Process to prepare aluminoxanes

Abstract

Process to prepare alkylaminoxane by reacting, in the absence of solvent, 1 molar equivalent of alkylaluminium with 0.1 to 0.8 molar equivalent of a substituted allylic alcohol of the formula (I) wherein R1 and R2 are independently selected from aliphatic and aromatic hydrocarbon groups, and each R3, R4, and R5 is independently selected from aliphatic and aromatic hydrocarbon groups and a hydrogen atom. ##STR00001##

Claims

1. Process for preparing alkylaluminoxane by reacting, in the absence of solvent, 1 molar equivalent of alkylaluminium with 0.1 to 0.8 molar equivalent of a substituted allylic alcohol of the formula ##STR00005## wherein R1 and R2 are independently selected from aliphatic and aromatic hydrocarbon groups, and R3, R4, and R5 are independently selected from aliphatic and aromatic hydrocarbon groups and a hydrogen atom.

2. Process according to claim 1 wherein between 0.5 and 0.8 molar equivalent of substituted allylic alcohol is used per molar equivalent of alkylaluminium.

3. Process according to claim 2 wherein R1 and R2 are independently selected from branched and linear alkyl or alkylene groups of up to 20 carbon atoms, and wherein R3, R4, and R5 are independently selected from branched and linear alkyl and alkylene groups of up to 20 carbon atoms and a hydrogen atom.

4. Process according to claim 3 wherein the substituted allylic alcohol is selected from the group consisting of 4-methyl-3-pentene-2-ol, 3-methyl-2-pentene-1-ol, 3-methyl-2-hexene-1-ol, 3-ethyl-2-pentene-1-ol, (trans)-3,7-dimethyl-2,6-octadien-1-ol, and 3-methyl-2-butene-1-ol.

5. Process according to claim 1 wherein R1 and R2 are independently selected from branched and linear alkyl or alkylene groups of up to 20 carbon atoms, and wherein R3, R4, and R5 are independently selected from branched and linear alkyl and alkylene groups of up to 20 carbon atoms and a hydrogen atom.

6. Process according to claim 5 wherein the substituted allylic alcohol is selected from the group consisting of 4-methyl-3-pentene-2-ol, 3-methyl-2-pentene-1-ol, 3-methyl-2-hexene-1-ol, 3-ethyl-2-pentene-1-ol, (trans)-3,7-dimethyl-2,6-octadien-1-ol, and 3-methyl-2-butene-1-ol.

7. Process according to claim 1 wherein between 0.6 and 0.75 molar equivalent of substituted allylic alcohol is used per molar equivalent of alkylaluminium.

8. Process according to claim 1 wherein between 0.6 and 0.75 molar equivalent of substituted allylic alcohol is used per molar equivalent of alkylaluminium and wherein R1 and R2 are independently selected from branched and linear alkyl or alkylene groups of up to 20 carbon atoms, and wherein R3, R4, and R5 are independently selected from branched and linear alkyl and alkylene groups of up to 20 carbon atoms and a hydrogen atom.

9. Process according to claim 8 wherein the substituted allylic alcohol is selected from the group consisting of 4-methyl-3-pentene-2-ol, 3-methyl-2-pentene-1-ol, 3-methyl-2-hexene-1-ol, 3-ethyl-2-pentene-1-ol, (trans)-3,7-dimethyl-2,6-octadien-1-ol, and 3-methyl-2-butene-1-ol.

10. Process for preparing alkylaluminoxane by reacting, in the absence of solvent, 1 molar equivalent of alkylaluminium with 0.6 to 0.75 molar equivalent of a substituted allylic alcohol selected from the group consisting of 4-methyl-3-pentene-2-ol, 3-methyl-2-pentene-1-ol, 3-methyl-2-hexene-1-ol, 3-ethyl-2-pentene-1-ol, (trans)-3,7-dimethyl-2,6-octadien-1-ol, and 3-methyl-2-butene-1-ol.

11. Process for preparing alkylaluminoxane by reacting, in the absence of solvent, alkyl aluminium with methacrylic acid or a conjugated unsaturated carbonyl-functional compound of the formula ##STR00006## wherein R1 and R2 are independently selected from aliphatic hydrocarbon groups, R3 is an aliphatic hydrocarbon group or a hydrogen atom, and R4 is an aliphatic hydrocarbon group, a hydrogen atom, or a hydroxyl group in a ratio of 0.1 to 0.8 molar equivalent oxygen atoms in the part CO(R4) of the methacrylic acid or conjugated unsaturated carbonyl-functional compound per molar equivalent of aluminium atoms in the alkylaluminium.

12. Process according to claim 11 wherein R1 and R2 are independently selected from branched and linear aliphatic alkyl and alkylene groups of up to 20 carbon atoms, R3 is a branched or linear aliphatic alkyl or alkylene group of up to 20 carbon atoms or a hydrogen atom, and R4 is a branched or linear aliphatic alkyl or alkylene group of up to 20 carbon atoms, a hydrogen atom, or a hydroxyl group.

13. Process according to claim 12 wherein methacrylic acid or one of the conjugated unsaturated carbonyl-functional compounds is selected from the group consisting of 3-methyl-2-butenoic acid, 2-methyl-2-propenoic acid, 4-methyl-3-pentene-2-one, 3-methyl-2-butenal.

14. Process according to claim 11 wherein methacrylic acid or one of the conjugated unsaturated carbonyl-functional compounds is selected from the group consisting of 3-methyl-2-butenoic acid, 2-methyl-2-propenoic acid, 4-methyl-3-pentene-2-one, 3-methyl-2-butenal.

15. Process according to claim 11 wherein the alkylaluminium is a trialkylaluminium wherein the alkyl groups are alkyl groups of up to 8 carbon atoms.

16. Process of claim 15 wherein one or more of the alkyl groups on the alkylaluminium are isobutyl, ethyl or methyl.

17. Process according to claim 15 wherein the alkylaluminium is a compound wherein at least 50% of the alkyl groups are methyl.

18. Process according to claim 17 wherein the alkylaluminium contains trimethylaluminium.

19. Process according to claim 18, wherein the obtained aluminoxane is subsequently dissolved in an aliphatic solvent.

20. Process according to claim 19 wherein the aliphatic solvent is hexane or heptane.

Description

EXAMPLES

Example 1

(1) A 50 ml glass vial was charged with 7 g (97.2 mmol) TMAL (ex-AkzoNobel). 3-Methyl-2-buten-1-ol (prenol, ex-Sigma Aldrich) was dosed at a rate of 0.1 ml/min.

(2) After 69 minutes, when 5.86 g (6.91 ml, 68.1 mmol, 0.7 eqv.) prenol had been dosed, the dosing was stopped. The reaction mixture was slowly dosed to a 30 ml vial containing 1 g of polymethylaluminoxane (PMAO), while keeping the reaction temperature between 40 C. and 60 C.

(3) The reaction resulted in the formation of PMAO, as confirmed by .sup.1H-NMR

(4) To a 2 gram sample of the formed PMAO, 1.18 g methylcyclohexane was added, which resulted in a clear slightly yellow solution.

(5) To another 2 gram sample, 1.2 g 1-octene was added, which resulted in a clear slightly yellow solution.

(6) To a further 2 gram sample, 1.19 g toluene was added, which resulted in a clear slightly yellow solution.

Example 2

(7) A 30 ml glass vial was charged with 3.5 g (48.6 mmol) TMAL (ex-AkzoNobel). 3-Methyl-2-buten-1-ol (prenol, ex-Sigma Aldrich) was dosed at a rate of 0.1 ml/min.

(8) After 33.5 minutes, when 2.86 g (3.36 ml, 33.0 mmol, 0.68 eqv.) prenol had been dosed, the dosing was stopped. The reaction mixture was slowly dosed to a 30 ml vial containing 1 g of polymethylalyminoxane (PMAO), while keeping the reaction temperature between 40 C. and 60 C.

(9) The formation of PMAO was confirmed by 1H-NMR

Example 3

(10) A 20 ml vial with a magnetic stir bar was charged with 3.5 g (48.6 mmol) TMAL (ex-AkzoNobel).

(11) Mesityloxide (4-methylpent-3-en-2-one, ex-Sigma Aldrich; 3.30 g; 33.6 mmol; 0.69 eqv.) was then dosed over a period of 47 minutes. The reaction temperature was kept below 50 C. A clear and slightly viscous intermediate reaction mixture was obtained.

(12) 1 g of the prepared intermediate reaction mixture was charged to a 20 ml vial equipped with a magnetic stir bar. The vial was placed in a heating block and heated to 100 C. After about 8 minutes of heating at 100 C., a violent uncontrollable exothermic reaction occurred. All the liquid present in the reaction mixture was boiled off leaving a foamy substance in the vial.

(13) In order to better control the exothermic reaction, a new 20 ml vial equipped with a magnetic stir bar was charged with 0.3 g of the prepared intermediate reaction mixture. The reaction mixture was diluted with 0.7 g TMAL and heated to 100 C. After 13 minutes, an exothermic, but controllable reaction occurred. Over a period of about 30 minutes, the remaining intermediate reaction mixture was dosed to the 20 ml vial. The reaction was exothermic and the reaction temperature was kept between 80 and 90 C. A clear, bright red, and slightly viscous liquid was obtained. The liquid solidified upon storage at 20 C.

(14) The formation of PMAO was confirmed by .sup.1H-NMR.

Example 4

(15) To a 20 ml vial with a magnetic stir bar were charged 3.5 g (48.6 mmol) TMAL (ex-Akzo Nobel).

(16) Within 72 minutes, 1.01 g (17 mmol, 0.35 eqv. (O/Al=0.7)) acetic acid was dosed to the TMAL, while keeping to temperature below 50 C.

(17) The reaction was violent and a dark brown reaction mixture was obtained. The reaction mixture contained some light brown solids.

(18) A sample was taken and filtrated over a PTFE Millipore filter. .sup.1H-NMR showed no PMAO formation.

(19) Next, the reaction mixture was heated to 100 C. No exothermic reaction was observed.

(20) After 22 hours of heating a dark brown, partially solidified gel was obtained.

(21) The reaction product only partially dissolved in THF.

(22) The formation of PMAO was confirmed by .sup.1H-NMR.

Example 5

(23) A 20 ml vial was charged with 3.5 g (48.6 mmol) TMAL.

(24) Water was slowly dosed to the TMAL using a 100 L syringe with a capillary needle.

(25) The reaction was very violent and solids were formed. Due to the vigorousness of the reaction, it was decided to stop the dosing of the water.