CA1124266A - Method for the removal of unsaturations from oligomers of alpha olefines - Google Patents
Method for the removal of unsaturations from oligomers of alpha olefinesInfo
- Publication number
- CA1124266A CA1124266A CA356,591A CA356591A CA1124266A CA 1124266 A CA1124266 A CA 1124266A CA 356591 A CA356591 A CA 356591A CA 1124266 A CA1124266 A CA 1124266A
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- Canada
- Prior art keywords
- oligomers
- reaction
- unsaturations
- temperature
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
ABSTRACT OF THE DISCLOSURE
Unsaturations are removed from oligomers obtained from alpha olefines by contacting these oligomers with a hydrogenation catalyst at a temperature of from 150°C to 300°C under a partial hydrogen pressure of from 20 to 150 atmospheres.
Unsaturations are removed from oligomers obtained from alpha olefines by contacting these oligomers with a hydrogenation catalyst at a temperature of from 150°C to 300°C under a partial hydrogen pressure of from 20 to 150 atmospheres.
Description
d~ .
~.2~2~6 This application is a di.vis;on of appending appli.cation N0. 304,610 fi.led on June 1, 1978.
This invention relates to a method for the removal unsaturations from oligomers prepared from alpha-olefines coming from the several distillation cuts of the crack.ing products of higher hydrocarbons.
It is known that the paraffin oils have found in recent .
times a wide number of applications in the food industry, in the pharmaceutical industry, in agriculture, as diluents for pest-control agents, rubber extenders, plasticizers and lubricantoils.
They generally obtained by refining appropriate.
fractions of crude oil but the situation which has arisen recently as to the shortage in crude supplies and the considerable price chalk up have originated a number of difficulties in the production of paraffin oils.
An alternative route towards the obtention of oils is the cationic oligomerization of the alpha olefines which contain, predominantly, from 3 to 6 carbon atoms, said oligomerization being conducive to oily products having a low mol wt and con-taining residual unsaturation in the chain: these latter can be removed by a hydrogenation process which gives a saturated product .
However, the conventional methods which are prevailingly based on the use of Friedel Crafts halides, are effected by a few considerable shortcomings, such as low reaction yieldc., dif-ficulties in the control of the reaction conditions and thus an uneasy performance of the reaction.
A new method has now been disclosed in the parent application No. 304,610 for the preparation of oligomers from alpha-olefines using a very specific catalyst system. This new method has the advantage, over the conventional procedures, of - 1- .
~.2~
giving higher polymer yelds, while being easier to carry out.
In this new method, the reaction is also more easily controllable and the reaction system is, moreoVer, wholl~
homogeneous.
The very specific catalytic system used in the method disclosed in the parent application, makes it possible to prepare oligomers from alpha-olefines having a number of carbon atoms of from 3 to 12 and especially oligomers of propylene, butene-l, pentene-l and hexene-l.
The catalytic system in question is composed by two components, selected from among the following classes of compounds :
(a) - an organic metallic compound of aluminium, as represented by the following general formula :
RmAlX3-m wherein X is a halogen atom, R is hydrogen or a monovalent redical selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, alkaryl, alcoxyl and ester radicalshaving from 1 to 12 carbon atoms, and m is a number comprised between 1 and 3.
Examples of such compounds are: AlEtC12, AlEt2Cl, AlEtl 5 Cll 5 and others.
(b) _ a compound capable of reacting with the compounds of the class (a) above to give the catalytic species capable of initia-ting polymerization, and having the formula HX, wherein X is a halogen.
Examples o~ the latter compounds are : HCl. Hbr, HF r HI .
The reaction is carried out in a homogeneous phase and with a solvent means being present which is selected, as a rule, among the hydrocarbons or halogen-substituted hydrocarbons having a number of carbon atoms of from 3 to 12. It is possible, never-theless, to operate with no solvent being present, the solvent phase being in such a case the excess of the monomer. The two ~L~.2~266 components of the catalytic system can be introduced in the reaction medium either simultaneously or separately and the order of addition has no significant bearing on the catalytic species which can be obtained.
The molar ratio of the component (a) to the component (b) may be comprised be~ween 0.1 and 5, the preferred range being from 0.5 to 3.
The reaction is conducted at a temperature comprised between -30C and +100C, the preferred range being from -10C
to +80C.
The products which are obtained from the polymerization have a numeric average mol wt of from 200 to 3000 and contain residual unsaturations which can be expressed in terms of bromine number ~i.e. grams of Br absorbed by 100 g of polymer), which is determined according to several methods, such as ASTM
D 1159.
It is the object of the present invention to provide a method for either reducing or completely removing the unsaturations which are left on completion of the oligomeri2ation.
This method consists m hydrogenating the unsaturated oligomer at a temperature comprised between 150C and 300C, under partial hydrogen pressures comprised between 20 atm and 150 atm, in the presence of hydrogenation catalyst such as Ni on kieselguhr, Ni-Raney, Pd on charcoal, Pt on charcoal.
Possible trace residues of unsaturated products (the Br number of the treated product being below 0.1) can eventually be removed by having the compounds flowing through adsorbing siliceous earths at a temperature comprised between 50C and 100C, to give the desired saturated products.
The foregoing and the operational details will become more clearly apparent from the ensuing illustrative examples which are not to be construed as limitations to this invention.
E X A M P L E
, A 10~ ml steel autoclave hav;ng a magnetic st;rrer and a thermometer well, and whi.ch has previously been dried in a vacuum, is charged, by siphoning thereinto a solution containing 1.5 millimol of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 hydrocarbon cut having the following composition :
Propane 1.22%
Propylene 0.29%
Isobutane 3.68%
Nor.butane 17.08%
Butene-l 61.64~
Butene-2-trans 10.30%
Butene-2-cis 2.15~
Isobutene 3.64%
The temperature is stabilized on + 20 C, whereafter there is introduced, by nitrogen overpressure, a solution containing 1.5 millimol of AlEtC12 diluted in 10 mls of nor.
pentane (Molar ratio of HCl to AlEtC12 = 1.0).
A temperature rise up to 28C is experi.enced. The reaction is continued for 30 mins and is then discontinued by addition of methanol.
The unreacted monomers are flashed and the resultant product is washed with water supplemented with NaOH to remove the traces of the catalyst, and subsequently with distilled water until neutrality is attained.
The hydrocarbonaceous phase is then evaporated to dryness to remove the solvent completely. There are obtained 7.85 g of dry oligomer (yeld 85.9~ calculated with respect to butene-l and i.sobutene which are present), which has an average osmometric mol wt, Mn of 592 and a contents of unsaturations, expressed in terms of Br number, of 38.5 as determi~ed according to the method ASTM D 1159, and a contents of residual C12 of ~.Z~66 1144 ppm ~parts per million) as determined with an X-ray fluo-rescence apparatus. Simultaneously, with the same procedl~re, a sample procedure, a sample test has been carried out by introducing in the autoclave the same quantities of C4 hydro-carbon fraction and introducing then 1.5 millimol of AlEtC12.
A temperature increase of 1.5 C (from +21 C to 22.5 C) has been noted and, after discontinuation of the reaction there have been obtained 0.35 g (yield 4.0~) of polymer on which it has not been possible to determine any property.
The product obtained by using the catalytic system AlEtC12 plus HCl has been subjected to hydrogenation in order to remove the unsaturations present in the polymeric chain by following the procedure indicated hereinafter: an autoclave having a mechanical stirrer and thermometer well is charged with 5.0 g of product and 0.34 g of Ni Raney prepared according to the indications reported in A.I. Vogel, Practical Organic Chemistry, Longmans, Green & Co. Edit page 870 (1956). The temperature is brought to 270C with a hydrogen pressure of 90 atm for a time of 20 hrs. Upon cool~ng, the autoclave is discharged and, on the hydrogenated product, the residual unsaturations are determined and a bromine number of 0.15 is obtained.
With the same procedure as in Example 1, the autoclave is charged with 1.27 millimol of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 fraction having the same composition as reported in Example 1.
The reaction is started at the temperature of +20 C
with the addition of a solution containing 1.5 mïllimol of AlEtC12 diluted in 10 mls of nor.pentane (molar ratio of HC1 to AlEtC12 = 0.85).
A temperature increase up to 27 C is noted and the reaction is continued for 30 mins. There are obtained 7.70 g of dry product (yield 84.2%) which has an average osmometric mol wt Mn of 643, a Br number of 34.3 and a contents of C12 (residual) of 1262 ppm.
Hydrogenation has been carried out on this product according to the procedure a set forth in Example l, the residual unsaturations being subsequently on the hydrogenated product.
A value of 0.20 has been obtained for the bromine number.
With the same procedure as in example 1 the autoclave has been charged with 0.7S millimol of anhydrous HCl diluted in , 1 ml of nor.pentane and 14 g of a C4 fraction having the same composition reported in Example l.
The reaction is started at a temperature of ~120C by the addition of a solution containing 1.5 millimol of AlEtC12 diluted in 10 mls of nor.pentane (Molar ration of HCl to AlEtC12=
0.5)-A temperature increase to as much as 26C is noted and the reaction is continued during 30 mins. After discountinuation of the reaction there are obtained 4.0 g of a dry product (yeld 43.8%) having an Mn of 433, a Br number of 41.7 and a contents of residual C12 of 1670 ppm. Hydrogenation has been carried out on this product according to the procedure reported in Example 1 with results which are essentially equivalent.
With the same procedure as reported in Example l there are charged 2.0 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 hydrocarbonaceous fraction having a composition equal to the reported in E~ample l.
~he reaction is started at the temperatureof 20C by introducing 1.5 millimol of AlEtC12 diluted in lO mls of nor.
pentane.
$~.2~ 6 (Molar ratio of HCl to AlEtC12 = 1.33).
The temperature rises to 2gC and the reaction is continued for 30 mins.
There are obtained 9.1 g of a dry product (yield 100~) which has an Mn of 538, a bromine number of 36.3 and a contents of residual C12 of 1190 ppm.
With the same procedure as set forth in Example 1 there are charged the same quantities of C4 hydrocarbonaceous fraction and of HC1.
The temperature is set to 0C and the reaction is started with the same amount of AlEtC12 as reported in Example 1. The temperature rises to 4C and the reaction is allowed to proceed for 30 minutes whereafter there are obtained 5.0 g of a dry product (yield 54.7%) having an Mn of 524, a bromine number of 32.5 and a contents of residual C12 of 1080 ppm.
With the same procedure as in Example 1 there are introduced the same amounts of C4 hydrocarbonaceous fraction and HCl, and the temperature is set to 80C and the same amount of AlEtC12 reported in Example 1 are introduced.
A temperature increase to 85 C is experienced and the reaction is allowed to proceed for 30 mins. There are obtained 6.10 g of a dry product (yield 66.8%) having an Mn of 215 a Br number of 54.5 and a contents of residual C12 of 1850 ppm.
With the same procedure as in Example 1 there are charged 4.5. millimol of anhydrous HCl diluted in 1 ml of nor.
pentane and 14.0 of a C4 hydrocarbonaceous fraction having a composition equal to that reported in Example 1.
The temperature is stabilized to 20C and the reaction is started by introducing 1.5 millimol of AlEt3 diluted in 10 mls l~.Z4Z6Çi of nor.pentane (Molar ratio of HCl to AlEt3 = 3.0).
The temperature rises to 30C and there are obtained 7.82 g of a dry product (yield 85.6%) having an Mn = 405, a bromine number of 39.5 and a contents of residual C12 of 1058 ppm.
With the same procedure as in Example 1 there are introduced 3.0 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14.0 g of a C4 hydrocarbonaceous fractions having the same composition as reported in Example 1.
The temperature is stabilized to 20 C and there introduced 1.5 millimols of AlEt2Cl diluted in 10 mls of nor.
pentane.
The molar ratio of HCl to AlEt2Cl is 2Ø
The temperature rises to 31C, the reaction is allowed to proceed for 30 mins. and there are obtained 8.90 g of a dry oligomer (yield 97.4%) having in Mn of 363, a bromine number of 40.4 and a contents of residual C12 of 1080 ppm.
With the procedure as reported in Example 1 there are introduced 2.25 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14.0 g of a C4 hydrocarbonaceous fraction having the same composition as reported in Example 1.
The temperature is stabilized to 20C and the reaction is started by adding 1.5 millimol of AlEt sesquichloride diluted in 10 mls of nor.pentane, the molar ratio of HC1 to AlEt sesqui-chloride being 1.5.
The temperature rises to 29C, the reaction is continued for 3¢ mins. and there are obtained 8.5 g of~a dry product (yield 89.8~) having an Mn of 450, a bromine number of 39.5 and a contents of residual C12 of 1120.
~.2~2~6 This application is a di.vis;on of appending appli.cation N0. 304,610 fi.led on June 1, 1978.
This invention relates to a method for the removal unsaturations from oligomers prepared from alpha-olefines coming from the several distillation cuts of the crack.ing products of higher hydrocarbons.
It is known that the paraffin oils have found in recent .
times a wide number of applications in the food industry, in the pharmaceutical industry, in agriculture, as diluents for pest-control agents, rubber extenders, plasticizers and lubricantoils.
They generally obtained by refining appropriate.
fractions of crude oil but the situation which has arisen recently as to the shortage in crude supplies and the considerable price chalk up have originated a number of difficulties in the production of paraffin oils.
An alternative route towards the obtention of oils is the cationic oligomerization of the alpha olefines which contain, predominantly, from 3 to 6 carbon atoms, said oligomerization being conducive to oily products having a low mol wt and con-taining residual unsaturation in the chain: these latter can be removed by a hydrogenation process which gives a saturated product .
However, the conventional methods which are prevailingly based on the use of Friedel Crafts halides, are effected by a few considerable shortcomings, such as low reaction yieldc., dif-ficulties in the control of the reaction conditions and thus an uneasy performance of the reaction.
A new method has now been disclosed in the parent application No. 304,610 for the preparation of oligomers from alpha-olefines using a very specific catalyst system. This new method has the advantage, over the conventional procedures, of - 1- .
~.2~
giving higher polymer yelds, while being easier to carry out.
In this new method, the reaction is also more easily controllable and the reaction system is, moreoVer, wholl~
homogeneous.
The very specific catalytic system used in the method disclosed in the parent application, makes it possible to prepare oligomers from alpha-olefines having a number of carbon atoms of from 3 to 12 and especially oligomers of propylene, butene-l, pentene-l and hexene-l.
The catalytic system in question is composed by two components, selected from among the following classes of compounds :
(a) - an organic metallic compound of aluminium, as represented by the following general formula :
RmAlX3-m wherein X is a halogen atom, R is hydrogen or a monovalent redical selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl, alkaryl, alcoxyl and ester radicalshaving from 1 to 12 carbon atoms, and m is a number comprised between 1 and 3.
Examples of such compounds are: AlEtC12, AlEt2Cl, AlEtl 5 Cll 5 and others.
(b) _ a compound capable of reacting with the compounds of the class (a) above to give the catalytic species capable of initia-ting polymerization, and having the formula HX, wherein X is a halogen.
Examples o~ the latter compounds are : HCl. Hbr, HF r HI .
The reaction is carried out in a homogeneous phase and with a solvent means being present which is selected, as a rule, among the hydrocarbons or halogen-substituted hydrocarbons having a number of carbon atoms of from 3 to 12. It is possible, never-theless, to operate with no solvent being present, the solvent phase being in such a case the excess of the monomer. The two ~L~.2~266 components of the catalytic system can be introduced in the reaction medium either simultaneously or separately and the order of addition has no significant bearing on the catalytic species which can be obtained.
The molar ratio of the component (a) to the component (b) may be comprised be~ween 0.1 and 5, the preferred range being from 0.5 to 3.
The reaction is conducted at a temperature comprised between -30C and +100C, the preferred range being from -10C
to +80C.
The products which are obtained from the polymerization have a numeric average mol wt of from 200 to 3000 and contain residual unsaturations which can be expressed in terms of bromine number ~i.e. grams of Br absorbed by 100 g of polymer), which is determined according to several methods, such as ASTM
D 1159.
It is the object of the present invention to provide a method for either reducing or completely removing the unsaturations which are left on completion of the oligomeri2ation.
This method consists m hydrogenating the unsaturated oligomer at a temperature comprised between 150C and 300C, under partial hydrogen pressures comprised between 20 atm and 150 atm, in the presence of hydrogenation catalyst such as Ni on kieselguhr, Ni-Raney, Pd on charcoal, Pt on charcoal.
Possible trace residues of unsaturated products (the Br number of the treated product being below 0.1) can eventually be removed by having the compounds flowing through adsorbing siliceous earths at a temperature comprised between 50C and 100C, to give the desired saturated products.
The foregoing and the operational details will become more clearly apparent from the ensuing illustrative examples which are not to be construed as limitations to this invention.
E X A M P L E
, A 10~ ml steel autoclave hav;ng a magnetic st;rrer and a thermometer well, and whi.ch has previously been dried in a vacuum, is charged, by siphoning thereinto a solution containing 1.5 millimol of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 hydrocarbon cut having the following composition :
Propane 1.22%
Propylene 0.29%
Isobutane 3.68%
Nor.butane 17.08%
Butene-l 61.64~
Butene-2-trans 10.30%
Butene-2-cis 2.15~
Isobutene 3.64%
The temperature is stabilized on + 20 C, whereafter there is introduced, by nitrogen overpressure, a solution containing 1.5 millimol of AlEtC12 diluted in 10 mls of nor.
pentane (Molar ratio of HCl to AlEtC12 = 1.0).
A temperature rise up to 28C is experi.enced. The reaction is continued for 30 mins and is then discontinued by addition of methanol.
The unreacted monomers are flashed and the resultant product is washed with water supplemented with NaOH to remove the traces of the catalyst, and subsequently with distilled water until neutrality is attained.
The hydrocarbonaceous phase is then evaporated to dryness to remove the solvent completely. There are obtained 7.85 g of dry oligomer (yeld 85.9~ calculated with respect to butene-l and i.sobutene which are present), which has an average osmometric mol wt, Mn of 592 and a contents of unsaturations, expressed in terms of Br number, of 38.5 as determi~ed according to the method ASTM D 1159, and a contents of residual C12 of ~.Z~66 1144 ppm ~parts per million) as determined with an X-ray fluo-rescence apparatus. Simultaneously, with the same procedl~re, a sample procedure, a sample test has been carried out by introducing in the autoclave the same quantities of C4 hydro-carbon fraction and introducing then 1.5 millimol of AlEtC12.
A temperature increase of 1.5 C (from +21 C to 22.5 C) has been noted and, after discontinuation of the reaction there have been obtained 0.35 g (yield 4.0~) of polymer on which it has not been possible to determine any property.
The product obtained by using the catalytic system AlEtC12 plus HCl has been subjected to hydrogenation in order to remove the unsaturations present in the polymeric chain by following the procedure indicated hereinafter: an autoclave having a mechanical stirrer and thermometer well is charged with 5.0 g of product and 0.34 g of Ni Raney prepared according to the indications reported in A.I. Vogel, Practical Organic Chemistry, Longmans, Green & Co. Edit page 870 (1956). The temperature is brought to 270C with a hydrogen pressure of 90 atm for a time of 20 hrs. Upon cool~ng, the autoclave is discharged and, on the hydrogenated product, the residual unsaturations are determined and a bromine number of 0.15 is obtained.
With the same procedure as in Example 1, the autoclave is charged with 1.27 millimol of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 fraction having the same composition as reported in Example 1.
The reaction is started at the temperature of +20 C
with the addition of a solution containing 1.5 mïllimol of AlEtC12 diluted in 10 mls of nor.pentane (molar ratio of HC1 to AlEtC12 = 0.85).
A temperature increase up to 27 C is noted and the reaction is continued for 30 mins. There are obtained 7.70 g of dry product (yield 84.2%) which has an average osmometric mol wt Mn of 643, a Br number of 34.3 and a contents of C12 (residual) of 1262 ppm.
Hydrogenation has been carried out on this product according to the procedure a set forth in Example l, the residual unsaturations being subsequently on the hydrogenated product.
A value of 0.20 has been obtained for the bromine number.
With the same procedure as in example 1 the autoclave has been charged with 0.7S millimol of anhydrous HCl diluted in , 1 ml of nor.pentane and 14 g of a C4 fraction having the same composition reported in Example l.
The reaction is started at a temperature of ~120C by the addition of a solution containing 1.5 millimol of AlEtC12 diluted in 10 mls of nor.pentane (Molar ration of HCl to AlEtC12=
0.5)-A temperature increase to as much as 26C is noted and the reaction is continued during 30 mins. After discountinuation of the reaction there are obtained 4.0 g of a dry product (yeld 43.8%) having an Mn of 433, a Br number of 41.7 and a contents of residual C12 of 1670 ppm. Hydrogenation has been carried out on this product according to the procedure reported in Example 1 with results which are essentially equivalent.
With the same procedure as reported in Example l there are charged 2.0 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14 g of a C4 hydrocarbonaceous fraction having a composition equal to the reported in E~ample l.
~he reaction is started at the temperatureof 20C by introducing 1.5 millimol of AlEtC12 diluted in lO mls of nor.
pentane.
$~.2~ 6 (Molar ratio of HCl to AlEtC12 = 1.33).
The temperature rises to 2gC and the reaction is continued for 30 mins.
There are obtained 9.1 g of a dry product (yield 100~) which has an Mn of 538, a bromine number of 36.3 and a contents of residual C12 of 1190 ppm.
With the same procedure as set forth in Example 1 there are charged the same quantities of C4 hydrocarbonaceous fraction and of HC1.
The temperature is set to 0C and the reaction is started with the same amount of AlEtC12 as reported in Example 1. The temperature rises to 4C and the reaction is allowed to proceed for 30 minutes whereafter there are obtained 5.0 g of a dry product (yield 54.7%) having an Mn of 524, a bromine number of 32.5 and a contents of residual C12 of 1080 ppm.
With the same procedure as in Example 1 there are introduced the same amounts of C4 hydrocarbonaceous fraction and HCl, and the temperature is set to 80C and the same amount of AlEtC12 reported in Example 1 are introduced.
A temperature increase to 85 C is experienced and the reaction is allowed to proceed for 30 mins. There are obtained 6.10 g of a dry product (yield 66.8%) having an Mn of 215 a Br number of 54.5 and a contents of residual C12 of 1850 ppm.
With the same procedure as in Example 1 there are charged 4.5. millimol of anhydrous HCl diluted in 1 ml of nor.
pentane and 14.0 of a C4 hydrocarbonaceous fraction having a composition equal to that reported in Example 1.
The temperature is stabilized to 20C and the reaction is started by introducing 1.5 millimol of AlEt3 diluted in 10 mls l~.Z4Z6Çi of nor.pentane (Molar ratio of HCl to AlEt3 = 3.0).
The temperature rises to 30C and there are obtained 7.82 g of a dry product (yield 85.6%) having an Mn = 405, a bromine number of 39.5 and a contents of residual C12 of 1058 ppm.
With the same procedure as in Example 1 there are introduced 3.0 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14.0 g of a C4 hydrocarbonaceous fractions having the same composition as reported in Example 1.
The temperature is stabilized to 20 C and there introduced 1.5 millimols of AlEt2Cl diluted in 10 mls of nor.
pentane.
The molar ratio of HCl to AlEt2Cl is 2Ø
The temperature rises to 31C, the reaction is allowed to proceed for 30 mins. and there are obtained 8.90 g of a dry oligomer (yield 97.4%) having in Mn of 363, a bromine number of 40.4 and a contents of residual C12 of 1080 ppm.
With the procedure as reported in Example 1 there are introduced 2.25 millimols of anhydrous HCl diluted in 1 ml of nor.pentane and 14.0 g of a C4 hydrocarbonaceous fraction having the same composition as reported in Example 1.
The temperature is stabilized to 20C and the reaction is started by adding 1.5 millimol of AlEt sesquichloride diluted in 10 mls of nor.pentane, the molar ratio of HC1 to AlEt sesqui-chloride being 1.5.
The temperature rises to 29C, the reaction is continued for 3¢ mins. and there are obtained 8.5 g of~a dry product (yield 89.8~) having an Mn of 450, a bromine number of 39.5 and a contents of residual C12 of 1120.
Claims (3)
1. A method for the removal of unsaturations from oligomers of alpha-olegins, comprising the step of contacting said oligomers with a hydrogenation catalyst at a temperature variable from 150°C to 300°C under a partial pressure of hydrogen comprised between 20 atm and 150 atm.
2. A method as claimed in claim 1, comprising the additional step of flowing the obtained hydrogenated oligomers through a bed of siliceous adsorbent earths at a temperature comprised between 50°C and 100°C.
3. A method as claimed in claim 1 or 2, wherein the starting oligomers result from the polymerization alpha-olegins in the presence of a catalytic system composed of :
a) an organic metallic compound of aluminum having the following general formula :
RmA1X3-m wherein X is a halogen atom, R is hydrogen or a monovalent radical selected from the group consisting of alkyl, aryl, cycloalkyl, aralky , alkaryl, alkoxyl and ester radicals having from 1 to 12 carbon atoms, and m is between 1 and 3;
and b) a compound having the formula HX in which X is halogen and which is capable of reacting with the compounds defined above under a) to produce a catalytic species capable of starting the polymerization.
a) an organic metallic compound of aluminum having the following general formula :
RmA1X3-m wherein X is a halogen atom, R is hydrogen or a monovalent radical selected from the group consisting of alkyl, aryl, cycloalkyl, aralky , alkaryl, alkoxyl and ester radicals having from 1 to 12 carbon atoms, and m is between 1 and 3;
and b) a compound having the formula HX in which X is halogen and which is capable of reacting with the compounds defined above under a) to produce a catalytic species capable of starting the polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA356,591A CA1124266A (en) | 1977-07-18 | 1980-07-18 | Method for the removal of unsaturations from oligomers of alpha olefines |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25811/77A IT1077342B (en) | 1977-07-18 | 1977-07-18 | PROCESS FOR THE PRODUCTION OF LINEAR ALFAOLEFINS OLIGOMERS, SUBSEQUENT HYDROGENATION OF THE SAME AND SATURATED PRODUCTS SO OBTAINED |
| CA304,610A CA1102358A (en) | 1977-07-18 | 1978-06-01 | Method for producing oligomers from alpha-olefines |
| IT25811A/77 | 1979-07-18 | ||
| CA356,591A CA1124266A (en) | 1977-07-18 | 1980-07-18 | Method for the removal of unsaturations from oligomers of alpha olefines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1124266A true CA1124266A (en) | 1982-05-25 |
Family
ID=27165687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA356,591A Expired CA1124266A (en) | 1977-07-18 | 1980-07-18 | Method for the removal of unsaturations from oligomers of alpha olefines |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1124266A (en) |
-
1980
- 1980-07-18 CA CA356,591A patent/CA1124266A/en not_active Expired
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