate” of St in Table 2 is obtained by comparing the peak value measured by UV absorption spectrum with the theoretical fitting curve.

[0102] The “block ratio” of IBVE and β-pinene was obtained by the functional group ratio in NMR.

[0103] As shown in Table 1, at -60°C, without adding a quencher, 100% chlorine-terminated polyisobutylene was obtained. After adding the quencher, the content of the external olefin double bond in the obtained polyisobutylene reached more than 90%, and with the increase of the quencher content, the external olefin double bond reached the highest value when the main initiator: quencher = 1:4. After further increasing the amount of quencher, the content of the external olefin double bond gradually decreased. When reacting at -80°C, the external olefin content was as high as 99.01%, and even at -40°C, the reaction conversion rate could reach more than 85%. And there is no need to add a proton scavenger, and the molecular weight distribution of the product is less than 1.6.

[0104] As shown in Table 2, after the polyisobutylene is completely converted at -60°C, a small amount of IBVE, St, or β-pinene is added to carry out block polymerization. The block ratio of the obtained polymer is greater than 50% and the molecular weight distribution is less than 2.0.

[0105] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A composition for catalyzing the preparation of polyisobutylene from isobutylene, characterized in that: include: Main initiators, co-initiators, terminators and quenchers; Wherein, the main initiator is selected from at least one of water, 2-chloro-2,4,4-trimethylpentane, cumyl chloride, tert-butyl chloride, 5-tert-butyl-1,3-di(1-methyl-1-methoxyethyl)benzene, 5-tert-butyl-1,3-di(2-isopropyl chloride)benzene, and 5-tert-butyl-1,3-dimethylbenzene; The co-initiator is a substance formed by aging and complexing of an Fe-based compound and a complexing agent; The Fe-based compounds include FeCl3 and FeCl3·xH2O, wherein x=1, 3, 4 or 6; The complexing agent is at least one of an ether compound (preferably ethyl ether, butyl ether, isopropyl ether), an alcohol compound (preferably isopropanol, tert-butyl alcohol, dicumyl alcohol, dipentaerythritol, tripentaerythritol), a thiol compound (preferably dithiothreitol, dithiothreitol, methyl mercaptan, dimercaptopropanol, dodecanethiol), and an amino acid compound (preferably alanine, lysine, etc.); The quencher is at least one of a pyrrole compound (preferably 2,5-dimethylpyrrole, 1,2,2,6,6-pentylmethylpyrrole), a pyridine compound (preferably 2-tert-butylpyridine), and an ether compound (preferably ethyl ether, isopropyl ether, cyclopentyl methyl ether). The terminator is at least one of water, alcohol (preferably methanol, ethanol, n-butanol, isopropanol), ammonia compound (preferably ammonia water), and alkali metal hydroxide (preferably sodium hydroxide aqueous solution).

2. The composition according to claim 1, characterized in that The molar ratio of ferric chloride or FeCl3·xH2O to the co-initiator formed by the complex is (0.1-1):1; Preferably, the molar ratio of the main initiator to the co-initiator is 1:(2-100); Preferably, the mass molar ratio of the main initiator to the quencher is 1:(1-50).

3. A method for preparing polyisobutylene by catalyzing isobutylene with the composition according to claim 1 or 2, characterized in that: The steps include: isobutylene is polymerized in the presence of a primary initiator and a co-initiator, a quencher is used to quench the reaction, and a terminator is used to terminate the polymerization reaction; The main initiator, co-initiator, terminator and quencher have the definitions as described in claim 1 or 2.

4. The method according to claim 3, characterized in that The mass of the isobutylene monomer accounts for 10wt% to 55wt% of the total mass of the isobutylene monomer, the composition and the solvent; Preferably, the molar ratio of isobutylene monomer to the main initiator in the composition is (100-1000):1; Preferably, the reaction is carried out in an inert gas atmosphere; Preferably, the polymerization reaction temperature is below -10°C.

5. The polyisobutylene prepared by the method of claim 3 or 4, characterized in that: The α-terminal double bond content% 1 The H nuclear magnetic resonance measurement showed that the content was above 80%.

6. The polyisobutylene according to claim 5, characterized in that The Mn of the polyisobutylene is 2000 to 20000 g / mol; Preferably, the molecular weight distribution of the polyisobutylene is 1.0-2.

0.

7. A method for catalyzing isobutylene to prepare a block copolymer containing polyisobutylene, characterized in that: include: Isobutylene is polymerized in the presence of a main initiator and a co-initiator, and after a period of reaction, a third component and a second monomer are added to carry out polymerization, and then a terminator is used to terminate the polymerization; The main initiator, co-initiator and terminator have the definitions and metering relationships as described in claim 1 or 2; The second monomer is selected from at least one of vinyl ether monomers, styrene and its derivatives, and bio-based monomers.

8. The method according to claim 7, characterized in that When the second monomer is a vinyl ether monomer (such as isobutyl vinyl ether), the third component is a styrene compound (preferably 1,1-stilbene, bromotriphenylethylene, 2-methylstilbene, 4-bromostilbene); Preferably, when the second monomer is styrene and its derivatives, the third component is an ester compound (preferably dimethylaminoethyl methacrylate, 2-carboxyethyl methacrylate, ethylene glycol dimethacrylate); Preferably, when the second monomer is a bio-based monomer, the bio-based monomer is β-pinene, β-myrcene, limonene, myrcene, ocimene, etc.; the third component is a pyridine compound (2-vinylpyridine or 2,5-dimethylpyridine), an ester compound (such as dimethylaminoethyl methacrylate, 2-carboxyethyl methacrylate, ethylene glycol dimethacrylate).

9. The polyisobutylene-containing block copolymer prepared by the method of claim 7 or 8, characterized in that: The block ratio of the second monomer is 50% or more.

10. The polyisobutylene-containing block copolymer according to claim 9, characterized in that The Mn of the block copolymer is 2000-50000 g / mol; and the molecular weight distribution thereof is 1.1-2.5.

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