KR20010056179A - A method for preparation of polyalphaolefins by reacting 1-octene with preliminary-polymerized 1-decene - Google Patents

Abstract

PURPOSE: Provided is a process for producing poly alpha-olefin from 1-octene by using prepolymer of 1-decene, which is a high yield by prepolymerizing 1-decene and reacting 1-octene with it under a high temperature and a high pressure. CONSTITUTION: The poly alpha-olefin being 90cSt or more of coefficient of kinematic viscosity and 135 or more of index of viscosity at 40deg.C is obtained by reacting ethyl aluminum dichloride with t-butyl chloride to prepolymerize 1-decene, and reacting 1-octene with the prepolymerized 1-decene as a catalyst under a high temperature and a high pressure.

Description

A method for preparation of polyalphaolefins by reacting 1-octene with preliminary-polymerized 1-decene}

The present invention uses a product obtained by prepolymerizing 1-decene with ethylaluminum dichloride (EADC) and t-butyl chloride (TBC) as a catalyst and 1-octene as a raw material. The present invention relates to a method for producing an alpha olefin in a high yield at room temperature and atmospheric pressure.

In general, polyalphaolefins have fluidity in a wide temperature range due to high viscosity index and low low temperature fluidity, so they have excellent low temperature fluidity and narrow molecular weight distribution, so they have a low evaporation loss and excellent stability. Synthetic oil suitable as base oil for engine oil or industrial engine oil.

Therefore, with the development of the conventional industry, research on the production of polyalphaolefins is also actively progressed, and the contents thereof are as follows.

USP 4,532,061 discloses a R ₃ Al ₂ X ₃ or R _n AlX _3-n (wherein, R is an aryl group, a C _7~9 alkyl group of C _1~18, C _7~9 alkaryl group or a C _6~10 An aryl group, X is Cl, Br or I, n is an integer of 1 to 3; and an aluminum compound represented by (-CH ₂ CR ¹ R ^2- ) _m Y _p (R ¹ is hydrogen or C _Is an alkyl group of _{1 to 3} , R ² is a linear or branched C _1-30 alkyl group, Y is Cl, Br or I, m is an integer of 3 to 3000, and p is an integer of at least 3). A method of preparing a high viscosity polyalphaolefin is disclosed by diluting a polyhalogenated organic hydrocarbon catalyst represented by an alpha olefin having 3 or more carbon atoms, followed by mixing and reacting under a temperature condition of 0 to 60 ° C., US Pat. No. 4,469,910 The alkyl halide catalyst having an alkyl aluminum and at least one halide group is diluted with an alpha olefin having at least 3 carbon atoms, and then mixed And a method of producing a high viscosity polyalphaolefin by reacting at a temperature of 42 ± 2 ° C., and also disclosed in USP 4,594,469 is an alkyl aluminum bromide or an iodine compound and a promoter (alkyl iodide and alkyl bromide). A method of producing a high viscosity polyalphaolefin having a kinematic viscosity of at least 300 cSt at 40 ° C. by reacting a catalyst composition consisting of C) and an alpha olefin having 3 or more carbon atoms is disclosed.

However, in the past, polyalphaolefins have been prepared using various catalysts and one type of alpha olefins, particularly 1-decene, as described above, but since the price and demand of 1-decene are increasing, supply of raw materials is also difficult. Therefore, poly-alpha olefins are produced by using 1-hexene or 1-octene, which are cheaper than 1-decene, but a polyalpha olefin produced by using 1-hexene or 1-octene as a raw material. Viscosity index, which is a measure of stability, is lower than polyalphaolefin made of 1-decene.

Thus, the present inventors have studied a method for preparing a polyalphaolefin having a viscosity index similar to that of a polyalphaolefin prepared with 1-decene even with a small amount of 1-decene, and as a result, ethyl aluminum dichloride ( EADC) and t-butyl chloride (TBC) as a catalyst to prepolymerize a small amount of 1-decene and then react the product with 1-octene, which is cheaper than 1-decene and easier to supply, at room temperature and atmospheric pressure. The present inventors have found that a polyalphaolefin having a kinematic viscosity at 40 ° C. of 90 cSt or more and a viscosity index of 135 or more can be produced and completed the present invention.

Accordingly, it is an object of the present invention to provide a method for producing high viscosity polyalphaolefins having a kinematic viscosity at 40 ° C of 90 cSt or more and a viscosity index of 135 or more using a small amount of 1-decene in high yield.

In order to achieve the above object, the preparation method according to the present invention is ethyl aluminum di chloride (hereinafter referred to as 'EADC') and t -butyl chloride (hereinafter referred to as 'TBC') After the pre-polymerization of 1-decene, the product is used as a catalyst and reacted with 1-octene at room temperature and atmospheric pressure.

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

The polyalphaolefin may be used as an automotive lubricant or industrial engine oil, but the polyalphaolefin prepared according to the manufacturing method of the present invention has a kinematic viscosity at 40 ° C of 90 cSt or more, a viscosity index of 135 or more, and may be used as industrial engine oil. It can be a high viscosity oil.

The preparation method of the present invention is a method in which 1-decene prepolymerized by EADC and TBC is reacted with 1-octene at room temperature and atmospheric pressure to obtain a polyalphaolefin having a desired kinematic viscosity and viscosity index, wherein 1-octene and preparative It is preferable to adjust the molar ratio of 1-decene superposed | polymerized by the ratio of 10-50: 1. This is because when the molar ratio is 10 or less, the amount of 1-decene to be used is inefficient, and when it is 50 or more, there is little effect of improving the viscosity index.

On the other hand, in the production method of the present invention, the reaction temperature and the reaction pressure were set to normal temperature and normal pressure, the normal temperature means a temperature range of 20 ~ 40 ℃, the normal pressure means about 760mmHg.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to these examples.

<Example 1>

After equipping a 1 L reactor with a stirrer, a cooling coil, and a thermometer, nitrogen was flowed into a nitrogen atmosphere while maintaining 30 ° C, and 300 ml of octene was added thereto. Mix 1-decene with 5.4 ml of 3.4 M EADC and 2.1 ml of 8.99 M TBC to make 21 ml so that the molar ratio of ethylaluminum dichloride (EADC) and t-butyl chloride (TBC) is 1: 1. I put it. At this time, the molar ratio of 1-octene and 1-decene is 10: 1. A 500 ml 4-neck flask was equipped with a stirrer, a condenser equipped with a cooling coil, and a thermometer, and nitrogen was flowed into a nitrogen atmosphere while maintaining the temperature at 30 ° C. While stirring with a stirrer, EADC and TBC diluted in 1-decene were injected for 5 minutes using a microinjector, followed by stirring for 5 minutes. The syringe then quickly fills the prepolymerized stomach product. This product was injected into a 1 L reactor containing 1-octene using a microinjector for 20 minutes. After injection of the prepolymerized product, the mixture was stirred for 30 minutes and then catalyst residue was removed using 200 ml of 0.1 M NaOH. The reaction product from which the residue was removed was vacuum distilled at 180 ° C. to 1 torr to remove the low boiling point product and unreacted monomer, and then the distillation residue was filtered to obtain a final product (yield: 77.3 wt%). After measuring the kinematic viscosity and viscosity index of the produced polyalphaolefin based on the KSM 2014 method, the result is shown in Table 1.

<Example 2>

The polyalphaolefin was obtained in the same manner as in Example 1 except that the 1-decene prepolymerized product was injected into a 1 L reactor using a microinjector for 10 minutes (yield: 76.8 wt%). The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

<Example 3>

300 ml of 1-octene was added to the same 1 L reactor as in Example 1. The molar ratio of EADC and TBC was 1: 1, and 1-decene was mixed in 5.4 ml of 3.4 M EADC and 2.1 ml of 8.99 M TBC, respectively, to 12.4 ml, and then placed in a syringe. The molar ratio of 1-octene and 1-decene is 20: 1.

After the prepolymerization was carried out in the same manner as in Example 1, the prepolymerization product was injected into the 1 L reactor using a microinjector for 20 minutes in the same manner. Polyalphaolefin was obtained by the catalyst residue removal, distillation and filtration in the same manner as in Example 1 (yield: 80.4 wt%). The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

<Example 4>

In the same manner as in Example 1, the catalyst and 1-decene were charged into a syringe, and then pre-polymerized by injecting the same in a 1 L reactor for 5 minutes. After 5 minutes, 300 ml of 1-octene was injected into the prepolymer product while stirring with a stirrer for 20 minutes using a microinjector. Polyalphaolefin was obtained by the catalyst residue removal, distillation and filtration in the same manner as in Example 1 (yield: 75.4 wt%). The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

Comparative Example 1

After installing a stirrer, a cooling coil, and a thermometer in a 1 L reactor, nitrogen was flowed into a nitrogen atmosphere while maintaining 30 ° C. 300 ml of 1-octene was added thereto. The molar ratio of ethylaluminum dichloride and t-butyl chloride was 1: 1, mixed with 1-octene in 5.4 ml of 3.4 M EADC and 2.1 ml of 8.99 M TBC, respectively, to 21 ml, and then put in a syringe. While stirring with a stirrer, EADC and TBC diluted in 1-octene were injected for 20 minutes using a microinjector. After the injection, the mixture was stirred for 30 minutes, and the catalyst residue was removed using 200 ml of 0.1 M NaOH. Distillation and filtration were carried out in the same manner as in Example 1 to obtain a polyalphaolefin (yield: 80.4 wt%). The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

Comparative Example 2

After installing a stirrer, a cooling coil, and a thermometer in a 1 L reactor, nitrogen was flowed into a nitrogen atmosphere while maintaining 30 ° C. 300 ml of 1-octene and 34.4 ml of 1-decene were added thereto. The ratio of 1-octene and 1-decene is 10: 1. After preparing the catalyst in the same manner as in Comparative Example 1 and injecting into the reactor for 20 minutes in the same manner, the final product was obtained by removing the catalyst residue, distillation, and filtration in the same manner as in Comparative Example 1 (yield: 79.4wt%) . The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

Comparative Example 3

After installing a stirrer, a cooling coil, and a thermometer in a 1 L reactor, nitrogen was flowed into a nitrogen atmosphere while maintaining 30 ° C. 344 ml of 1-decene was added thereto. 1-decene was mixed in 5.4 ml of 3.4M EADC and 2.1 ml of 8.99M TBC so that the molar ratio of ethylaluminum dichloride and t-butyl chloride was 1: 1 to 21 ml, and then put in a syringe. While stirring with a stirrer, EADC and TBC diluted in 1-decene were injected into a 1 L reactor for 20 minutes using a microinjector. After the injection, the mixture was left for 30 minutes and the catalyst residue was removed using 200 mL of 0.1 M NaOH. Polyalphaolefin was obtained by distillation and filtration in the same manner as in Example 1 (yield: 82.4 wt%). The kinematic viscosity and viscosity index of the resulting polyalphaolefin were also measured in the same manner as in Example 1 and shown in Table 1.

Molar ratio of 1-octene / 1-decene Preliminary polymerization time (minutes) Response time (minutes) 40 ° C kinematic viscosity (cSt.) Viscosity index Example One 10 10 20 124.6 138 2 10 10 10 94.7 135 3 20 10 20 108.4 136 4 10 10 20 101.5 135 Comparative example One ∞ 0 20 77.1 130 2 10 0 20 93.5 132 3 0 0 20 103.3 139

As can be seen from the above description, when 1-decene is prepolymerized as a catalyst and reacted with 1-octene at room temperature and atmospheric pressure, polyalphaolefin having a high viscosity index of 135 or more even when a small amount of 1-decene is used. Can be prepared in high yield.

Claims (2)

Ethyl aluminum dichloride (ethyl aluminum dichloride; EADC) and t - butyl chloride (t -butyl chloride; TBC) and then pre-polymerized with 1-decene using the catalyst, by using this as a catalyst temperature of 20~40 ℃, A method of producing a polyalphaolefin having a kinematic viscosity index of 90 cSt or more and a viscosity index of 135 or more from 1-octene by reaction under a pressure of 760 mmHg. The method according to claim 1, wherein the molar ratio of 1-decene used for prepolymerization with 1-octene is adjusted in the range of 10 to 50: 1.