Method for preparing polybutene by using catalyst containing N-propanol

Abstract

Disclosed a method for preparing polybutene by using a catalyst including normal propanol, wherein the polybutene has 40 to 70% of vinylidene content and 10% or more of tetra-substituted double bond content by using a complex catalyst including normal propanol as a cocatalyst and a main catalyst such as boron trifluoride. The method comprises: introducing, to a raw reaction material including 10 wt % or more of isobutene, a complex catalyst including normal propanol as a cocatalyst and boron trifluoride as a main catalyst; and polymerizing the raw reaction material at a reaction temperature of 33 to 33 C. under a reaction pressure of 3 to 50 kg/cm.sup.2, wherein the vinylidene content is adjusted by adjusting the reaction temperature.

Claims

1. A method for preparing polybutene having 40 to 70% of vinylidene content and 10% or more of tetra-substituted double bond content, the method comprising: introducing, to a raw reaction material including 10 wt % or more of isobutene, a complex catalyst, including normal propanol as a cocatalyst and boron trifluoride as a main catalyst in a molar ratio of normal propanol/boron trifluoride of 1 to 1.5; and polymerizing the raw reaction material at a reaction temperature of 33 to 33 C. under a reaction pressure of 3 to 50 kg/cm.sup.2, wherein the vinylidene content is adjusted by adjusting the reaction temperature; wherein the vinylidene content is adjusted by adjusting the reaction temperature according to Formula 1:
1.2|T|V3|T|[Formula 1] wherein, T represents the reaction temperature; |T| represents variation of the reaction temperature based on a reaction temperature of 0 C.; and V represents variation of the vinylidene content.

2. The method for preparing polybutene of claim 1, wherein the boron trifluoride is 0.02 to 1 parts by weight with respect to 100 parts by weight of isobutene.

3. The method for preparing polybutene of claim 1, wherein the polymerization is carried out for 5 to 100 minutes.

4. The method for preparing polybutene of claim 1, wherein for adjusting terminal vinylidene, the isobutene conversion rate is 80% or more.

5. The method for preparing polybutene of claim 1, wherein a number average molecular weight of polybutene is 300 to 5,000.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an image for illustrating a method for preparing polybutene by using a catalyst including normal propanol according to an embodiment of the present invention; and

(2) FIG. 2 is a graph showing relation between the vinylidene content and reaction temperature in the method for preparing polybutene according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(3) Hereinafter, the present invention will be described in more detail with reference to accompanying drawings.

(4) FIG. 1 is an image for illustrating a method for preparing polybutene by using a catalyst including normal propanol according to an embodiment of the present invention. FIG. 1 shows one of methods for preparing polybutene by using a catalyst including normal propanol, and does not include all features of the present invention. As shown in FIG. 1, to prepare polybutene by using a catalyst including normal propanol according to the present invention, a raw reaction material including 10 wt % or more of isobutene and a complex catalyst including normal propanol, as a cocatalyst, and boron trifluoride, as a main catalyst, are prepared.

(5) The cocatalyst is essentially supplied for preparation of polybutene and acts as a proton (H.sup.+) donor for initiation of reaction. As the cocatalyst, water (H.sub.2O) or an alcohol compound having a carbon number of 1 to 4 may be typically used without limitation, however only normal propanol is used in the present invention. By adjusting input of the cocatalyst, a molar ratio of cocatalyst/main catalyst is adjusted so that reactivity of the complex catalyst may be increased or decreased. As a result, the molecular weight, vinylidene content and catalyst mileage and so forth may be adjusted.

(6) As the main catalyst, lewis acids such as boron trifluoride, and aluminum trichloride, which is a typical friedel craft type catalyst, may be used as needed. Boron trifluoride having excellent ability to induce terminal vinylidene production, and advantageous in the conventional purpose is the most preferably used. When the boron trifluoride is used as the main catalyst, the content thereof is 0.02 to 1 parts by weight with respect to 100 parts by weight of isobutene.

(7) A molar ratio of the cocatalyst/main catalyst included in the complex catalyst, for example, normal propanol/boron trifluoride is 1 to 2, preferably 1 to 1.8, and more preferably 1 to 1.5. When the molar ratio of normal propanol/boron trifluoride is less than 1, the complex catalyst may be modified. When the molar ratio is excessively high, i.e. above 2, reactivity becomes too low, so that it is difficult to adjust the vinylidene content and preparation cost may be increased.

(8) For preparation of the complex catalyst, for example, preparation may be performed by introducing normal propanol, which is a cocatalyst, into a complex catalyst preparation device 10; and then introducing a main catalyst such as boron trifluoride for 2 to 6 hours, preferably 3 to 5 hours, and more preferably 3.5 to 4.5 hours bewaring of exothermic reaction, while maintaining a temperature of 20 to 5 C., preferably 15 to 7 C., and more preferably 10 C. to adjust the molar ratio of cocatalyst/main catalyst

(9) For the complex catalyst, as shown in FIG. 1, each of the cocatalyst and main catalyst is introduced to the complex catalyst preparation device 10. However, the main catalyst may be introduced to a cocatalyst introduction pipe coupled to the complex catalyst preparation device 10, or the cocatalyst and main catalyst may be introduced to a pipe for supplying a raw reaction material to a reactor 20. In other word, the method is not specifically limited as long as the cocatalyst and main catalyst may be mixed.

(10) The raw reaction material includes 10 wt % or more, preferably 25 to 60 wt % of isobutene, and is, for example, C4 raffinate-1 which is a remainder after 1,3 butadiene extraction from a hydrocarbon mixture having a carbon number of 4 derived during the naphtha degrading process or crude oil refining process. In addition, a method of diluting pure isobutene with alkanes and using the diluent is also available. In that case, the isobutene concentration is preferably 25 to 60 wt % for proper polymerization of products.

(11) Sequentially, the raw reaction material is polymerized for 5 to 100 minutes at a reaction temperature of 33 to 33 C. under a reaction pressure of 3 to 50 kg/cm.sup.2, wherein the reaction temperature is adjusted to adjust the vinylidene content so that polybutene having 40 to 70% of vinylidene content and 10% or more of tetra-substituted double bond is prepared.

(12) The polymerization should be performed in the rector 20 which maintains a reaction temperature of 33 to 33 C., preferably 30 to 30 C. and a reaction pressure of 3 to 50 kg/cm.sup.2, preferably 3.5 to 10 kg/cm.sup.2 for 5 to 100 minutes, preferably 10 to 45 minutes of retention time to allow the raw reaction material to be maintained at a liquid state. In addition, for appropriately adjusting terminal vinylidene, the isobutene conversion rate should become 80% or more, and preferably 90 to 99%.

(13) When the vinylidene and molecular weight are determined through the polymerization, the vinylidene content may be adjusted by adjusting the reaction temperature during the polymerization as the following Formula 1.
1.2|T|V3|T|[Formula 1]

(14) Wherein, T represents a reaction temperature (33 C.T33 C.); |T| represents variation of a reaction temperature (based on a reaction temperature of 0 C.); and V represents variation of a vinylidene content. For example, when the reaction temperature is changed by 5 C., the vinylidene content is changed by 6 to 15%. FIG. 2 is a graph showing relation between the reaction temperature and vinylidene content in the method for preparing polybutene according to an embodiment of the present invention, and shows the result according to Formula 1.

(15) The Formula 1 is applied in the case where normal propanol is used as a cocatalyst; the same raw reaction material is used; and the same molecular weight grade product is produced (the amount of used catalyst may vary depending on the raw reaction material and condition of the process).

(16) The vinylidene content is measured through carbon-13 nuclear magnetic resonance (CNMR). Also, the vinylidene content may be measured through proton nuclear magnetic resonance (HNMR). For vinylidene of the present specification, a polybutene sample is dissolved by using deuterated chloroform (CDCL.sub.3), as a nuclear magnetic resonance (NMR) reagent, placed in a nuclear magnetic resonance (NMR) tube and scanned 1,024 times by using a magnetic resonance image device (Bruker Biospin AVANCE III 500 (500 MHz)) at a temperature of 27 C. Then, peaks in an olefin region are integrated to be used as a total value. Then, an integrated value of alpha vinylidene peaks at 135.5 ppm, and 143.5 ppm is divided by the total olefin integrated value to obtain the content.

(17) $\mathrm{Alpha}\mathrm{Vinylidene},\%=\frac{\mathrm{Alpha}\mathrm{Vinylidene}\mathrm{Area}}{\mathrm{Total}\mathrm{Olefin}\mathrm{Area}}*100$

(18) Depending on a device specification (MHz), molecular weight, and sample quantity, the number of scan (analysis time) may vary. In addition, analysis may be performed by introducing an internal standard material (1,3,5-tri-tert-butylbenzene).

(19) In sequence, when the polymerization is terminated, polybutene having 40 to 70% vinylidene at the terminal, among the whole double bond of polybutene, and 10% or more of tetra-substituted double bond which has the number of an alkyl group substituted at the double bond is 4, i.e., mid-reactive polybutene is prepared. The number average molecular weight (Mn) of the mid-reactive polybutene is 300 to 5,000, preferably 400 to 2,000, and more preferably 500 to 1,500.

(20) As shown in FIG. 1, the complex catalyst supplied to the reactor 20, which is prepared in the complex catalyst preparation device 10, may be supplied to the reactor via a complex catalyst supply device 12 for adjusting supply of the complex catalyst, or be directly supplied to the reactor 20 from the complex catalyst preparation device 10 without the complex catalyst supply device 12.

(21) Additionally, a process as follows may further be included as needed. In a neutralization and washing bath 22, a neutralization solution including water and a neutralizing agent (for example, sodium hydroxide) is added to a reactant released from the reactor 20 to remove a catalytic component from the reactant for neutralization and washing. A separation bath 24 into which the catalytic component-removed reactant is introduced, liquid-liquid separation into organic compound and water layers, i.e., hydro carbon and water layers is performed by using phase separation principle of water and oil. Therefore, a mixture in the water layer including the catalytic component is released and the organic compound which is remained after catalyst elimination in the reactant is supplied to a C4 distillation column 26. In the C4 distillation column 26, unreacted C4 in the organic compound is released and recovered through distillation, and the remaining organic compound is supplied to a LP (light polymer) distillation column 28. The LP distillation column 28, LP (light polymer) in the remaining organic compound is released and recovered through distillation, and remaining mid-reactive polybutene is stored in a product tank.

(22) Hereinafter, the present invention will be described in more detail with reference to specific examples. The examples below are only to illustrate the present invention, and the present invention is not limited to the examples below. The molecular weight grade in the examples and comparative examples below is a target molecular weight for industrial production, and the molecular weight (Mn) value of the actual product may be a slightly different.

Example 1

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 1,000

(23) Polymerization was performed by continuously introducing a complex catalyst of normal propanol/boron trifluoride having a molar ratio of 1.1, which is prepared in a complex catalyst preparation device, and a raw reaction material having composition as described in Example 1 in Table 1 below (C4 raffinate-1), while maintaining the temperature of a reactor at 6 C. To allow the raw reaction material to maintain a liquid state, the pressure of the reactor was maintained at 3 kg/cm.sup.2 or more. The average retention time was 45 minutes. In terms of the amount of used catalyst, 0.1 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. After 180 minutes, the reactant released from the reactor was mixed with 5 wt % of a sodium hydroxide solution, and transferred to a neutralization and washing bath to terminate polymerization and remove the catalyst. Sequentially, the reactant was transferred to a separation bath to release and remove waste water including the catalyst. Then, the remaining reactant was introduced to a C4 distillation column. By heating the reactant at 100 C. in the C4 distillation column, C4 was released and recovered, and the remaining reactant was transferred to a LP distillation column. The reactant transferred to the LP distillation column was heated at 230 C. under 25 torr for 30 minutes of retention time to release and recover light polymer (LP) in the reactant. Remaining mid-reactive polybutene was transferred to a product tank and stored. The molecular weight of the prepared mid-reactive polybutene was measured through gel permeation chromatography (GPC), and vinylidene in polybutene was analyzed by using C13-NMR. As a result, the isobutene conversion rate was 94%, and the vinylidene content was 58%. In addition, the tetra-substituted double bond content was 23% (number average molecular weight (Mn)=980).

(24) TABLE-US-00001 TABLE 1 Raw reaction material (C4 raffinate-1) cocatalyst isobutane n-butane 1-butene C-2-butene T-2-butene isobutene Example 1 a-propanol 2.7 10.0 26.1 4.5 9.3 47.4 Example 2 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 3 a-propanol 3.7 16.1 35.0 2.3 7.5 35.4 Example 4 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 5 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 6 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 7 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 8 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 9 a-propanol 45.5 4.4 0.1 0.2 54.8 Example 10 a-propanol 45.5 4.4 0.1 0.2 54.8 Comparative methanol 45.5 4.4 0.1 0.2 54.8 Example 1 Comparative isopropanol 2.7 10.0 25.1 4.5 9.3 47.4 Example 2 Comparative ethanol 3.7 16.1 35.0 2.3 7.5 35.4 Example 3

Example 2

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade of 1,000

(25) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 6 C.; a raw reaction material having composition as described in Example 2 in Table 1 above (i.e., pure isobutylene) was used; and 0.08 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 97%, and the vinylidene content was 63%. In addition, the tetra-substituted double bond content was 18% (number average molecular weight (Mn)=980).

Example 3

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 1,000

(26) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 8 C.; a raw reaction material having composition as described in Example 3 in Table 1 above (i.e., butane-butene oil (B-B oil)) was used; and 0.17 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 88%, and the vinylidene content was 56%. In addition, the tetra-substituted double bond content was 25% (number average molecular weight (Mn)=960).

Example 4

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(27) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 5 C.; a raw reaction material having composition as described in Example 4 in Table 1 above (i.e., pure isobutylene; which is the same as the raw reaction material used in Example 2) was used; and 0.081 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 66%. In addition, the tetra-substituted double bond content was 18% (number average molecular weight (Mn)=560).

Example 5

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(28) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 3 C.; a raw reaction material having composition as described in Example 5 in Table 1 above (i.e., pure isobutylene) was used; and 0.080 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 64%. In addition, the tetra-substituted double bond content was 22% (number average molecular weight (Mn)=540).

Example 6

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(29) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 2 C.; a raw reaction material having composition as described in Example 6 in Table 1 above (i.e., pure isobutylene) was used; and 0.080 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 63%. In addition, the tetra-substituted double bond content was 21% (number average molecular weight (Mn)=560).

Example 7

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(30) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 0 C.; a raw reaction material having composition as described in Example 7 in Table 1 above (i.e., pure isobutylene) was used; and 0.079 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 60%. In addition, the tetra-substituted double bond content was 23% (number average molecular weight (Mn)=530).

Example 8

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(31) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 2 C.; a raw reaction material having composition as described in Example 8 in Table 1 above (i.e., pure isobutylene) was used; and 0.078 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 56%. In addition, the tetra-substituted double bond content was 24% (number average molecular weight (Mn)=540).

Example 9

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(32) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 3 C.; a raw reaction material having composition as described in Example 9 in Table 1 above (i.e., pure isobutylene) was used; and 0.078 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 53%. In addition, the tetra-substituted double bond content was 25% (number average molecular weight (Mn)=550).

Example 10

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 550

(33) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that the reaction temperature was maintained at 5 C.; a raw reaction material having composition as described in Example 10 in Table 1 above (i.e., pure isobutylene) was used; and 0.077 parts by weight of boron trifluoride was introduced with respect to 100 parts by weight of isobutene. The isobutene conversion rate was 98%, and the vinylidene content was 45%. In addition, the tetra-substituted double bond content was 25% (number average molecular weight (Mn)=550).

Comparative Example 1

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 1,000

(34) To obtain mid-reactive polybutene, polymerization was performed as described in Example 2 except that a raw reaction material having composition the same as that of Example 4 (i.e. pure isobutylene) was used; a complex catalyst of methanol/boron trifluoride having a molar ratio of 1.1 and prepared in a complex catalyst preparation device was used; and the reaction temperature was maintained at 17 C. to adjust the vinylidene content. The isobutene conversion rate of was 97%, and the vinylidene content was 60%. In addition, the tetra-substituted double bond content was 25% (number average molecular weight (Mn)=330). Due to too high vinylidene content, when decreasing the vinylidene content (by increasing the reaction temperature), the molecular weight was decreased too much so that preparation of polybutene having a desired molecular weight (1,000) was unavailable.

Comparative Example 2

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 1,000

(35) To obtain mid-reactive polybutene, polymerization was performed as described in Example 1 except that a raw reaction material having composition the same as that of Comparative Example 2 in Table 1 above (i.e. C4 raffinate-1 which was the same as the raw reaction material used in Example 1) was used; a complex catalyst of isopropanol/boron trifluoride having a molar ratio of 1.1 and prepared in a complex catalyst preparation device was used; and the reaction temperature was maintained at 13 C. to adjust the vinylidene content. The isobutene conversion rate of was 94%, and the vinylidene content was 59%. In addition, the tetra-substituted double bond content was 21% (number average molecular weight (Mn)=370). Since the activity of the catalyst was decreased due to 1-butene in the raw reaction material, preparation of mid-reactive polybutene having a high molecular weight (1,000) was unavailable.

Comparative Example 3

Polymerization of Mid-Reactive Polybutene Having Molecular Weight of Grade 1,000

(36) To obtain mid-reactive polybutene, polymerization was performed as described in Example 3 except that a raw reaction material having composition as described in Comparative Example 3 in Table 1 above was used; a complex catalyst of ethanol/boron trifluoride having a molar ratio of 1.1 and prepared in a complex catalyst preparation device was used; and the reaction temperature was maintained at 7 C. to adjust the vinylidene content. The isobutene conversion rate of was 88%, and the vinylidene content was 58%. In addition, the tetra-substituted double bond content was 19% (number average molecular weight (Mn)=500). In Comparative Example 3, the molecular weight was decreased too much when adjusting the vinylidene content so that preparation of mid-reactive polybutene having a desired molecular weight (1,000) was unavailable. Like Comparative Example 2, due to 1-butene in the raw reaction material, the activity of the catalyst was decreased so that mid-reactive polybutene having a high molecular weight (1,000) was unavailable.

(37) Table 2 below shows physical properties and reaction conditions of polybutene prepared in Examples 1 to 10 and Comparative Examples 1 to 3 described above.

(38) TABLE-US-00002 TABLE 2 Vinylidene amount (%)/tetra- Isobutene reaction substituted Molecular conversion Catalyst temperature double bond weight of grade rate (%) (wt %) ( C.) amount (%) (grade) MN Example 1 94 0.1 6 58/23 1000 980 Example 2 97 0.08 6 63/18 1000 980 Example 3 88 0.17 8 56/25 1000 960 Example 4 98 0.081 5 66/18 550 560 Example 5 98 0.080 3 64/22 550 540 Example 6 98 0.080 2 63/21 550 560 Example 7 98 0.079 0 60/23 550 530 Example 8 98 0.078 2 56/24 550 540 Example 9 98 0.078 3 53/25 550 550 Example 10 98 0.077 5 45/25 550 550 Comparative 97 0.08 17 60/25 1000 330 Example 1 Comparative 94 0.1 13 59/21 1000 370 Example 2 Comparative 88 0.17 7 58/19 1000 500 Example 3

(39) As shown in Tables 1 and 2 above, it can be found that mid-reactive polybutene having a mid-range vinylidene content may be prepared even when any type of raw reaction material is supplied during the operation of a plant for polybutene preparation according to the method for preparing polybutene by using a catalyst including normal propanol according to the present invention. In other word, even in the case where 3 types of raw reaction materials used in Examples 1 to 10 or a C4 raw material having various compositions is supplied, mid-reactive polybutene may be prepared by adjusting introduction quantity of the catalyst and temperature, thereby easily adjusting vinylidene and the molecular weight.

(40) Namely, the method for preparing polybutene using a catalyst including normal propanol according to the present invention may adjust the vinylidene content by adjusting the reaction temperature. The results shown in Table 3 below were obtained through the repetitive experiments.

(41) TABLE-US-00003 TABLE 3 reaction Reaction Vinylidene Vinylidene temperature temperature amount amount ( C.) variation(|T|) (%) variation(|V|) Example 4 5 5 66 6 [(1) in FIG. 2] Example 5 3 3 64 4 [(2) in FIG. 2] [ Example 6 2 2 63 3 [(3) in FIG. 2] Example 7 0 60 Example 8 2 2 56 4 [(4) in FIG. 2] Example 9 3 3 53 7 [(5) in FIG. 2] Example 10 5 5 45 15 [(1) in FIG. 2]

(42) As shown in Table 3 above and FIG. 2 below, it can be found that the vinylidene content was distributed in a certain range depending on the reaction temperature. For example, when the reaction temperature was changed by 5 C. based on 0 C. (5 C. and 5 C.), although the increased and decreased amounts of the vinylidene content were different (for 5 C., the vinylidene content was increased to 66%, and, for 5 C., the vinylidene content was decreased to 45%), the variation thereof was included in the range of the Formula 1 (1.2|T|V3|T|) above.

(43) Further, for Comparative Examples 1 to 3, high purity isobutene, raffinate-1, and butane-butene oil are respectively used with a typical alcohol cocatalyst without normal propanol. In that case, to adjust the vinylidene content to a descried content, the reaction temperature should be greatly increased during polymerization. For that case, the vinylidene content is adjusted, however the molecular weight is deceased too much so that preparation of mid-reactive polybutene having a desired polybutene content of 40 to 70% becomes difficult. Generally, the high molecular weight is obtained at a low temperature, and a low molecular weight is obtained at a high temperature. Also, 1-butene decreases the vinylidene content, and the activity of the catalyst, so that the molecular weight was decreased. However, as the polymerization temperature decreases, the amount of deceased vinylidene content and molecular weight due to the influence of 1-butene is reduced. Therefore, when polybutene is polymerized at a relatively low temperature, the vinylidene content may be easily adjusted and mid-reactive polybutene having a desired molecular weight may be prepared.

(44) When the complex catalyst including a normal propanol cocatalyst and a main catalyst such as boron trifluoride of the present invention is used, the vinylidene content included in polybutene may be adjusted. In addition to the property in that, when the reaction temperature is increased, the vinylidene content is decreased and, when the reaction temperature is reduced, the vinylidene content is increased, polybutene having a high molecular weight with respect to the typical complex catalyst (main catalyst/cocatalyst) may be prepared. Further, when the normal propanol cocatalyst is used, unlike the typical alcohol cocatalyst, yield of a liquid phase polymer product may be enhanced even when the isobutene conversion rate is increased.

(45) As described above, according to the method for preparing polybutene by using a catalyst including normal propanol according to the present invention, both production efficiency and quality may be satisfied, so that preparation of a competitive product may be prepared by reducing production cost. In addition, unless a polybutene manufacturing company prepares a raw material by itself and uses, the raw material is generally supplied by a raw material manufacturing company so that supply of the raw material may be difficult. However, by using the method for preparing polybutene according to the present invention, even in the case where a certain raw material is not provided, a product may be easily prepared. Further, preparation may be efficient relative to typical preparation of highly reactive polybutene, because a product may be prepared by adjusting the reaction temperature depending on the molecular weight and isobutene concentration after the reaction, and preparation was performed at room temperature due to highly active complex catalyst including normal propanol.

(46) The method for preparing polybutene using a catalyst including normal propanol according to the present invention facilitates adjustment of the vinylidene content and molecular weight, thereby allowing mid-reactive polybutene to be prepared at a high conversion rate and yield. In the method, even though any type of raw material including an economical C4 mixture such as C4 raffinate-1 having low cost, an isobutene mixture, or high purity isobutene having relatively high cost is supplied, the vinylidene content in polybutene may be adjusted to 40 to 70%, so that preparation of polybutene is economical. In addition, by including 10% or more tetra-substituted double bond in polybutene, compatibility with lubricating oil or fuel of an internal combustion engine, as well as heat stability and reactivity are increased.