Process for preparing high-reactivity isobutene homo- or copolymers
A novel process can be used for preparing high-reactivity isobutene homo- or copolymers, by polymerizing isobutene or an isobutene-containing monomer mixture in the presence of a polymerization catalyst.
1 . A bulk- or solution polymerisation process for preparing a high-reactivity isobutene homo- or copolymer with a combined content of α-double bonds and β-double bonds per polyisobutene chain end of at least 60 mol %, the process comprising:
polymerizing isobutene or an isobutene-comprising monomer mixture in the presence of a polymerization catalyst formed with at least one Lewis Acid and a donor, to obtain the high-reactivity isobutene homo- or copolymer, wherein the polymerization catalyst is selected from the group consisting of an aluminum trihalide-donor complex, an alkylaluminum halide-donor complex, an iron trihalide-donor complex, a gallium trihalide-donor complex, a titanium tetrahalide-donor complex, a zinc dihalide-donor complex, a tin dihalide-donor complex, a tin tetrahalide-donor complex, and a boron trihalide-donor complex,
wherein the donor of said polymerization catalyst comprises a mixture of
at least one organic compound (II) comprising at least one dihydrocarbyl ether of the general formula R 8 —O—R 9 , wherein R 8 and R 9 are each independently a C 1 - to C 20 -alkyl radical, a C 1 - to C 20 -haloalkyl radical, a C 5 - to C 8 -cycloalkyl radical, a C 6 - to C 20 -aryl radical, a C 6 - to C 20 -haloaryl radical, or a C 7 - to C 20 -arylalkyl radical, and
at least one phosphorus-containing compound of formula (I)
or
P(OR 1 )(OR 2 )(OR 3 ),or formula (Ia)
P(OR 1 )(OR 2 )(OR 3 )(OR 4 )(OR 5 ), formula (Ib)
wherein
X 1 , X 2 , and X 3 independently of another are oxygen, sulphur, or a single bond, and
R 1 , R 2 , R 3 , R 4 , and R 5 independently of another are an organic residue with up to 20 carbon atoms,
with the proviso that a complex formed from the at least one Lewis Acid and the at least one phosphorus-containing compound of formula (I), formula (Ia), or formula (Ib) has a melting point of not more than 60° C.,
said at least one organic compound (II) and said at least one phosphorus-containing compound of formula (I), formula (Ia), or formula (Ib) are present in a molar ratio of 0.1:1 to 1:0.1, and
said high-reactivity isobutene homo- or copolymer has a number-average molecular weight Mn, determined by gel permeation chromatography of 500 to 5,000 g/mol.
2 . The process according to claim 1 , wherein the at least one organic compound (II) comprises at least one oxygen atom with at least one lone electron pair.
3 . The process according to claim 1 , wherein the at least one organic compound (II) is selected from the group consisting of organic compounds with at least one ether function, organic compounds with at least one carboxylic ester function, organic compounds with at least one aldehyde function, and organic compounds with at least one keto function.
4 . The process according to claim 1 , wherein the at least one organic compound (II) is at least one organic compound with at least one ether function, and is selected from the group consisting of diethyl ether, di-n-butyl ether, di-isopropyl ether, di-n-propyl ether, bis(2-chloroethyl) ether, and 2-chloroethyl ethyl ether.
5 . The process according to claim 1 , wherein X 1 , X 2 , and X 3 each are a single bond.
6 . The process according to claim 1 , wherein R 1 to R 5 each are C 2 -C 18 -alkyl or C 6 -C 12 -aryl.
7 . The process according to claim 1 , wherein the at least one phosphorus-containing compound is at least one selected from the group consisting of tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, tri iso-nonyl phosphine oxide, tri-n-decylphosphine oxide, tri-n-dodecylphosphine oxide, tri iso-tridecyl phosphine oxide, tri-n-tetradecylphosphine oxide, tri iso-heptadecyl phosphine oxide, triphenylphosphine oxide, tritolylphosphine oxide, trinaphtylphosphine oxide, phosphorous acid tri (n-butyl) ester, phosphorous acid tri (n-hexyl) ester, phosphorous acid tri (2-ethylhexyl) ester, phosphorous acid tri (n-octyl) ester, phosphorous acid tri (2-propylheptyl) ester, phosphorous acid tri (n-decyl) ester, phosphorous acid tri (n-dodecyl) ester, phosphorous acid tri (n-tetradecyl) ester, phosphorous acid tri (n-hexadecyl) ester, tri-ethylphosphite, tri-n-butylphosphite, tri-n-hexylphosphite, tri-n-octylphosphite, tri iso-nonyl phosphite, tri-n-decylphosphite, tri-n-dodecylphosphite, tri iso-tridecyl phosphite, tri-n-tetradecylphosphite, tri iso-heptadecyl phosphite, triphenylphosphite, penta (ethoxy) phosphorane, penta (n-butyloxy) phosphorane, penta (hexyloxy) phosphorane, penta (n-octyloxy) phosphorane, penta (2-ethylhexyloxy) phosphorane, and penta (phenoxy) phosphorane.
8 . The process according to claim 1 , wherein the polymerization catalyst is the aluminum trihalide-donor complex, the alkylaluminum halide-donor complex, or the iron trihalide-donor complex.
9 . The process according to claim 1 , wherein the polymerization catalyst is the iron-trihalide donor complex.
10 . The process according to claim 1 , wherein a molar ratio of the at least one Lewis Acid to the compound of formula (I) is from 1:0.1 to 10.
11 . The process according to claim 1 , wherein a molar ratio of aluminum trihalide or alkylaluminum halide to isobutene monomer in the case of homopolymerization of isobutene, or to a total amount of polymerizable monomers in the case of copolymerization of isobutene, based on each individual functional site of the aluminum trihalide or the alkylaluminum halide, is from 0.001:1 to 0.2:1.
12 . The process according to claim 1 , wherein the polymerization is performed with a mono- or polyfunctional initiator which is at least one selected from the group consisting of an organic hydroxyl compound in which one or more hydroxyl groups are each bonded to an sp 3 -hybridized carbon atom, an organic halogen compound in which one or more halogen atoms are each bonded to an sp 3 -hybridized carbon atom, and water.
13 . The process according to claim 12 , wherein the initiator is at least one selected from the group consisting of water, methanol, ethanol, 1-phenylethanol, 1-(p-methoxyphenyl) ethanol, n-propanol, isopropanol, 2-phenyl-2-propanol, n-butanol, isobutanol, secbutanol, tert-butanol, 1-phenyl-1-chloroethane, 2-phenyl-2-chloropropane, tert-butyl chloride, and 1,3- or 1,4-bis(1-hydroxy-1-methylethyl) benzene.
14 . The process according to claim 12 , wherein a molar ratio of the initiator to isobutene monomer in the case of homopolymerization of isobutene, or to a total amount of polymerizable monomers in the case of copolymerization of isobutene, based on each individual functional site of the initiator, is from 0.0005:1 to 0.1:1, or
wherein when the initiator is water or water in combination with the organic hydroxyl compound and/or the organic halogen compound, a molar ratio of water to the isobutene monomer in the case of homopolymerization of isobutene, or to the total amount of the polymerizable monomers in the case of copolymerization of isobutene, is from 0.0001:1 to 0.1:1.
15 . The process according to claim 1 , wherein the polymerization is performed at a temperature of −90° C. to +30° C.