KR102121959B1 - Method for polymerizating alpha-olefin - Google Patents

Abstract

The present invention includes the step of preparing a polyalpha (α-olefin) by polymerizing alpha-olefin by adding an additive to a mixture of α-olefin and solvent under a Lewis acid catalyst, wherein the alpha-olefin It relates to a polymerization method of the alpha-olefin, by adjusting the molecular weight and / or viscosity of the polyalpha olefin by adjusting the amount of the solvent for. As a result, a high-viscosity alpha-olefin can be produced by adjusting the molecular weight and viscosity of the poly-alpha-olefin in a simple way to control the amount of the solvent while using the alpha-olefin polymerization method using a Lewis acid catalyst.

Description

METHOD FOR POLYMERIZATING ALPHA-OLEFIN

The present invention relates to a method for polymerizing alpha olefins, and more particularly, to a method for polymerizing alpha olefins capable of controlling molecular weight and viscosity in various ranges in order to prepare a lubricating base oil utilized in various fields.

Conventional lubricating base oils were manufactured using crude oil, that is, mineral lubricating oil. Although used in a variety of applications, such lubricants have a narrow viscosity range and contain impurities such as aromatic compounds, which has a problem of limited use for high performance machinery and equipment designed to operate under harsh conditions. Correspondingly, a synthetic base oil having higher performance is used. Among them, a polyalphaolefin (PAO) produced by polymerizing a long-chain α-olefin is a representative product.

Lubricants made of polyalphaolefin synthetic base oils extend the life of the machine, reduce maintenance and improve energy efficiency. In particular, operation at extremely high or low temperatures is only possible with polyalphaolefin lubricant base oils.

In the synthesis of polyalphaolefins, boron or aluminum Lewis acid-mediated cationic polymerization of long-chain α-olefins is mainly used, and is typically performed with 1-decene. Fast chain transfer, a common phenomenon of cationic polymerization reactions, produces polyalphaolefins with low degrees of polymerization, thus obtaining products of low viscosity in general. In addition, there is no limitation in the production of various product lines due to the lack of molecular weight control technology.

Therefore, the polymer thus prepared is used for manufacturing low-viscosity lubricants, and generally has a viscosity of 10 cSt or less at 100°C. However, in order to prevent lubrication and abrasion, ultra-high viscosity polyalphaolefin is required, and when polymerizing polyalphaolefin with ultra-high viscosity, a method using a Ziegler-Natta catalyst or a metallocene catalyst is used. The use of such a catalyst has a problem in that the manufacturing cost of the catalyst is improved and the process is complicated.

On the other hand, the conventional cationic polymerization using a Lewis acid catalyst has the advantage that it is simple and does not require strict conditions, but there is a problem in that the range of products applied is narrow because it is a polymerization method applied only to production of low viscosity polyalphaolefins.

Korean Registered Patent Publication No. 10-1721277 Korean Patent Publication No. 10-2015-0109361

The object of the present invention is to solve the above problems, and while using an alpha olefin polymerization method using a Lewis acid catalyst, it is a simple method of controlling the amount of the solvent, and also controls the molecular weight and viscosity of the poly alpha olefin to polymerize to high viscosity alpha olefin. By providing a method for polymerizing alpha olefins, the process is very simple, manufacturing a high-viscosity lubricating base oil while reducing the process cost, and broadening the utilization range of the lubricating base oil.

According to one aspect of the invention,

And adding an additive to the mixture of α-olefin and solvent under a Lewis acid catalyst to polymerize alpha-olefin, thereby producing poly(α-olefin). It provides a polymerization method of the alpha olefin, which controls the molecular weight and/or viscosity of the polyalpha olefin by controlling the amount of the solvent.

The polymerization method of the alpha olefin comprises the steps of adding a Lewis acid catalyst to a reaction vessel and creating a nitrogen or argon atmosphere; Adding an alpha olefin and a hydrocarbon solvent to the reaction vessel; And polymerizing the alpha olefin while slowly adding the additive to the reaction vessel to produce a polyalpha olefin.

The Lewis acid catalyst may be at least one selected from AlCl ₃ , EtAlCl ₂ , Et ₂ AlCl, ZnCl ₂ , ZnBr ₂ , BF ₃ (OEt ₂ ), TiCl ₄ , AlF ₃ , SnCl ₄ and SbCl ₅ .

Preferably, the Lewis acid catalyst may be at least one selected from AlCl ₃ , EtAlCl ₂ and Et ₂ AlCl.

More preferably, the Lewis acid catalyst may be AlCl ₃ .

The Lewis acid catalyst may be used in an amount of 0.5 to 5.0 mol% with respect to the alpha olefin and additives.

The alpha olefin may be at least one selected from ethylene and an alpha olefin of C3 to C20.

The alpha olefin may be at least one selected from 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1-tetradecene.

The solvent may be a hydrocarbon solvent.

The hydrocarbon solvent may be any one selected from butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, and ethylbenzene.

Preferably, the hydrocarbon solvent may be any one selected from hexane, heptane and octane.

The hydrocarbon solvent may control the molecular weight and/or viscosity of the polyalpha olefin by adjusting the content in the range of 1 to 100 equivalent parts, with respect to the 1 equivalent part of the alpha olefin, preferably with respect to the 1 equivalent part of the alpha olefin, The molecular weight and/or the viscosity of the polyalphaolefin finally produced can be increased by using 1 to 10 equivalents of a hydrocarbon solvent.

The additive may be any one selected from water, methanol, ethanol, isopropyl alcohol, cyclohexanol, t-butyl alcohol, and t-butyl chloride.

Preferably, the additive may be water.

The additive may be used in an amount of 0.5 to 5.0 mol% with respect to the alpha olefin and Lewis acid catalyst.

The viscosity of the polyalpha olefin may be adjusted to 100 to 400 cSt based on 40°C.

The viscosity of the polyalpha olefin can be adjusted to 10 to 50 cSt based on 100 ℃.

The polymerization reaction can be terminated by adding sodium hydroxide.

The polyalpha olefin may be used as a lubricant base oil.

The polymerization method of the alpha olefin of the present invention is a simple method of controlling the amount of the solvent while using the alpha olefin polymerization method using a Lewis acid catalyst to control the molecular weight and viscosity of the poly alpha olefin to polymerize to a high viscosity alpha olefin. It is very simple and has the effect of manufacturing a high-viscosity lubricating base oil while reducing the process cost, thereby broadening the utilization range of the lubricating base oil.

1 is a result of ¹ H-NMR analysis after poly(1-decene) polymerization according to Experimental Example 2.
2 is a result of gel permeation chromatography (GPC) analysis according to Experimental Example 3.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted. .

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, or combination thereof described in the specification exists, or that one or more other features or It should be understood that the existence or addition possibilities of numbers, steps, actions, elements, or combinations thereof are not excluded in advance.

Hereinafter, a method for polymerizing the alpha olefin of the present invention will be described.

In the polymerization method of alpha olefin of the present invention, an additive is added to a mixture of α-olefin and hydrocarbon solvent under a Lewis acid catalyst to polymerize alpha-olefin to produce poly(α-olefin). Including, by adjusting the amount of the hydrocarbon solvent for the alpha-olefin may control the molecular weight and / or viscosity of the polyalpha-olefin.

Specifically, the polymerization method of the alpha olefin first, it is preferable to put a Lewis acid catalyst in a reaction vessel to create a nitrogen or argon atmosphere, but the scope of the present invention is not limited thereto, and polymerization in air or other possible gas atmosphere You can also do

Next, it is preferable to polymerize the alpha olefin at a polymerization start temperature of 35° C. or lower while gradually adding an additive to the reaction vessel to produce a polyalpha olefin. The polymerization start temperature may be more preferably 30° C. or less, and even more preferably 25° C. or less.

The Lewis acid catalyst may be AlCl ₃ , EtAlCl ₂ , Et ₂ AlCl, ZnCl ₂ , ZnBr ₂ , BF ₃ (OEt ₂ ), TiCl ₄ , AlF ₃ , SnCl ₄ , SbCl _5, etc., but preferably AlCl ₃ , EtAlCl ₂ , and Et ₂ AlCl, and the like, and even more preferably AlCl ₃ .

The Lewis acid catalyst is preferably used in an amount of 0.5 to 5.0 mol% with respect to the alpha olefin and additives, more preferably 1.0 to 4.0 mol%, and even more preferably 2.0 to 4.0 mol%.

The alpha olefin is preferably at least one selected from ethylene and an alpha olefin of C3 to C20, more preferably 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1 -It may be one or more selected from tetradecene.

The solvent may be a hydrocarbon solvent, preferably any one selected from butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, and ethylbenzene, even more preferably hexane, heptane, and It may be any one selected from octane.

The hydrocarbon solvent may control the molecular weight and/or viscosity of the polyalpha olefin by adjusting the content in the range of 1 to 100 equivalent parts, with respect to the 1 equivalent part of the alpha olefin, preferably with respect to the 1 equivalent part of the alpha olefin, The molecular weight and/or viscosity of the polymerized polyalphaolefin can be increased by using 1 to 10 equivalents of a hydrocarbon solvent. At this time, the molecular weight and/or viscosity of the polyalpha olefin polymerized in proportion to the content of the solvent in the range of 1 to 10 equivalents of the hydrocarbon solvent may be increased.

The additive may be any one selected from water, methanol, ethanol, isopropyl alcohol, cyclohexanol, t-butyl alcohol, and t-butyl chloride, and preferably water.

The additive is preferably used in an amount of 0.5 to 5.0 mol% with respect to the alpha olefin and Lewis acid catalyst, more preferably 1 to 3.0 mol%, even more preferably 1.5 to 2.5 mol%.

The viscosity of the polyalpha olefin may be adjusted to 100 to 400 cSt based on 40°C.

In addition, the viscosity of the polyalpha olefin can be adjusted to 10 to 50 cSt based on 100 ℃.

It is preferable to terminate the polymerization reaction by addition of sodium hydroxide.

The polyalpha olefin may be used as a lubricating base oil, and may be particularly made of a high viscosity lubricating base oil.

Hereinafter, an embodiment according to the present invention will be described in detail.

[ Example ]

(1) 1- Desen polymerization

Example 1 to 9: 1- Dessen By polymerization Poly(1-decene) Produce

After adding AlCl ₃ to a 1L round-bottomed flask and making it into a nitrogen state, 1-decene (50 mL) and a hydrocarbon solvent hexane were added at 0° C., and then H ₂ O was slowly added at room temperature. After reacting for 1 hour, 5 wt% NaOH was added to terminate the reaction. The amount of AlCl ₃ , H ₂ O, and hexane is as summarized in Table 1 below according to the corresponding example, and the molecular weight and viscosity of the poly(1-decene) prepared according to each example are also described.

Comparative example 1: 1- Dessen By polymerization Poly(1-decene) Produce

Poly(1-decene) was synthesized in the same manner as in Example 1, except that hexane, a hydrocarbon solvent, was not used.

The catalysts, additives, solvent content, and molecular weight and viscosity of the synthesized poly(1-decene) used in the preparation of Examples 1 to 9 and Comparative Example 1 are summarized in Table 1 below. Here, the viscosity is ASTM-445, the viscosity index (Viscosity Index) is measured in accordance with ASTM-2270.

division catalyst
AlCl ₃
(mol%) additive
H ₂ O
(mol%) menstruum
(Hexane) Conversion rate (%) Number average molecular weight (M _n )
(g/mol) Weight average molecular weight
(M _W )
(g/mol) Viscosity (cSt) Viscosity index
(Viscosity Index) 40℃ 100℃ Sigma PAO - - - - 940 990 46.9 8.0 143 Comparative Example 1 1.2 2.4 None 39 1240 1630 - - - Example 1 1.2 2.4 1equiv 98 1300 1540 - - - Example 2 1.2 1.2 1 equiv 97 1200 1450 - - - Example 3 0.6 2.4 1 equiv 54 1130 1470 - - - Example 4 2.4 2.4 1 equiv >99 1280 1560 - - - Example 5 3.6 2.4 1 equiv >99 1480 1840 123 16.7 148 Example 6 3.6 2.4 2 equiv >99 1610 2010 173 21.7 149 Example 7 3.6 2.4 5 equiv >99 1770 2280 195 24.3 154 Example 8 3.6 2.4 10 equiv >99 1880 2450 323 34.3 150 Example 9 3.6 2.4 20 equiv >99 1770 2330 98.5 20.9 240

(2) 1- Octenic polymerization

Example 10 to 12: 1- Octene By polymerization Poly(1-octene) Produce

AlCl ₃ in a 1L round bottom flask (5.96 mmol, 0.759 g) was added and made into a nitrogen state. After adding 1-Octene (159 mmol, 25 mL) and hexane (2-octene 2,5,10 equiv.) at 0°C, H ₂ O (3.79 mmol, 68 μL) was added at room temperature. After reacting for 1 hour, 5 wt% NaOH was added to terminate the reaction.

Example 13-15: 1- Octene By polymerization Poly(1-octene) Produce

Poly(1-octene) was prepared in the same manner as in Examples 10 to 12, except that a heptane solvent was used instead of hexane.

Comparative example 2: 1- Octene By polymerization Poly(1-octene) Produce

Poly(1-octene) was prepared in the same manner as in Example 10, except that no hexane solvent was used.

The molecular weight of the poly(1-octene) prepared by the 1-octene polymerization and the polydispersity index (PDI) accordingly are summarized in Table 2 below.

division Solvent type Solvent consumption Molecular weight ( M _n / M _w ) Comparative Example 2 not used - 1160/1450
PDI=1.25 Example 10 Hexane 2equiv 1350/1690
PDI=1.25 Example 11 Hexane 5equiv 1590/2040
PDI=1.28 Example 12 Hexane 10equiv 1620/2130
PDI=1.31 Example 13 Heptane 2equiv 1320/1640
PDI=1.24 Example 14 Heptane 5equiv 1630/2090
PDI=1.28 Example 15 Heptane 10equiv 1800/2320
PDI=1.29

According to this, it can be seen that the molecular weight increases as the amount of the solvent (hexane or heptane) increases from 2equiv to 10equiv.

(3) 1- Dodecene polymerization

Example 16 to 18: 1- Dodesen By polymerization Poly(1-dodecene) Produce

AlCl ₃ in a 1L round bottom flask (4.02 mmol, 0.536 g) was added and made into a nitrogen state. After adding 1-dodecene (113 mmol, 25 mL) and hexane (1, 2-dodecene 1,2,5,10 equiv.) at 0°C, H ₂ O (2.69 mmol, 48 μL) was added at room temperature. After reacting for 1 hour, 5 wt% NaOH was added to terminate the reaction.

Example 19-21: 1- Dodesen By polymerization Poly(1-dodecene) Produce

Poly(1-dodecene) was prepared in the same manner as in Examples 16 to 18, except that a heptane solvent was used instead of hexane.

Comparative example 3: 1- Dodesen By polymerization Poly(1-dodecene) Produce

Poly(1-dodecene) was prepared in the same manner as in Example 16, except that no hexane solvent was used.

The molecular weight of the poly(1-dodecene) prepared by the 1-dodecene polymerization and the polydispersity index (PDI) accordingly are summarized in Table 3 below.

division Solvent type Solvent consumption Molecular weight ( M _n / M _w ) Comparative Example 3 not used - 1530/1970
PDI=1.29 Example 16 Hexane 2equiv 1750/2160
PDI=1.23 Example 17 Hexane 5equiv 1990/2450
PDI=1.23 Example 18 Hexane 10equiv 2020/2550
PDI=1.26 Example 19 Heptane 2equiv 1810/2560
PDI=1.41 Example 20 Heptane 5equiv 2080/2500
PDI=1.20 Example 21 Heptane 10equiv 2280/2670
PDI=1.17

According to this, in the case of 1-dodecene polymerization, the molecular weight increased when the hexane solvent was used in 2equiv to 5equiv, but the molecular weight decreased when 10equiv was used. On the other hand, in the case of using a heptane solvent, it was found that the molecular weight also increases when the amount is increased from 2equiv to 10equiv.

[ Experimental Example ]

Experimental Example 1: Measurement of conversion rate by catalyst and additive type

In a glove box, a catalyst (0.19 mmol) is added to a 20 ml reaction vial, 1-Decene (16 mmol, 3 ml) is added at 0°C, and then an additive (1 equiv for catalyst, 1 equiv for t-BuCl is 1 equiv and 5 equiv at 30°C). ). After reacting for 1 hour, 5 wt% NaOH was added to terminate the reaction. Different types of catalysts and additives are used according to the above method, and the conversion to poly(1-decene) is measured and the results are shown in Table 4 below.

catalyst
additive AlCl ₃ EtAlCl ₂ Et ₂ AlCl H ₂ O 65% 84% X MeOH 46% 74% X EtOH - X - i-PrOH 52% X - CyOH 59% X - t-BuOH 40% X - t-BuCl(1eq) - - <10% t-BuCl(5eq) - - 91%

Experimental Example 2: Analysis of conversion rate according to the amount of solvent input

After the reactions of Examples 1 to 9 and Comparative Example 1, ¹ H-NMR analysis was performed, and the results are shown in FIG. 1. According to Table 1 and Figure 1, Comparative Example 1 exhibited a conversion rate of 39%. Compared to commercial low-viscosity polyalphaolefins, both number average molecular weight (M _n ) and mass average molecular weight (M _w ) were measured higher. However, uncontrolled exothermicity in Comparative Example 1 without using solvents required special attention during polymerization. In an embodiment of the present invention, in order to control an uncontrolled reaction temperature, a hydrocarbon solvent, hexane, was introduced, and when an equimolar amount of hexane was used for 1-decene, the consumption of 1-decene in Example 1 was 98%. Was observed.

Next, the effects of AlCl ₃ and water were investigated. In Example 2, when the water additive was reduced to 1.2 mol%, the molecular weight was found to decrease slightly. In Example 3, when the amount of AlCl ₃ was reduced in half to 0.6 mol%, the proportion of oligomerization was found to drop rapidly to 54%.

In the AlCl ₃ usage increase experiment, when 2.4 mol% AlCl _{3 was} used, 1-decene was completely converted to poly(1-decene), but the molecular weight was not significantly increased. However, in Example 5, when 3.0 mol% of AlCl ₃ was used, the molecular weight increased to 1480 g/mol, and 1-decene was also completely converted.

Since a dramatic change was observed using a small amount of solvent hexane, in order to observe the change in molecular weight and viscosity according to the amount of solvent, let's change the addition amount of hexane to 1 to 10 equiv with respect to the amount of 1-decene. hexane). example 8 (10 equiv hexane) was shown to and from the content of hexane increasing M _n = 1880 g / mol with a molecular weight M _w = 2450 g / mol by about 50%. However, as in Example 9, when hexane exceeds 20 equiv, the molecular weight tends to decrease.

Experimental Example 3: Gel permeation Chromatography ( GPC ) analysis

The results of gel permeation chromatography for commercial PAO, Comparative Example 1, and Examples 1 to 9 are shown in FIG. 2. According to this, commercial PAOs (black line, Mn = 940 g/mol, Mw = 990) consisted of low molecular weight oligomers, but it was clearly shown that the cationic polymerization initiated with AlCl ₃ and water had a higher degree of polymerization.

The hexane-free polymerization of Comparative Example 1 showed a sharp peak corresponding to 1-decene in the vicinity of 32 mL THF elution due to low conversion (black dotted line). It was found that the addition of hexane moves the GPC trace to the high molecular weight region while simultaneously reducing the portion of low polymerization degree.

Similar molecular weight distributions were formed when Example 7 (yellow line) using 5 equiv hexane, Example 8 (green line) using 10 equiv hexane, and Example 9 (blue dotted line) using 20 equiv hexane were used. It was shown in 8 that more poly(1-decene) was prepared compared to Example 9. Therefore, it was found that the molecular weight was lowered when 20 equiv hexane was used.

The embodiments of the present invention have been described above, but those skilled in the art can add, change, delete, or add components within the scope of the present invention described in the claims. It will be said that the present invention can be variously modified and changed by the like, and this is also included within the scope of the present invention.

Claims (17)

Producing a poly(α-olefin) by polymerizing alpha-olefin by adding an additive to a mixture of alpha olefin and solvent under a Lewis acid catalyst,
Adjusting the molecular weight and/or viscosity of the polyalphaolefin by controlling the amount of the solvent relative to the alphaolefin,
The Lewis acid catalyst is AlCl ₃ ,
The solvent is a hydrocarbon solvent,
The hydrocarbon solvent is characterized in that the higher the content in the range of 1 to 10 equivalents relative to 1 equivalent by weight of the alpha olefin, the higher the molecular weight and/or viscosity of the polyalpha olefin, the polymerization method of the alpha olefin. According to claim 1,
The polymerization method of the alpha olefin,
Adding a Lewis acid catalyst to the reaction vessel to create a nitrogen or argon atmosphere;
Adding an alpha olefin and a hydrocarbon solvent to the reaction vessel; And
Polymerizing an alpha olefin while slowly adding an additive to the reaction vessel to produce a poly alpha olefin; delete delete delete According to claim 1,
The Lewis acid catalyst is a method for polymerization of alpha olefins, characterized in that it is used in an amount of 0.5 to 5.0 mol% relative to the alpha olefin and additives. According to claim 1,
The alpha olefin is ethylene, and an alpha olefin polymerization method characterized in that at least one selected from C3 to C20 alpha olefin. The method of claim 7,
The alpha olefin polymerization method of alpha olefins, characterized in that at least one selected from 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and 1-tetradecene. delete According to claim 1,
The hydrocarbon solvent is a butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, and ethylbenzene polymerization method characterized in that any one selected from ethylbenzene. The method of claim 10,
The hydrocarbon solvent is a method for polymerization of alpha olefins, characterized in that any one selected from hexane, heptane, and octane. delete According to claim 1,
The additive is a polymerization method of alpha olefins, characterized in that any one selected from water, methanol, ethanol, isopropyl alcohol, cyclohexanol, t-butyl alcohol, and t-butyl chloride. The method of claim 13,
The additive is a polymerization method of alpha olefin, characterized in that the water. According to claim 1,
The additive is a method for polymerization of alpha olefins, characterized in that it is used in an amount of 0.5 to 5.0 mol% relative to the alpha olefin and Lewis acid catalysts. According to claim 1,
The viscosity of the polyalpha olefin is a polymerization method of alpha olefin, characterized in that adjusted to 100 to 400 cSt based on 40 ℃. According to claim 1,
The polymerization method of the alpha olefin, characterized in that the viscosity of the polyalpha olefin is adjusted to 10 to 50 cSt based on 100°C.

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