CATALYST COMPOSITION FOR POLYMERIZATION OF a-OLEFIN AND PREPARATION AND USE THEREOF

Abstract

The present disclosure discloses a catalyst composition for polymerization of an α-olefin and preparation and use thereof. The catalyst composition comprises boron trifluoride and at least one protic cocatalyst; the protic cocatalyst has a structural formula of X—(CH.sub.2).sub.n—OH, where n is an integer selected from 1 to 10; X is selected from nitro, halogen, cyano, sulfonic acid group, aldehyde group, acyl, carboxyl and amino. The catalyst can be used in production of a poly(α-olefin) synthetic base oil, and is particularly suitable for a low viscosity poly(α-olefin) synthetic base oil with high selectivity of the target product.

Claims

1. A catalyst composition for polymerization of an α-olefin, comprising boron trifluoride and at least one protic cocatalyst; wherein the protic cocatalyst has a structural formula of:
X—(CH.sub.2).sub.n—OH where n is an integer selected from 1 to 10; X is selected from nitro, halogen, cyano, sulfonic acid group, aldehyde group, acyl group, carboxyl, and amino.

2. The catalyst composition according to claim 1, wherein a molar ratio of boron trifluoride to the protic cocatalyst is from 0.1 to 3.0.

3. The catalyst composition according to claim 1, wherein the acyl group has a structure of —COR, where R is alkyl, preferably methyl.

4. The catalyst composition according to claim 1, wherein the protic cocatalyst is one or a combination of two or more selected from 2-nitroethanol, 3-nitropropanol, 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 7-chloro-1-heptanol, 8-chloro-1-octanol, 9-chloro-1-nonanol, 10-chloro-1-decanol, 2-fluoroethanol, 3-fluoro-1-propanol, 4-fluoro-1-butanol, 5-fluoro-1-pentanol, 6-fluoro-1-hexanol, 7-fluoro-1-heptanol, 8-fluoro-1-octanol, 9-fluoro-1-nonanol, 10-fluoro-1-decanol, 2-bromoethanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 2-iodoethanol, 3-iodo-1-propanol, 4-iodo-1-butanol, 5-iodo-1-pentanol, 6-iodo-1-hexanol, 7-iodo-1-heptanol, 8-iodo-1-octanol, 9-iodo-1-nonanol, 10-iodo-1-decanol, 3-hydroxypropionitrile, 4-hydroxybutyronitrile, 2-hydroxyethanesulfonic acid, 3-hydroxypropanesulfonic acid, 4-hydroxybutanesulfonic acid, hydroxyacetaldehyde, 3-hydroxypropionaldehyde, 4-hydroxybutyraldehyde, 5-hydroxyvaleraldehyde, 6-hydroxyhexanal, 8-hydroxyoctanal, 6-hydroxy-2-hexanone, 5-hydroxy-2-hexanone, hydroxyacetic acid, 3-hydroxypropionic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, and 10-amino-1-decanol.

5. The catalyst composition according to claim 1, wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 3-chloro-1-propanol, 3-iodo-1-propanol, 4-bromo-1-butanol, 6-hydroxyhexanoic acid, 3-nitropropanol, 2-hydroxyethanesulfonic acid, 4-hydroxybutanesulfonic acid, 6-hydroxy-2-hexanone, 5-hydroxypentanal, 8-hydroxyoctanoic acid and 10-hydroxydecanoic acid.

6. The catalyst composition according to claim 1, wherein X is selected from halogen and carboxyl.

7. The catalyst composition according to claim 6, wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 4-bromo-1-butanol and 8-hydroxyoctanoic acid.

8. The catalyst composition according to claim 1, wherein a molar ratio of boron trifluoride to the protic cocatalyst is from 0.5 to 2.0.

9. The catalyst composition according to claim 1, wherein a molar ratio of boron trifluoride to the protic cocatalyst is from 0.8 to 1.5.

10. The catalyst composition according to claim 1, wherein the protic cocatalyst is one or a combination of two or more selected from 4-fluoro-1-butanol, 4-bromo-1-butanol and 8-hydroxyoctanoic acid, and a molar ratio of boron trifluoride to the protic cocatalyst is from 1 to 1.2.

11. A method for preparing a catalyst composition according to claim 1, comprising: mixing the protic cocatalyst with boron trifluoride and carrying out a reaction at a predetermined temperature for a predetermined time to obtain the catalyst composition.

12. The method according to claim 11, wherein the mixing the protic cocatalyst with boron trifluoride comprises: thermally purging with nitrogen a reactor for preparing a catalyst; after purging with nitrogen, adding the protic cocatalyst while turning on stirring; raising the temperature to a predetermined temperature; and adding boron trifluoride in proportion.

13. The method according to claim 11, wherein the predetermined temperature is −30° C. to 50° C., preferably −10° C. to 30° C.

14. The method according to claim 11, wherein the predetermined time is 0.5 h to 4.0 h, preferably 0.5 h to 3.0 h.

15. The method according to claim 11, wherein the protic cocatalyst has been subjected to a refining treatment.

16. The method according to claim 15, wherein the refining treatment includes distillation and/or adsorbent removal method, and the water content of the protic cocatalyst after the refining treatment is less than 100 ppm.

17. The method according to claim 11, comprising: thermally purging with nitrogen a reactor for preparing a catalyst for 5 min to 10 min; after purging with nitrogen, adding the refined protic cocatalyst while turning on stirring; controlling the temperature at −30° C. to 50° C.; adding boron trifluoride in proportion; and reacting for 0.5 h to 4.0 h to obtain the catalyst composition.

18. Use of the catalyst composition according to claim 1 in synthesis of a poly(α-olefin) synthetic base oil.

19. The use according to claim 18, wherein the use comprises the following steps: adding a raw material α-olefin to a tank polymerization reactor; adding the catalyst composition continuously to the tank polymerization reactor; controlling the reaction temperature at 20° C. to 50° C. with a residence time of 20 min to 100 min; after the reaction, separating the catalyst, and carrying out hydrogenation to obtain the poly(α-olefin) synthetic base oil.

20. The use according to 19, wherein the catalyst composition is added in an amount of 0.1% to 2.0% by mass of the raw material α-olefin.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG. 1 is the NMR carbon spectrum of boron trifluoride-4-fluoro-1-butanol complex prepared in Example 1.

[0044] FIG. 2 is the NMR carbon spectrum of boron trifluoride-3-chloro-1-propanol complex prepared in Example 2.

[0045] FIG. 3 is the NMR hydrogen spectrum of boron trifluoride-3-chloro-1-propanol complex prepared in Example 2.

[0046] FIG. 4 is the NMR carbon spectrum of boron trifluoride-hydroxyacetic acid complex prepared in Example 6.

[0047] FIG. 5 is the gas chromatogram of the product obtained with the catalyst composition of Example 1.

[0048] FIG. 6 is the gas chromatogram of the product obtained with the catalyst composition of Comparative Example 3.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0049] In order to illustrate the present disclosure more clearly, the present disclosure is further described below in connection with preferred embodiments. It should be understood by those skilled in the art that what is specifically described below is illustrative and not limiting and should not be used to limit the protection scope of the present disclosure.

[0050] All numerical designations of the present disclosure (e.g., temperature, time, concentration, and weight, including ranges for each of these) may generally be approximated by varying (+) or (−) in appropriate increments of 0.1 or 1.0. All numerical designations can be understood to be preceded by the term “approximately”.

[0051] The cocatalysts in the following examples are obtained commercially and refined to remove as much impurities and moisture as possible. Specific refining treatments include, but are not limited to, conventional process methods such as distillation or physical adsorption, and the water content of the refined protic cocatalyst is less than 100 ppm.

Example 1

[0052] The example prepared a catalyst composition, specifically comprising the following steps.

[0053] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-fluoro-1-butanol (1 mol) was added, while stirring was turned on, and the temperature was raised to 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1:1. After 0.5 h of reaction, the prepared polymerization catalyst (boron trifluoride-4-fluoro-1-butanol complex) was obtained and stored for use.

[0054] With tetramethylsilane (TMS) as the internal standard and D.sub.2O as the external standard lock solvent, the NOVA 400 MHz NMR spectrometer was set to adjust the relevant parameters of the instrument and the resultant boron trifluoride-4-fluoro-1-butanol complex was characterized by .sup.13C NMR to obtain the NMR carbon spectrum as shown in FIG. 1.

[0055] As shown in FIG. 1, the δ values of α-C, β-C, ω-C, and γ-C atoms of the boron trifluoride-4-fluoro-1-butanol complex were located at 61.6 ppm, 44.3 ppm, 28.4 ppm, and 30 26.6 ppm, respectively. In addition, the NMR carbon spectra of the catalyst compositions in Example 3, Example 5, and Example 10 were similar to this spectrum, except that there were some shifts in α-C and β-C. As the electron-withdrawing ability of the introduced group increases, the α-C atom shifts toward the low field and high δ value, while the β-C atom changes in the opposite trend. In addition, the main catalyst BF.sub.3 molecule itself has a strong electron-withdrawing induction effect. When forming the B—O coordination bond, BF.sub.3 also has an electron-withdrawing induction effect on the adjacent atoms (C and H atoms on α-C) in order to attract electrons as much as possible, resulting in enhanced de-shielding effect and decreased electron cloud density in the corresponding atom, with its δ value showing a shift toward the low field and high shift.

Example 2

[0056] The example prepared a catalyst composition, specifically comprising the following steps.

[0057] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 3-chloro-1-propanol (1 mol) was added, while stirring was turned on, and the temperature was raised to 40° C. The main catalyst of Lewis acid, boron trifluoride, was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.5. After 0.8 h of reaction, the prepared polymerization catalyst (boron trifluoride-3-chloro-1-propanol complex) was obtained and stored for use.

[0058] With tetramethylsilane (TMS) as the internal standard and D.sub.2O as the external standard lock solvent, the NOVA 400 MHz NMR spectrometer was set to adjust the relevant parameters of the instrument and the boron trifluoride-3-chloro-1-propanol complex was characterized by .sup.1H NMR and .sup.13C NMR, as shown in FIGS. 2 and 3.

[0059] As shown in FIG. 2, the δ values of α-C, β-C, and ω-C atoms of the boron-3-chloro-1-propanol trifluoride complex were located at 59.1 ppm, 41.3 ppm, and 35.4 ppm, respectively. In addition, the NMR carbon spectra of the catalyst compositions in Example 4 and Example 8 were similar to this spectrum, except that there were some shifts in α-C and β-C. The electron-withdrawing ability of the end-site group is enhanced, and the α-C atom shifts toward the low field and high δ value, while the β-C atom changes in the opposite trend.

[0060] As shown in FIG. 3, the δ values of the hydrogen protons in the α-CH.sub.2—, β-CH.sub.2-, and ω-CH.sub.2— groups of the boron trifluoride-3-chloro-1-propanol complex were located at 3.83 ppm to 3.85 ppm, 2.05 ppm to 2.08 ppm and 3.62 ppm to 3.66 ppm, respectively. Boron trifluoride exerts an electron-withdrawing induction effect on the hydrogen protons (2.19 ppm, alcohol hydroxyl hydrogen proton peak) on the 3-chloro-1-propanol ligand, resulting in enhanced de-shielding effect and decreased electron cloud density in the respective hydrogen atoms, and a shift of the corresponding hydrogen atoms toward the low field and high δ values.

Example 3

[0061] The example prepared a catalyst composition, specifically comprising the following steps.

[0062] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-chloro-1-butanol (1 mol) was added, while stirring was turned on, and the temperature was raised to 30° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.8. After 1.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 4

[0063] The example prepared a catalyst composition, specifically comprising the following steps.

[0064] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 3-iodo-1-propanol (1 mol) was added, while stirring was turned on, and the temperature was raised to 20° C. The main catalyst aluminum trichloride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 1.0. After 1.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 5

[0065] The example prepared a catalyst composition, specifically comprising the following steps.

[0066] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-bromo-1-butanol (1 mol) was added, while stirring was turned on, and the temperature was raised to 10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 1.5. After 2.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 6

[0067] The example prepared a catalyst composition, specifically comprising the following steps.

[0068] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst hydroxyacetic acid (1 mol) was added, while stirring was turned on, and the temperature was controlled to 0° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 2.0. After 2.5 h of reaction, the prepared polymerization catalyst (boron trifluoride-hydroxyacetic acid complex) was obtained and stored for use.

[0069] With tetramethylsilane (TMS) as the internal standard and D.sub.2O as the external standard lock solvent, the NOVA 400 MHz NMR spectrometer was set to adjust the relevant parameters of the instrument and the resultant boron trifluoride-hydroxyacetic acid complex was characterized by .sup.13C NMR to obtain the NMR carbon spectrum as shown in FIG. 4.

[0070] As shown in FIG. 4, the 6 values of the carbon atom at the carboxyl position and α-C of the boron trifluoride-hydroxyacetic acid complex were located at 177.1 ppm and 60.5 ppm, respectively. In addition, the NMR carbon spectra of the catalyst compositions in Example 7, Example 9, Example 10, Example 13, and Example 14 are similar to this spectrum in that they all have distinct peaks generated by carbon on the carboxyl group, except the number of carbons, and peaks generated by a plurality of secondary carbons.

Example 7

[0071] The example prepared a catalyst composition, specifically comprising the following steps.

[0072] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 6-hydroxyhexanoic acid (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −10° C. The main catalyst iron bromide was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 2.5. After 3.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 8

[0073] The example prepared a catalyst composition, specifically comprising the following steps.

[0074] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 3-nitropropanol (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 3.0. After 4.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 9

[0075] The example prepared a catalyst composition, specifically comprising the following steps.

[0076] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 2-hydroxyethanesulfonic acid (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −20° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 2.0. After 1.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 10

[0077] The example prepared a catalyst composition, specifically comprising the following steps.

[0078] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-hydroxybutanesulfonic acid (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −30° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.5. After 2.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 11

[0079] The example prepared a catalyst composition, specifically comprising the following steps.

[0080] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 6-hydroxy-2-hexanone (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 1.5. After 0.7 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 12

[0081] The example prepared a catalyst composition, specifically comprising the following steps.

[0082] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 5-hydroxyvaleraldehyde (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −30° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.6. After 1.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 13

[0083] The example prepared a catalyst composition, specifically comprising the following steps.

[0084] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 8-hydroxyoctanoic acid (1 mol) was added, while stirring was turned on, and a circulation cooler was turned on to control the temperature at −20° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 1.2. After 2.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 14

[0085] The example prepared a catalyst composition, specifically comprising the following steps.

[0086] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 10-hydroxydecanoic acid (1 mol) was added, while stirring was turned on, and the temperature was controlled at 10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.5. After 4.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 15

[0087] The example prepared a catalyst composition, specifically comprising the following steps.

[0088] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, refined cocatalysts 4-fluoro-1-butanol (0.5 mol) and 6-hydroxy-hexanoic acid (0.5 mol) (a molar ratio of 4-fluoro-1-butanol to 6-hydroxy-hexanoic acid of 1:1) were added, while stirring was turned on, and the temperature was controlled at 10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.6. After 3.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 16

[0089] The example prepared a catalyst composition, specifically comprising the following steps.

[0090] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, refined cocatalysts 3-nitropropanol (1 mol) and 4-hydroxybutanesulfonic acid (0.5 mol) (a molar ratio of 3-nitropropanol to 4-hydroxybutanesulfonic acid of 2:1) were added, while stirring was turned on, and the temperature was controlled at 10° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 1.0. After 2.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Example 17

[0091] The example prepared a catalyst composition, specifically comprising the following steps.

[0092] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, refined cocatalysts 5-hydroxyvaleraldehyde (1 mol), 10-hydroxydecanoic acid (1 mol) and 4-chloro-1-butanol (1 mol) (a molar ratio of 5-hydroxyvaleraldehyde, 10-hydroxydecanoic acid and 4-chloro-1-butanol of 1:1:1) were added, while stirring was turned on, and the temperature was controlled at 20° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.8. After 4.0 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 1

[0093] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0094] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-fluoro-1-butanol (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 4.0. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 2

[0095] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0096] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst 4-fluoro-1-butanol (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.05. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 3

[0097] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0098] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst butanol (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1.

[0099] After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 4

[0100] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0101] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst isopropyl alcohol (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 5

[0102] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0103] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst acetic acid (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst for use.

Comparative Example 6

[0104] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0105] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst deionized water (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 7

[0106] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0107] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst ethyl acetate (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 8

[0108] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0109] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst phosphoric acid (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

Comparative Example 9

[0110] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0111] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst dimethyl ether (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst for use.

Comparative Example 10

[0112] The comparative example prepared a catalyst composition, specifically comprising the following steps.

[0113] The reactor for preparing the catalyst was thermally purged with nitrogen for 10 min, and after purging with nitrogen, a refined cocatalyst acetone (1 mol) was added, while stirring was turned on, and the temperature was controlled at 50° C. The main catalyst boron trifluoride was added in proportion, and the molar ratio of the main catalyst to the cocatalyst was 0.1. After 0.5 h of reaction, the prepared polymerization catalyst was obtained and stored for use.

[0114] Catalyst Performance Evaluation Test:

[0115] Using 1-decene as the raw material, the raw material was firstly fed into the tank polymerization reactor, and each of the catalyst compositions prepared in Examples 1 to 17 15 and Comparative Examples 1 to 4 was added to the polymerization reactor continuously, where the amount of the catalyst composition was 1.0 wt. % (mass fraction of 1-decene raw material), and the reaction temperature was controlled at 25° C., and the residence time was all 60 min. After the reaction, the catalyst was separated and the product was obtained after hydrogenation. The product was collected for chromatographic analysis and performance testing, and the results were shown in Tables 1 and 2.

TABLE-US-00001 TABLE 1 Preparation conditions of the catalyst compositions in each of Examples and Comparative Examplex and the performance parameters of the obtained corresponding product Molar Catalyst preparation ratio of conditions BF.sub.3 to Temperature/ KV100º C./ Viscosity Pour No. Cocatalyst cocatalyst ° C. Time/h mm.sup.2/s index point/° C. Example 1 4-fluoro-1-butanol 0.1 50 0.5 4.03 137 −60° C. Example 2 3-chloro-1-propanol 0.5 40 0.8 5.02 139 −60° C. Example 3 4-chloro-1-butanol 0.8 30 1.0 4.06 136 −60° C. Example 4 3-iodo-1-propanol 1.0 20 1.5 4.12 135 −60° C. Example 5 4-bromo-1-butanol 1.5 10 2.0 6.04 142 −60° C. Example 6 hydroxyacetic 2.0 0 2.5 4.18 138 −57° C. acid Example 7 6-hydroxyhexanoic 2.5 −10 3.0 4.01 135 1 acid Example 8 3-nitropropanol 3.0 −10 4.0 4.10 139 −60° C. Example 9 2-hydroxyethanesulfonic 2.0 −20 1.0 5.21 140 −57° C. acid Example 10 4-hydroxy 0.5 −30 2.0 6.12 142 −57° C. butanesulfonic acid Example 11 6-hydroxy-2- 1.5 −10 0.7 5.42 142 −57° C. hexanone Example 12 5-hydroxyvaleraldehyde 0.6 −30 1.0 6.35 145 −57° C. Example 13 8-hydroxyoctanoic 1.2 −20 2.0 6.32 149 −57° C. acid Example 14 10-hydroxydecanoic 0.5 10 4.0 4.15 136 −57° C. acid Example 15 4-fluoro-1-butanol 0.6 10 3.0 4.25 140 −60° C. 6-hydroxy-hexanoic acid Example 16 4-hydroxy butan 1.0 10 2.0 4.11 138 −60° C. 3-nitropropanol esulfonic acid Example 17 5-hydroxyvaleraldehyde 0.8 20 4.0 6.53 147 −60° C. 10-hydroxydecanoic acid 4-chloro-1-butanol Comparative 4-fluoro-1-butanol 4.0 50 0.5 4.26 125 −57° C. Example 1 Comparative 4-fluoro-1-butanol 0.05 50 0.5 4.18 127 −54° C. Example 2 Comparative butanol 0.1 50 0.5 4.02 120 −60° C. Example 3 Comparative isopropyl 0.1 50 0.5 4.11 123 −60° C. Example 4 alcohol Comparative acetic acid 0.1 50 0.5 4.30 130 −54° C. Example 5 Comparative deionized water 0.1 50 0.5 3.98 121 −54° C. Example 6 Comparative ethyl acetate 0.1 50 0.5 4.01 123 −57° C. Example 7 Comparative phosphoric acid 0.1 50 0.5 4.14 125 −60° C. Example 8 Comparative dimethyl ether 0.1 50 0.5 4.24 126 −57° C. Example 9 Comparative acetone 0.1 50 0.5 3.59 118 −57° C. Example 10

TABLE-US-00002 TABLE 2 Composition distribution of products prepared by catalyst compositions of each of Examples and Comparative Examples C.sub.60 or NO. C.sub.10 C.sub.20 C.sub.30 C.sub.40 C.sub.50 above C.sub.30 + C.sub.40 Example 1 1.5 4.4 57.3 33.5 1.4 1.9 90.8 Example 2 0.7 2.1 56.2 35.6 1.5 3.9 91.8 Example 3 2.2 1.7 54.3 36.3 4.3 1.2 1 90.6 Example 4 2.1 3.5 53.2 37.0 1.6 2.6 90.2 Example 5 1.0 2.2 58.8 31.9 2.7 3.4 90.7 Example 6 1.2 5.8 56.3 35.2 1.3 0.2 91.5 Example 7 0.9 5.2 55.9 34.3 0.9 2.8 90.2 Example 8 1.6 4.3 55.3 35.3 2.8 0.7 90.6 Example 9 0.1 4.4 57.3 34.9 1.4 1.9 92.2 Example 10 0.5 2.3 52.2 39.6 1.6 3.8 91.8 Example 11 0.2 1.2 56.5 36.3 4.8 1.0 92.8 Example 12 0.1 5.5 50.2 40.0 1.0 3.2 90.2 Example 13 0.4 2.2 52.3 39.0 2.7 3.4 91.3 Example 14 0.6 2.3 52.6 38.2 1.3 0.2 90.8 Example 15 0.9 0.8 51.6 38.4 0.9 0.7 90.0 Example 16 0.2 4.2 60.1 32.0 2.8 0.7 92.1 Example 17 0.3 2.1 50.6 39.4 1.6 6.0 90.0 Comparative 10.7 9.1 46.2 24.6 7.5 1.9 70.8 Example 1 Comparative 8.6 8.3 44.5 24.3 6.5 7.8 68.8 Example 2 Comparative 5.9 10.3 35.6 26.3 9.6 12.3 61.9 Example 3 Comparative 6.2 14.3 39.2 24.3 5.9 10.1 63.5 Example 4 Comparative 0.7 9.1 56.2 24.6 7.5 1.9 80.8 Example 5 Comparative 3.8 10.8 34.8 32.9 6.9 10.8 67.7 Example 6 Comparative 4.3 7.8 29.9 34.8 9.7 13.5 64.7 Example 7 Comparative 2.5 8.5 40.1 29.9 10.7 8.3 70.0 Example 8 Comparative 2.9 11.5 37.8 34.7 6.9 6.2 72.5 Example 9 Comparative 3.5 9.9 40.8 33.2 8.9 3.7 74.0 Example 10

[0116] From the product performance parameters and composition distributions of the above examples, it can be seen that with Lewis acid as the main catalyst and each of 4-fluoro-1-butanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 3-iodo-1-propanol, 4-bromo-1-butanol, hydroxyacetic acid, 6-hydroxy-hexanoic acid, 3-nitropropanol, 4-amino-1-butanol, 4-hydroxybutanesulfonic acid, 6-hydroxy-2-hexanone, 5-hydroxyvaleraldehyde, 8-hydroxyoctanoic acid and 10-hydroxydecanoic acid as the cocatalyst, the obtained base oil has a kinematic viscosity of 4-10 mm.sup.2/s at 100° C., a viscosity index greater than 130, and much more target products (C.sub.30+C.sub.40) than Comparative Examples 3 to 10 (using conventional butanol, isopropanol, acetic acid, deionized water, ethyl acetate, phosphoric acid, dimethyl ether, or acetone as cocatalysts).

[0117] The products obtained with the catalyst compositions in Example 1 and Comparative Example 3 are analyzed by gas chromatography, and the results are shown in FIGS. 5 and 6. The product composition obtained with the initiator of the present disclosure is mainly C.sub.30 and C.sub.40 (the retention times are 15 to 17 min and 20 to 23 min, respectively, in FIG. 5), while the product composition obtained with butanol as the initiator has a wider distribution, as shown in FIG. 6. The chromatographic analysis is performed using a hydrogen flame ionization detector with a carrier gas of nitrogen and a precolumn pressure of 0.07 MPa, a hydrogen flow rate of 30 mL/min and an air flow rate of 250 mL/min. The inlet temperature is 250° C., the detector temperature is 400° C., the vaporizer temperature is 450° C., and the split ratio is 100:1. Programmed heating is used: the initial temperature is 50° C. and maintained for 10 min; then, the temperature is ramped up to the termination temperature of 380° C. at a heating rate of 9° C./min and maintained for 10 min.

[0118] As seen by comparing Example 1 with Comparative Examples 1 and 2, good product performance and high selectivity of target products can be obtained in the range of molar ratios of the main catalyst to the cocatalyst given by the present disclosure.

[0119] In addition, performance tests of other α-olefins as the raw material were carried out with the catalyst compositions prepared in Example 1 according to the following process: 1-octene, 1-dodecene, and coal-based α-olefins were used as the raw material, respectively, and the raw material was firstly fed into the tank polymerization reactor, and the catalyst composition prepared in Example 1 was continuously added into the polymerization reactor, wherein the amount of the catalyst composition was 1.0 wt. % (as the mass fraction of α-olefin raw material), the reaction temperature was controlled at 25° C., and the residence time was 60 min. After the reaction, the catalyst was separated and the product was obtained after hydrogenation. The product was collected for chromatographic analysis and performance testing, and the results were shown in Table 3.

[0120] As seen from Table 3, the catalyst compositions of the present disclosure are suitable for the polymerization reactions of various α-olefins (1-octene, 1-dodecene, and coal-based α-olefins), and the resultant polymerization products have relatively good viscosity-temperature and low-temperature properties.

TABLE-US-00003 TABLE 3 Performance parameters of products obtained with different α-olefin raw materials α-olefin Viscosity Pour NO. raw materials KV100° C./mm.sup.2/s index point/° C. 1 1-octene 3.03 125 −60° C. 2 1-dodecene 5.07 132 −60° C. 3 coal-based α-olefins 4.15 134 −60° C. (C.sub.6-C.sub.14 fraction)

[0121] Obviously, the above examples of the present disclosure are only examples to clearly illustrate the present disclosure, and not limiting the implementation of the present disclosure. For a person of ordinary skill in the art, other variations or changes can be made in different forms on the basis of the above description. It is not possible to exhaust all embodiments herein, but all obvious variations or changes derived from the technical solutions of the present disclosure are still within the protection scope of the present disclosure.