KR101898378B1 - Method of producing high reactive polyisobutene - Google Patents

Abstract

The present invention relates to a process for producing highly reactive polyisobutene, and more particularly to a process for producing polyisobutene using a boron trifluoride complex catalyst; And an organic compound containing 10 or less carbon atoms containing oxygen atoms, and which is excellent in molecular weight control and has an? -Vinylidene content of 80% or more.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing highly reactive polyisobutene,

The present invention relates to a process for producing highly reactive polyisobutene, and more particularly to a process for producing polyisobutene using a boron trifluoride complex catalyst; And an organic compound containing 10 or less carbon atoms containing oxygen atoms, and which is excellent in molecular weight control and has an? -Vinylidene content of 80% or more.

Polyisobutene (PIB) is a polymer of isobutene. Polyisobutene is classified according to the content of? -Vinylidene located at the terminal, and? -Vinylidene content is 20% or less as general polyisobutene (conventional PIB), and? -Vinylidene content More than 80% of this is referred to as highly reactive polyisobutene (high reactive PIB).

General polyisobutene is mainly used as a pressure-sensitive adhesive, an adhesive, and an insulating oil, while highly reactive polyisobutene is used as an anti-wear agent and a fuel detergent for engine oil.

In the past, in order to increase the reactivity of general polyisobutene, a method of chlorinating polyisobutene with chlorine gas and reacting with maleic anhydride was used. In this case, however, it is not preferable because the apparatus cost for chlorine treatment and the environmental problem due to unreacted chlorine gas treatment may occur.

Since highly reactive polyisobutene has a high content of alpha -vinylidene and can react directly with maleic anhydride, polyisobutenylsuccinic anhydride (PIBSA), polyisobutenyl succinimide (polyisobutenyl succinimide), which is a derivative of various additives, PIBSI).

It is now known that commercially available polyisobutene is produced using aluminum trichloride catalysts and that highly reactive polyisobutene is produced using boron trifluoride catalysts.

U.S. Patent No. 4,605,808 discloses a process for producing a 1-olefin-containing raw material which comprises polymerizing a 1-olefin-containing raw material in the presence of a boron trifluoride complex catalyst comprising boron trifluoride and an alcohol at a temperature of -100 to +50 ° C for 8 minutes or more, By weight or more and 70% or more by weight of the polyisobutene. However, the above patent has a problem in that the reaction activity is lowered when the content of? -Vinylidene is increased.

The present invention provides a method for producing highly reactive polyisobutene having excellent molecular weight control and having an? -Vinylidene content of 80% or more.

In order to achieve the above object, the present invention provides a method for producing high-reactivity polyisobutene, comprising the steps of adding a boron trifluoride complex compound to a mixture of C4 oil fraction containing isobutene and an organic compound having 1 to 10 carbon atoms, And introducing a catalyst, wherein the boron trifluoride complex catalyst catalyst comprises boron trifluoride; And a second co-catalyst, wherein the first co-catalyst is an alcohol compound having 1 to 4 carbon atoms, and the second co-catalyst is an alkyl ether compound having 3 to 10 carbon atoms , And a process for producing highly reactive polyisobutene satisfying the following formula (1) is provided.

<Formula 1>

50 < Mn - 520 x Z < 2000

이고, 0.3 < Z < 1.4Z =

, 0.3 < Z < 1.4

Mn: number average molecular weight of highly reactive polyisobutene

Y: content of organic compounds (mmol)

Xa: the content of boron trifluoride in the boron trifluoride complex (mmol)

Xc: the content (mmol) of the second co-catalyst in the above-

According to the method for producing highly reactive polyisobutene according to the present invention, highly reactive polyisobutene having an improved .alpha.-vinylidene content and excellent molecular weight control can be produced than when the boron trifluoride complex catalyst is used alone.

In addition, the highly reactive polyisobutene produced by the above method is highly economical and eco-friendly since it has high reactivity with high? -Vinylidene content and can be applied to lubricating oil and fuel detergent without using chlorine gas.

Hereinafter, the present invention will be described in more detail.

The method for producing highly reactive polyisobutene according to the present invention includes the step of introducing a boron trifluoride complex catalyst into a mixture of C4 olefins containing isobutene and an organic compound having 1 to 10 carbon atoms containing oxygen atoms , Said boron trifluoride complex catalyst catalyst is selected from the group consisting of boron trifluoride; And a second co-catalyst, wherein the first co-catalyst is an alcohol compound having 1 to 4 carbon atoms, and the second co-catalyst is an alkyl ether compound having 3 to 10 carbon atoms And satisfies the following formula (1).

&Lt; Formula 1 >

50 < Mn - 520 x Z < 2000

이고, 0.3 < Z < 1.4Z =

, 0.3 < Z < 1.4

Mn: number average molecular weight of highly reactive polyisobutene

Y: content of organic compounds (mmol)

Xa: the content of boron trifluoride in the boron trifluoride complex (mmol)

Xc: the content (mmol) of the second co-catalyst in the above-

The organic compounds containing oxygen atoms and containing 1 to 10 carbon atoms used in the present invention are preferably those selected from secondary or tertiary alcohols and alkyl ethers having 3 to 10 carbon atoms.

Examples of the secondary alcohols include 2-propanol, 2-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, Methyl-3-pentanol, 2,4-dimethyl-3-pentanol, 4,4-dimethyl-2-pentanol, Methyl-2-heptanol, 6-methyl-2-heptanol, 6-methyl-2-heptanol, 3-heptanol, 2-octanol, 4-octanol, 2,2-dimethyl-3-octane Methyl-3-octanol, 2-methyl-3-octanol, 6-ethyl-3-octanol, Methyl-4-nonanol, 3-methyl-4-nonanol, 2-decanol, 3-decanol and the like.

Examples of the tertiary alcohols include 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 3-heptanol, 3-methyl-3-heptanol, 3-methyl-2-pentanol, , 3,7-dimethyl-3-octanol, 3-methyl-3-octanol, 4-methyl-4-nonanol and the like.

Examples of the alkyl ethers include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, isoamyl ether, dihexyl ether, butyl methyl ether, butyl ethyl ether, sec- sec-butyl methyl ether, sec-butyl ethyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-amyl methyl ether and the like.

The organic compound having 1 to 10 carbon atoms and containing oxygen atoms used in the present invention is preferably added in an amount of 0.05 to 1.0 part by weight based on 100 parts by weight of isobutene. If the amount of the organic compound exceeds 1.0 part by weight, the activity is lowered and the conversion of isobutene is lowered, resulting in lower productivity.

The boron trifluoride complex catalyst used in the present invention is prepared by introducing boron trifluoride into at least one of the first catalyst and the second catalyst, and it is preferable to use at least two catalysts as the promoter.

The promoter to be added to the catalyst is represented by the first co-catalyst (Xb) and the second co-catalyst (Xc) according to the order of addition.

The boron trifluoride complex catalyst used in the present invention may be a mixture of boron trifluoride Xa and first co-catalyst Xb, boron trifluoride Xa, first co-catalyst Xb and second co- . The first co-catalyst (Xb) is composed of an alcohol compound having 1 to 4 carbon atoms, and the second co-catalyst (Xc) is preferably composed of an alkyl ether having 3 to 10 carbon atoms.

The amount of the catalyst used in the polymerization reaction of the present invention is preferably such that the amount of boron trifluoride in the catalyst component is 0.05 to 1.0 part by weight based on 100 parts by weight of isobutene. If the amount of the boron trifluoride in the catalyst component exceeds 1.0 part by weight, the productivity per catalyst is low and it is not economical. If the amount is less than 0.05 part by weight, the yield of the polymer is low and the economical efficiency is also low.

According to one embodiment, in the boron trifluoride complex catalyst, the molar ratio of boron trifluoride to the first cocatalyst is 1: 1.1 to 2.0, preferably 1.1 to 1.7.

According to one embodiment, in the boron trifluoride complex catalyst catalyst, the molar ratio of boron trifluoride: first promoter: and second promoter is 1: 1.1 to 2.0: 0.1 to 1.0, preferably 1: 1.1 to 1.7 : 0.1 to 0.6.

When the molar ratio of the boron trifluoride complex catalyst is out of the above range, the activity of the boron trifluoride complex catalyst is lowered or the content of the? -Vinylidene in the polymer is lowered to less than 80%.

In the preparation of the boron trifluoride complex according to the present invention, the complex formation temperature is suitably 10 DEG C or less. The complex formation reaction of boron trifluoride with ethanol and alcohols is an exothermic reaction, and it is desirable to remove the reaction heat in order to maintain the stability of the catalyst and prevent the danger of explosion. Therefore, it is preferable to conduct the complex formation reaction at a low temperature of 10 ° C or less, preferably -40 ° C to 0 ° C.

The polymerization reaction temperature is preferably -40 ° C to 20 ° C. The reaction pressure is preferably 3 kg / cm ² or more, preferably 3 kg / cm 2 to 7 kg / cm ² to maintain the raw material in a liquid state, Preferably from 1 minute to 90 minutes.

The polymerization reactor may be a batch reactor or a continuous reactor. The continuous reactor may use a reactor such as a Continuous Flow Stirred Tank reactor, a Plug Flow Reactor or a Tubular Flow Reactor, and a loop reactor.

The highly reactive polyisobutene prepared according to the present invention has a number average molecular weight (Mn) of 300 to 5,000, a molecular weight distribution (Mw / Mn) of 1.3 to 5, and an alpha -vinylidene content of 80%

The molecular weight of the highly reactive poly isobutene (Mn, number average molecular weight) and the molecular weight distribution (Mw / Mn, Molecular weight distribution ) was analyzed by GPC (Gel permeation chromatography), α- vinylidene content is analyzed by ¹ H-NMR Respectively.

The following examples are intended to illustrate but not to limit the invention.

[ Manufacturing example  1] Preparation of boron trifluoride complex catalyst

The flask containing 23.67 g (514 mmol) of ethanol was kept at -20 ° C, and 23.4 g (344 mmol) of boron trifluoride was added in gaseous state for 2 hours while stirring to prepare a boron trifluoride complex catalyst.

[ Manufacturing example  2] Preparation of boron trifluoride complex catalyst

A flask containing 23.67 g (514 mmol) of ethanol and 16.79 g (164 mmol) of diisopropyl ether was kept at -20 ° C., and 34.1 g (463 mmol) of boron trifluoride was added in gaseous state for 3 hours while stirring to form boron trifluoride Complex catalyst was prepared.

[ Manufacturing example  3] Preparation of boron trifluoride complex catalyst

A flask containing 30.42 g (660 mmol) of propanol and 16.79 g (164 mmol) of diisopropyl ether was kept at -20 ° C. and 30.0 g (443 mmol) of boron trifluoride was added in gaseous state for 3 hours while stirring. .

[ Manufacturing example  4] Preparation of boron trifluoride complex catalyst

A flask containing 7.14 g (155 mmol) of ethanol and 16.2 g (158 mmol) of diisopropyl ether was kept at -20 ° C. and 9.5 g (140 mmol) of boron trifluoride was added in gaseous state for 1 hour while stirring, .

[ Example  One] High reactivity Polyisobutene  polymerization

A 2-liter batch reactor connected to a cooling line was charged with 100 g of the starting material of the composition shown in Table 1 and 300 g of hexane while maintaining the temperature at -20 캜. The reactor pressure is kept at 3 atm so that the raw material is in a liquid state, and the temperature is stabilized while turning the agitator. When the temperature was stabilized, 0.37 g (3.6 mmol) of diisopropyl ether was injected into the reactor and stirred. After 1 minute, the boron trifluoride complex catalyst prepared in Preparation Example 1 was added to the boron trifluoride complex And 0.3 parts by weight of boron trifluoride in the catalyst. After 30 minutes of the reaction time, the polymerization solution was poured into a 5 wt% caustic soda aqueous solution to stop the polymerization and neutralize the catalyst component. The water washing was further repeated twice to remove the catalyst, and then the solvent was removed using a rotary evaporator. Finally, distillation was conducted at 0.9 Torr at 150 DEG C to remove the remaining low-boiling components to obtain highly reactive polyisobutene. The resulting highly reactive polyisobutene had an isobutene conversion of 81%, a number average molecular weight (Mn) of 930 g / mol, a molecular weight distribution (Mw / Mn) of 2.2 and an alpha -vinylidene content of 92%. At this time, when Z is (3.45 / 3.6) = 0.958 and Mn = 930 is substituted, the formula 1 is satisfied.

ingredient Isobutene n-butane Isobutane 1-butene 2-butene Content (mol%) 78 10 7 2 3

[ Example  2] High reactivity Polyisobutene  polymerization

2-propanol (0.37 g, 3.6 mmol) instead of the diisopropyl ether of Example 1 was fed into the 2-liter batch reactor connected to the cooling line at -20 캜, and the boron trifluoride complex catalyst prepared in Preparation Example 1 Highly reactive polyisobutene was obtained in the same manner as in Example 1, except that 0.3 parts by weight of boron trifluoride was contained in the boron trifluoride complex compound catalyst based on 100 parts by weight of isobutene. The obtained highly reactive polyisobutene had an isobutene conversion of 85%, a number average molecular weight (Mn) of 1500 g / mol, a molecular weight distribution (Mw / Mn) of 2.0 and an alpha -vinylidene content of 89%. At this time, when Z is (3.45 / 3.6) = 0.958 and Mn = 1500 is substituted, equation (1) is satisfied.

[ Example  3] High reactivity Polyisobutene  polymerization

The boron trifluoride complex catalyst prepared in Preparation Example 2 was added to a boron trifluoride complex catalyst catalyst in an amount of 0.3 part by weight based on 100 parts by weight of isobutene while keeping the 2 liter batch reactor connected to the cooling line at -19 캜 High-reactivity polyisobutene was obtained in the same manner as in Example 1. The results are shown in Table 1. The obtained polymer had an isobutene conversion of 86%, a number average molecular weight (Mn) of 650 g / mol, a molecular weight distribution (Mw / Mn) of 1.8, and an alpha -vinylidene content of 93%. At this time, when Z is [3.45 / (1.22 + 3.6)] = 0.716 and Mn = 650 is substituted, expression 1 is satisfied.

[ Example  4] High reactivity Polyisobutene  polymerization

The boron trifluoride complex catalyst prepared in Preparation Example 3 was added to a boron trifluoride complex catalyst catalyst in an amount of 0.3 part by weight based on 100 parts by weight of isobutene while keeping the 2 liter batch reactor connected to the cooling line at -18 캜 High-reactivity polyisobutene was obtained in the same manner as in Example 1. The results are shown in Table 1. The obtained polymer had an isobutene conversion of 88%, a number average molecular weight of 980 g / mol, a molecular weight distribution (Mw / Mn) of 1.7, and an alpha -vinylidene content of 95%. At this time, when Z is [3.45 / (1.277 + 3.6)] = 0.707 and Mn = 980 is substituted, expression 1 is satisfied.

[ Example  5] High reactivity Polyisobutene  polymerization

0.73 g (7.2 mmol) of the diisopropyl ether of Example 1 was introduced while maintaining the 2-liter batch reactor connected to the cooling line at -19 캜, and the boron trifluoride complex catalyst prepared in Preparation Example 3 was added to 100 parts by weight of isobutene Highly reactive polyisobutene was obtained in the same manner as in Example 1, except that 0.3 parts by weight of boron trifluoride was contained in the boron trifluoride complex catalyst. The resulting polymer had an isobutene conversion of 85%, a number average molecular weight of 1300 g / mol, a molecular weight distribution (Mw / Mn) of 2.1, and an alpha -vinylidene content of 93%. At this time, when Z is [3.45 / (1.277 + 7.2)] = 0.407 and Mn = 1300 is substituted, the formula 1 is satisfied.

[ Example  6] High reactivity Polyisobutene  polymerization

1.0 g (9.8 mmol) of the diisopropyl ether of Example 1 was introduced while maintaining the 2-liter batch reactor connected to the cooling line at -19 캜, and the boron trifluoride complex catalyst prepared in Preparation Example 3 was added to 100 parts by weight of isobutene Highly reactive polyisobutene was obtained in the same manner as in Example 1, except that 0.3 parts by weight of boron trifluoride was contained in the boron trifluoride complex catalyst. The resulting polymer had an isobutene conversion of 81%, a number average molecular weight of 2000 g / mol, a molecular weight distribution (Mw / Mn) of 2.1, and an alpha -vinylidene content of 90%. At this time, if Z is [3.45 / (1.277 + 9.8)] = 0.311 and Mn = 2000 is substituted, equation (1) is satisfied.

[ Example  7] High reactivity Polyisobutene  polymerization

(1.6 mmol) of 4-methyl-2-propanol instead of the diisopropyl ether of Example 1 while keeping the 2-liter batch reactor connected to the cooling line at -18 占 폚, Highly reactive polyisobutene was obtained in the same manner as in Example 1, except that the boron complex catalyst was used in an amount of 0.3 parts by weight based on 100 parts by weight of isobutene and boron trifluoride in the boron trifluoride complex catalyst. The obtained polymer had an isobutene conversion of 91%, a number average molecular weight of 1100 g / mol, a molecular weight distribution (Mw / Mn) of 2.0, and an alpha -vinylidene content of 91%. At this time, if Z is [3.45 / (1.277 + 1.6)] = 1.199 and Mn = 1100 is substituted, expression 1 is satisfied.

[ Example  8] High reactivity Polyisobutene  polymerization

(1.8 mmol) of tert-amyl alcohol instead of the diisopropyl ether of Example 1 was fed while maintaining the 2-liter batch reactor connected with the cooling line at -19 캜, and the boron trifluoride complex catalyst Was prepared in the same manner as in Example 1, except that 0.3 parts by weight of boron trifluoride was contained in the boron trifluoride complex compound catalyst on the basis of 100 parts by weight of isobutene to obtain highly reactive polyisobutene. The obtained polymer had an isobutene conversion of 88%, a number average molecular weight of 960 g / mol, a molecular weight distribution (Mw / Mn) of 1.9 and an alpha -vinylidene content of 89%. At this time, when Z is [3.45 / (1.277 + 1.8)] = 1.121 and Mn = 960 is substituted, the formula 1 is satisfied.

[ Comparative Example  One] High reactivity Polyisobutene  polymerization

The 2-liter batch reactor connected to the cooling line was maintained at -19 ° C., and 100 g of the raw material having the composition shown in Table 1 and 300 g of hexane were injected. The reactor pressure is kept at 3 atm so that the raw material is in a liquid state, and the temperature is stabilized while turning the agitator. The boron trifluoride complex catalyst prepared in Preparation Example 1 was added to the temperature stabilized reactor so that boron trifluoride in the boron trifluoride complex catalyst was 0.3 part by weight based on 100 parts by weight of isobutene.

After 30 minutes of the reaction time, the polymerization solution was poured into a 5 wt% caustic soda aqueous solution to stop the polymerization and neutralize the catalyst component. The water washing was further repeated twice to remove the catalyst, and then the solvent was removed using a rotary evaporator. Finally, the remaining low boiling point components were removed using a distillation apparatus to obtain highly reactive polyisobutene. The resulting polymer had an isobutene conversion of 86%, a number average molecular weight of 2200 g / mol, a molecular weight distribution (Mw / Mn) of 3.5, and an alpha -vinylidene content of 76%.

At this time, Z is [3.45 / 0] = ∞ and does not satisfy the Z range of Equation 1. Further, there was no introduction of an organic compound containing oxygen in the polymerization step.

[ Comparative Example  2] High reactivity Polyisobutene  polymerization

Reactive polyisobutene was obtained in the same manner as in Comparative Example 1, except that the boron trifluoride complex catalyst prepared in Preparation Example 2 was used while maintaining the 2-liter batch reactor connected to the cooling line at -20 캜. The resulting polymer had an isobutene conversion of 73%, a number average molecular weight of 1800 g / mol, a molecular weight distribution (Mw / Mn) of 2.9 and an alpha -vinylidene content of 83%. At this time, Z is [3.45 / (1.22)] = 2.828, which does not satisfy the range of Z in Equation 1. Further, there was no introduction of an organic compound containing oxygen in the polymerization step.

[ Comparative Example  3] High reactivity Polyisobutene  polymerization

The boron trifluoride complex catalyst prepared in Preparation Example 3 was added to the boron trifluoride complex catalyst catalyst in an amount of 0.3 part by weight based on 100 parts by weight of isobutene while keeping the 2 liter batch reactor connected to the cooling line at -20 占 폚 High-reactivity polyisobutene was obtained in the same manner as in Comparative Example 1. The results are shown in Table 1. &lt; tb &gt; &lt; TABLE &gt; The obtained polymer had an isobutene conversion of 76%, a number average molecular weight of 2500 g / mol, a molecular weight distribution (Mw / Mn) of 2.6, and an alpha -vinylidene content of 84%. At this time, Z is [3.45 / 1.277] = 2.702, which does not satisfy the range of Z in Equation 1. Further, there was no introduction of an organic compound containing oxygen in the polymerization step.

[ Comparative Example  4] High reactivity Polyisobutene  polymerization

The boron trifluoride complex catalyst prepared in Preparation Example 4 was added to the boron trifluoride complex catalyst catalyst in an amount of 0.3 part by weight based on 100 parts by weight of isobutene while keeping the 2 liter batch reactor connected to the cooling line at -19 캜 High-reactivity polyisobutene was obtained in the same manner as in Comparative Example 1. [ The obtained polymer had an isobutene conversion of 21%, a number average molecular weight of 1800 g / mol, a molecular weight distribution (Mw / Mn) of 4.5, and an alpha -vinylidene content of 83%. At this time, when Z is [3.45 / 3.90] = 0.885 and Mn = 1800 is substituted, expression 1 is satisfied. However, there was no introduction of an organic compound containing oxygen in the polymerization process.

[ Comparative Example  5] High reactivity Polyisobutene  polymerization

0.18 g (3.83 mmol) of ethanol and 0.13 g (1.22 mmol) of diisopropyl ether were fed directly into the reactor instead of the boron trifluoride complex catalyst of Production Example 2 while maintaining the 2-liter batch reactor connected to the cooling line at -19 캜 Thereafter, highly reactive polyisobutene was obtained in the same manner as in Example 3, except that 0.23 g (3.45 mmol) of boron trifluoride was added. The obtained polymer had an isobutene conversion of 67%, a number average molecular weight of 610 g / mol, a molecular weight distribution (Mw / Mn) of 2.9 and an alpha -vinylidene content of 78%. At this time, Z satisfies Equation 1 as [3.45 / (1.22 + 3.6)] = 0.716. However, boron trifluoride, the first co-catalyst and the second co-catalyst were directly added to the reactor without being added as the boron trifluoride complex catalyst, thereby producing a polymer.

division Reaction temperature (캜) Isobutene conversion (%) Mn Mw / Mn ? -vinylidene content (%) Example 1 -20 81 930 2.2 92 Example 2 -20 85 1500 2.0 89 Example 3 -19 86 650 1.8 93 Example 4 -18 88 980 1.7 95 Example 5 -19 85 1300 2.1 93 Example 6 -18 81 2000 2.1 90 Example 7 -18 91 1100 2.0 91 Example 8 -19 88 960 1.9 89 Comparative Example 1 -19 86 2200 3.5 76 Comparative Example 2 -20 73 1800 2.9 83 Comparative Example 3 -20 76 2500 2.6 84 Comparative Example 4 -19 21 1800 4.5 83 Comparative Example 5 -19 67 610 2.9 78

From the above Table 2, it can be seen that, in the case of the examples according to the present invention, when the organic compound is added to the polybasic boron trifluoride complex catalyst from the boron trifluoride complex catalyst alone (Comparative Examples 1 to 3) It can be seen that tin is produced.

In addition, when the same molar ratio of alkyl ether was used (Example 3 and Comparative Example 4), when the boron trifluoride complex catalyst was prepared without adding the organic compound separately (Comparative Example 4), the reaction activity was extremely low, The vinylidene content is 10% lower and the molecular weight is increased and the highly reactive polyisobutene having a broad molecular weight distribution is produced.

Further, according to Comparative Example 5, when the polymerization process was carried out by introducing boron trifluoride, alcohol and alkyl ether into C4 oil fraction containing isobutene in the same molar ratio condition as in Example 3, the isobutene conversion And the content of alpha -vinylidene was also lowered.

The high-α-vinylidene content polymer has a high content of effective components which react in the production of lubricating oil, fuel detergent and the like, which is economically advantageous.

The number average molecular weight of the highly reactive polyisobutene being produced commercially is in the range of 750 to 2300 g / mol, and in the case of Examples 4 to 6 of Table 2, the boron trifluoride complex catalyst type, the catalyst feed amount, Can be adjusted to a desired molecular weight by changing the content of the organic compound in the same condition, which can be efficiently produced in view of the process.

Claims (10)

Comprising the step of introducing a boron trifluoride complex catalyst into a mixture of C4 olefins containing isobutene and an alkyl ether having 3 to 10 carbon atoms as an organic compound or a secondary or tertiary alcohol,
Wherein the boron trifluoride complex catalyst is selected from the group consisting of boron trifluoride; And a first co-catalyst; And a second co-catalyst,
The first co-catalyst is an alcohol compound having 1 to 4 carbon atoms,
The second co-catalyst is an alkyl ether compound having 3 to 10 carbon atoms,
(1): < EMI ID = 1.0 >
&Lt; Formula 1 &gt;
50 < Mn - 520 x Z < 2000
Z =

, 0.3 &lt; Z &lt; 1.4

Mn: number average molecular weight of highly reactive polyisobutene
Y: content of organic compounds (mmol)
Xa: the content of boron trifluoride in the boron trifluoride complex (mmol)
Xc: the content of the second co-catalyst in the boron trifluoride complex (mmol)
(The molar ratio of Xa: Y is 1: 0.47 to 2.85) delete The method according to claim 1,
Wherein the organic compound is contained in an amount of 0.05 to 1.0 part by weight based on 100 parts by weight of the isobutene. The method according to claim 1,
Wherein the boron trifluoride complex catalyst is used so that boron trifluoride is contained in an amount of 0.05 to 1.0 part by weight based on 100 parts by weight of isobutene. The method according to claim 1,
Wherein the molar ratio of the boron trifluoride to the first cocatalyst is 1: 1.1 to 2.0. The method according to claim 1,
Wherein the molar ratio of the boron trifluoride: the first co-catalyst: the second co-catalyst is 1: 1.1 to 2.0: 0.1 to 1.0. The method according to claim 1,
Wherein the boron trifluoride complex is prepared at a temperature of -40 to 10 占 폚. The method according to claim 1,
Wherein the reaction temperature in the polymerization step is -40 ° C to 20 ° C, the reaction pressure is 3 kg / cm ² or more, and the reaction time is 1 minute to 90 minutes. The method according to claim 1,
Wherein the highly reactive polyisobutene has a number average molecular weight (Mn) of 300 to 5,000. The method according to claim 1,
Wherein the highly reactive polyisobutene has a molecular weight distribution (Mw / Mn) of 1.3 to 5. [