CS209414B2 - Method of making the liquid polymeres of high viscosity - Google Patents

Description

The present invention relates to a process for the production of liquid polymers having a viscosity of 250 to 15,000 mm @ ^-1 at 98.9 DEG C. obtained by polymerizing mixtures of C8 -C10 n-α-olefins derived from the cracking of wax and / or individual Ce, C9 or C10 -α-olefin of general formula

R - CH - CH2 in which R contains 6 to 8 atoms, in the presence of a catalyst system consisting of titanium tetrachloride T1Cl4 and an aluminum compound of the linear polyimine polymer type, i.e. a polyiminoalan of the general formula

Al-N 1 H R wherein n is an integer from 1 to 50 and preferably from 4 to 25 a

R isopropyl.

The catalyst system may be formed in situ, preferably in the absence of a solvent, for 5 to 60 minutes, optionally pre-formed in a solvent. The reaction temperature in both cases ranges from 0 to 150 ° C. the ratio of α-olefin to titanium tetrachloride in the range from 50 to 2000 and the molar ratio between polyiminoalan and titanium tetrachloride in the range from 1.3 to 5. The polymerization time is 1 to 6 hours, preferably 3 hours. The polymerization is carried out in a hydrogen atmosphere to a pressure of 0.1 MPa.

Methods of polymerizing α-olefins for the production of synthetic lubricants are known which utilize a catalyst system comprising a transition metal compound IV. to VIII. and an aluminum compound, such as polyiminoalan (PIA), at a hydrogen pressure of from 0.2 to 10 MPa, or in the presence of alkyl aluminum chlorides in the form of molecular weight regulators.

It has now been found that using the same catalyst system of titanium tetrachloride and polyiminoalan under a hydrogen atmosphere up to a pressure of 0.1 MPa, polymerization can be carried out at high polymer yields. The polymers obtained exhibit considerably higher molecular weight, higher viscosity, and considerably lower dimer content compared to known processes.

The weight ratio of olefins to tin (IV) tetrachloride ranges from 50: 1 to 2,000: 1. The cleaner the alpha-olefin load, the higher the ratio. When 1-decene is used, smaller amounts of titanium tetrachloride and polyiminoalan are used.

When using high-purity α-olefin packings, such as 1-decene, polymers exhibit much higher viscosity compared to polymers obtained from mixtures of α-olefins derived from wax cracking.

The viscosity of the product can be controlled by using an equivalent charge by varying the temperature of the catalyst system formed. At temperatures of 60 to 150 ° C, preferably 80 to 120 degrees Celsius, polymers with a much higher viscosity are obtained compared to polymers obtained at a lower temperature of the catalyst system, for example 0 to 25 ° C.

After the formation of the catalyst complex, the polymerization itself is carried out at a temperature of 80 to 120 ° C. When polymerizing at lower temperatures, for example 25 ° C, polymer yields and viscosity values are considerably lower.

The addition of polyiminoalan to titanium tetrachloride, i.e. the titanium tetrachloride reduction reaction while forming the catalyst complex of the invention, can be carried out very slowly, dropwise, for example for one hour. In this case, a polymer of very high viscosity is obtained

The formation of the catalyst complex is preferably carried out "in situ" in the starting olefins without the use of a solvent.

When the olefins are diluted with a solvent or the catalyst system is preformed in a solvent, polymer yields and viscosity values are lower.

The following compounds may be used as solvents: n-heptene, cyclohexane, benzene, chlorobenzene and / or their homologues or mixtures thereof.

The polymerization time ranges from 2 to 6 hours and preferably is 3 hours.

Product yields, based on unreacted polymer, range from 68 to 78% by weight. These values are obtained when using a filler in the form of an olefin fraction obtained from wax cracking and containing 80% by weight of n-α-olefins. When using a purer hydrocarbon feed such as 1-decene, polymer yields are up to 94% by weight.

The viscosities of the polymers at 98.9 ° C range from 250 to 15,000 mm ² s ^-1 . The molecular weight, measured by osmometry, ranges from 1000 to 3000.

When using the catalyst system of the invention, the reaction vessels must be cleaned, dried and purged with a dry gas, such as nitrogen or hydrogen.

The α-olefins used as filler must be de-aerated, dehumidified and cleaned, for example by treatment with depleted catalyst or anhydrous titanium tetrachloride, or by percolation on silica and / or molecular sieves.

The compositions and properties of α-olefins used as fillers in the process of the invention are shown in Tables I and II.

Table I

Filling: a mixture of commercially available 8 to 10 carbon atoms α-olefins, obtained by wax cracking by weight

iso-Cs olefins 0.82 n-α-olefins Ce 14.42 iso-Ca olefins 5.21 n-α-olefins C9 37.81 iso-C10 olefins 9.95 n-α-olefins C10 28.18 100.00 Total amount of n-a -olefins 80.41 wt. % specific weight of the mixture at 20 ° C 0.741 refractive index, n _D ²⁰ 1,4217 bromine number, g / 100 G 125 Table II Refill: 1-decen weight% iso-C10 olefins 1.44 n-α-olefins C10 95.19 olefins iso-Cii 3.37 100.00 specific weight at 20 ° C 0.741 refractive index, n _D ²⁰ 1,4232 bromine number, g / 100 G 114

Like α-olefins and possible solvents, all components of the catalyst system must be maintained in a hydrogen-saturated atmosphere.

The following examples illustrate some of the polymerization reactions of the invention without limiting the scope of the invention. Examples 1, 2 and 3

A 2 liter reactor equipped with a stirrer and jacket for circulating the heat-regulating liquid, completely dried, vented and purged with dry nitrogen, was charged with 1 liter [741 g] of C8-C10 α-olefin cracking waxes titanium dioxide, followed by 9.3 ml of a 2.1 molar solution of titanium tetrachloride in hexane. The weight ratio of olefins to titanium tetrachloride was 200: 1.

Subsequently, a 1 molar solution of poly- (N-isopropyliminoalan) in hexane in an amount of 209414 δ was fed into the reactor in a reactor in which the mixture of olefins and titanium tetrachloride was thermostatized to 80 ° C for 5 minutes.

with an H / Ti molar ratio of 2.5, Example 1 2.75, Example 2 and Example 3 3.0 (48.8 mL, 53.7 mL, and 58.6 mL of a 1.0 molar solution of PIA, polyiminoalan) ). Subsequently, hydrogen was fed to the autoclave at a pressure of 0.015 MPa while maintaining a temperature of 80 ° C throughout the polymerization, i.e. 3 hours.

Then the catalyst was deactivated by adding first methanol, followed by hydrochloric acid and finally water. The lower aqueous phase was removed and an additional amount of methanol was added. Stirring was continued and the aqueous phase was removed again, the operation was repeated until the aqueous phase was neutral.

Fractions were distilled off from the polymerization product to a temperature of 175 ° C to give a residue with a boiling point above 175 ° C. This residue represents the product of the invention.

The yield in Example 1 was 72 weight percent of a polymer having a viscosity at 98.9 ° C of 1030 mm ² s ^-1 . In Example 2 the yield was 78% by weight and the viscosity at 98.9 ° C was 1160 mm ² s ^-1 and in Example 3 it was 75% by weight. % and viscosity at 98.9 ° C 1450 mm ² s ~ ^! . The molecular weight, determined osmometrically, was 1350.

Examples4a5

The process conditions in these examples were analogous to Example 2 (olefin to titanium tetrachloride ratio 200: 1, molar ratio H / Ti - 2.75, catalyst complex temperature 80 ° C, polymerization time 3 hours), except that manometric the hydrogen pressure in Example 4 was 0.1 MPa and in Example 5 it was 0.2 MPa.

After processing, polymerization products analogously to the previous examples did in Example 4, the yield of product of 75% by weight, a viscosity of 1010 MRN ² during ^_1

98.9 ° C and in Example 5 was 73% by weight at a viscosity of 250 mm ² s ^-1 at 98.9 ° C.

These results show that the viscosity of the polymer remains high when the process is carried out to a hydrogen overpressure of 0.1 MPa and greatly reduced at a hydrogen overpressure of 0.2 MPa.

Example 6

In this example, the same conditions were used as in Example 2 (ratio of olefins to titanium tetrachloride 200: 1, molar ratio H / Ti = 2.75, catalyst complex formation and polymerization temperature of 80 ° C, polymerization time of 3 hours), with the difference The process was carried out under a nitrogen pressure of 0.015 MPa.

The yield was 56% by weight of a polymer having a viscosity of 2050 mm ² s ¹ at 98.9 ° C.

When comparing these results to those of Example 2, it is clear that using nitrogen instead of hydrogen yielded lower polymer yields of higher viscosity.

Examples 7 and 8

The polymerization was carried out under the same conditions as in Example 2 (olefin to titanium tetrachloride weight ratio of 200:: 1 and molar ratio H / Ti = 2.75, manometric hydrogen pressure of 0.015 MPa), except that the reaction temperature of titanium tetrachloride s. The polyiminoalan in the formation of the catalyst complex was 0 ° C in Example 7 and 25 ° C in Example 8.

In both cases, the temperature was subsequently raised to 80 ° C and polymerization was carried out for 3 hours.

In Example 7, the yield of polymer 70% by weight and a viscosity at 98.9 ° C 305 iiiniV ^'1 and in Example 8 was 73 weight percent and a viscosity at 98.9 ° C was 660 mm ² s ^-1.

The results show that polymers of much lower viscosity and somewhat lower yields were obtained at low titanium tetrachloride reduction reaction temperatures compared to those obtained at a reaction temperature of 80 ° C.

Example 9

The procedure was carried out under the same conditions as in Example 2 (olefin to titanium tetrachloride weight ratio = 200: 1, H / Ti molar ratio - 2.75, TiCU - titanium tetrachloride reducing temperature - 80 ° C, hydrogen manometer pressure = 0.015 MPa (polymerization time 3 hours), except that the polymerization temperature was 120 ° C.

The polymer yield was 79 weight percent, the viscosity at 98.9 ° C 1100 mmY ¹ .

From the above results, it can be seen that the polymerization can take place at 120 ° C.

Example 10

The procedure was analogous to Example 8 (olefin to titanium tetrachloride weight ratio = 200: 1, H / Ti molar ratio = 2.75, titanium tetrachloride reducing temperature 25 ° C, hydrogen pressure manometer - = 0.015 MPa, polymerization time 3 hours ), except that the polymerization temperature was 25 ° C.

The polymer yield was 23% by weight, the viscosity at 98.9 ° C was 790 mm @ ^-1 .

The results show that at a titanium tetrachloride reduction temperature of 25 ° C and a polymerization temperature of 25 ° C, the yields are the same and the viscosity values of the polymers obtained are considerably lower.

Examples 11, 12 and 13

The procedure was analogous to that of Example 2 (olefin 129414n to titanium tetrachloride - 200: 1 weight ratio, titanium tetrachloride reducing temperature and polymerization temperature = 80 ° C, hydrogen pressure = 0.015 MPa). The H / Ti molar ratios and volumes of 1.0 molar polyiminoalan PIA solution were as follows:

Molar ratio ml 1.0 molar H / Ti PIA solution Example 11 2.5 48.8 Example 12 3.0 58.6 Example 13 3.5 68.3

The changes in values relative to the previous examples were due to the fact that the addition of a solution of polyiminoalan in one liter of olefins containing 9.3 ml of a 1.0 molar titanium tetrachloride solution was carried out for 1 hour.

In Example 11, the polymer yield was 64% by weight, the viscosity at 98.9 ° C was 5330 mm ² s -1.

In Example 12, the polymer yield was 70% by weight and the viscosity at 98.9 ° C was 8950 mm ² s ^-1 .

In Example 13, the yield was 68 wt. % at a viscosity of 14,900 at 98.9 ° C.

The results show that the slow addition of polyiminoalan increases the viscosity of the polymer considerably and the viscosity increases further with increasing (mol) H / Ti ratio.

The reaction conditions were in these examples. Example olefin / TiCl 2 mole ratio of 2.1 molar TiCl 4 solution was the same as in Example 2 (olefin to titanium tetrachloride weight ratio = 200: 1, H / Ti molar ratio - 2.75), with except that the catalyst complex in Example 14 was formed "in situ" at 80 ° C in one liter of olefins diluted with 500 ml of n-heptane, while in Example 15 it was preformed at 80 ° C in 500 ml of n-heptane, 1 liter of olefins was added.

In both cases the polymerization was carried out at 80 ° C, a manometer pressure of 0.015 MPa and a polymerization time of 3 hours.

In Example 14, the polymer yield was 65% by weight and the viscosity at 98.9 ° C was 990

In Example 15, the polymer yield was 52% by weight and the viscosity was 750 mm ² s ^-1 at

98.9 ° C.

These results indicate that in the presence of a solvent, the viscosity values are lower, which is particularly evident when the catalyst complex has been preformed before the olefins are added.

Examples 16 and 17

The polymerization reactions were carried out in the same manner as in the previous examples, using starting materials in the form of 1 liter of Cs-C 10 α-olefins obtained from wax cracking, except that the following ratios were used:

H / Ti molar ratio PIA 1.0 molar solution

50

350

37.2 1.9 143.4

5.3 4.0 44.6

As in Examples 1, 2 and 3, the catalyst was formed in situ, with a formation temperature of the catalyst complex and polymerization of 80 ° C, a manometer hydrogen pressure of 0.015 MPa and a reaction time of 3 hours.

In Example 16, the polymer yield was 76% by weight and the viscosity at 98.9 ° C was 1410 mm ² s ¹ .

In Example 17, the yield of polymer 68% by weight and a viscosity at 98.9 ° C with 2460 inm ^{2 _1.}

These results, when compared to the results of Examples 1, 2 and 3, show that lower mole ratios of H / Ti may be used at lower olefin to titanium tetrachloride ratios, while higher mole ratios of H / Ti must be at higher weight ratios of olefins to titanium tetrachloride.

In this latter example, a polymer having higher viscosities but lower yields was obtained.

Examples 18, 19, 20 and 21

1 liter (741 g 1-decene, 95% pure) was used as the charge. The ratios between the two catalyst components were as follows:

Example weight ratio of olefins / TiCU ml of TiCl4 2.1 molar solution H / Ti molar ratio ml of PIA 1.0 molar solution 18 200 9.3 1.5 29.3 19 Dec 500 3.7 2.1 16.4 20 May 1000 1.9 3.5 17.3 21 2000 0.9 4,5 8.8

As in Example 8, the formation of catalytic was obtained in the following complex by in situ at 25 ° C, whereupon the temperature was raised and maintained at ° C for 3 hours, with a manometric hydrogen pressure of 0.015 MPa. .

Polymer yield (% by weight) polymer viscosity mm ² s ¹ at 98.9 ° C Example 18 94 4550 Example 19 94 3150 Example 20 78 1200 Example 21 32 970

When comparing the results of Examples 18, 19 and 20 with those obtained in Example 8, it is clear that using a η-α-olefin purer cartridge, much smaller catalyst doses, especially polyiminoalan, can be used, with yields and viscosities much higher.

Example weight ratio of ml of 2.1 molar olefins / TiCl2 solution of T1Cl4

Examples 22 and 23

In these examples, 1 liter of 1-decene (741 gj of 95% purity with respect to n-α-olefins) was used as filler. The ratios used were as follows:

mole ratio ml PIA 1.0 Η / Ti molar solution

100 ALIGN!

500

9.3 1.3 25.4, 7 1.8 14.0

Catalyst complex formation was performed at 80 ° C and the polymerization temperature was also 80 ° C, the polymerization time was 3 hours and the manometer hydrogen pressure was 0.015 MPa.

In Example 22, the polymer yield was 93% by weight and the viscosity at 98.9 ° C was 12,240

In Example 23, 92% of the polymer having a viscosity at 98.9 ° C of 7 540 mm ^{-1 was obtained} .

When comparing these results with Examples 18 and 19, it is clear that at a catalyst complex temperature of 80 ° C instead of 25 ° C, lower amounts of polyiminoalan can be used, with higher polymer yields of very high viscosities being achieved.

Claims (1)

As in Example 8, the formation was catalytic. The results are shown in the following complex, in situ, at 25 ° C, whereupon the temperature was raised and maintained at 80 ° C for 3 hours, the hydrogen pressure was 0.015 MPa. Polymer yield (% by weight) viscosity of the polymer m 2 s 1 at 98.9 ° C Example 18 94 4550 Example 19 94 3150 Example 20 78 1200 Example 21 32 970 When comparing the results of Examples 18, 19 and 20 with the results obtained in Example 8, it is obvious that when used much lesser amounts of catalyst, mainly polyimino-alan, can be used to purify the contents of α-olefins, yields and viscosities being higher than those of Example 1, weight ratio ml of 2.1 molar olefin / TiCl solution of T1Cl4 Examples 22 and 23 1 liter of 1-decene (741 g) was used as filler with 95% pure to olefin olefins and the ratios used were as follows: molar ratio ml PIA 1.0Η / Ti molar solution 22 100 23 500 9.3 1 The formation of the catalytic complex was carried out on a sieve at 80 ° C and the polymerization temperature was also 80 ° C, the polymerization time was 3 hours and the manometric pressure of hydrogen amounted to 0.015 MPa. In Example 22, the yield of polymer 93hmotnostní% and a viscosity at 98.9 ° C 12,240 Example 23 yielded 92% of the polymer having a viscosity at 98.9 ° C 7540 mm _1%. Comparing these results to Examples 18 and 19, it is apparent that lower amounts of polyiminoalan can be used at a catalyst complex temperature of 80 ° C instead of 25 ° C, with higher polymer yields of very high viscosities. OBJECT OF THE INVENTION A process for the production of liquid polymers having a high viscosity in the range of 250 to 15,000 mm 2 s -1 at 98.9 ° C by polymerizing mixtures of 8 to 10 carbon atoms derived from the cracking of wax and / or individual C 5, C 9 or C 10 η the α-olefin of the formula R —CH = CH 2 in which R is an alkyl of 6 to 8 carbon atoms, in the presence of a titanium tetrachloride catalyst system and a linear polyimine polymer-type aluminum compound, i.e. the polyiminolan of the general formula in which R is isopropyl and R is an integer from 1 to 50, preferably from 4 to 25, wherein the catalyst system is formed in situ, preferably in the absence of a solvent, for 5 to 60 minutes, optionally pre-formed in a solvent, wherein the temperature in the solvent is not exceeded. both cases range from 0 to 150 ° C, the weight ratio of α-olefins to titanium tetrachloride ranges from 50 to 2000 and the molar ratio of polyiminoalme to chlori titanium dioxide in the range of from 1.3 to 5, and the polymerization time is from 1 to 6 hours, preferably 3 hours, characterized in that the sepolymerization is carried out under a hydrogen atmosphere of 0.1 MPa. Severografia, n. P., Plant 7, Most