PROCESS FOR PREPARING HIGH-REACTIVITY ISOBUTENE HOMO- OR COPOLYMERS

Abstract

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.

Claims

1-18. (canceled)

19: 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 oxygen or nitrogen atom with at least one lone electron pair, and at least one phosphorus-containing compound of formula (I) ##STR00009##  or
P(OR.sup.1)(OR.sup.2)(OR.sup.3), or  formula (Ia)
P(OR.sup.1)(OR.sup.2)(OR.sup.3)(OR.sup.4)(OR.sup.5),  formula (Ib) wherein X.sub.1, X.sub.2, and X.sub.3 independently of another are oxygen, sulphur, or a single bond, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.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., and wherein the at least one organic compound (III) comprises at least one dihydrocarbyl ether of the general formula R.sup.8—O—R.sup.9, wherein R.sup.8 and R.sup.9 are each independently a C.sub.1- to C.sub.20-alkyl radical, a C.sub.1- to C.sub.20-haloalkyl radical, a C.sub.5- to C.sub.8-cycloalkyl radical, a C.sub.6- to C.sub.20-aryl radical, a C.sub.6- to C.sub.20-haloaryl radical, or a C.sub.7- to C.sub.20-arylalkyl radical.

20: The process according to claim 19, wherein X.sub.1, X.sub.2, and X.sub.3 each are a single bond.

21: The process according to claim 19, wherein R.sup.1 to R.sup.5 each are C.sub.2-C.sub.18-alkyl or C.sub.6-C.sub.12-aryl.

22: The process according to claim 19, 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 in (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.

23: The process according to claim 19, wherein the polymerization catalyst is the aluminum trihalide-donor complex, the alkylaluminum halide-donor complex, or the iron trihalide-donor complex.

24: The process according to claim 19, wherein the polymerization catalyst is the iron-trihalide donor complex.

25: The process according to claim 19, wherein a molar ratio of the at least one Lewis Acid to the compound of formula (I) is from 1:0.1 to 10.

26: The process according to claim 19, 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.

27: The process according to claim 19, 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.

28: The process according to claim 19, 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.

29: The process according to claim 19, wherein the polymerization is performed with an additional 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.sup.3-hybridized carbon atom, an organic halogen compound in which one or more halogen atoms are each bonded to an sp.sup.3-hybridized carbon atom, and water.

30: The process according to claim 29, 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.

31: The process according to claim 29, 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.

32: The process according to claim 19, wherein the polymerization is performed at a temperature of −90° C. to +30° C.

33: An iron trihalide-donor complex, consisting of: at least one iron trihalide, optionally, at least one organic compound (II) comprising at least one oxygen or nitrogen atom with at least one lone electron pair, and at least one phosphorus-containing compound of formula (I) ##STR00010##  or
P(OR.sup.1)(OR.sup.2)(OR.sup.3), or  formula (Ia)
P(OR.sup.1)(OR.sup.2)(OR.sup.3)(OR.sup.4)(OR.sup.5),  formula (Ib) wherein X.sub.1, X.sub.2, and X.sub.3 independently of another are oxygen, sulphur, or a single bond, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with up to 20 carbon atoms, wherein a complex formed from the at least one iron trihalide 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.

34: A boron trihalide-donor complex, consisting of: at least one boron trihalide, optionally, at least one organic compound (II) comprising at least one oxygen or nitrogen atom with at least one lone electron pair, and at least one phosphorus-containing compound of formula (I) ##STR00011##  or
P(OR.sup.1)(OR.sup.2)(OR.sup.3), or  formula (Ia)
P(OR.sup.1)(OR.sup.2)(OR.sup.3)(OR.sup.4)(OR.sup.5),  formula (Ib) wherein X.sub.1, X.sub.2, and X.sub.3 independently of another are oxygen, sulphur, or a single bond, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with up to 20 carbon atoms, wherein a complex formed from the at least one boron trihalide 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.

35: A metal halide-donor complex, consisting of: at least one metal halide, selected from the group consisting of aluminum trihalide, alkylaluminum halide, gallium trihalide, titanium tetrahalide, zinc dihalide, tin dihalide, tin tetrahalide, and boron trihalide, at least one organic compound (II) comprising at least one oxygen or nitrogen atom with at least one lone electron pair, and at least one phosphorus-containing compound of formula (I) ##STR00012##  or
P(OR.sup.1)(OR.sup.2)(OR.sup.3), or  formula (Ia)
P(OR.sup.1)(OR.sup.2)(OR.sup.3)(OR.sup.4)(OR.sup.5),  formula (Ib) wherein X.sub.1, X.sub.2, and X.sub.3 independently of another are oxygen, sulphur, or a single bond, and R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.5 independently of another are an organic residue with up to 20 carbon atoms.

36: The process according to claim 19, wherein the high-reactivity isobutene homo- or copolymer has a number-average molecular weight M.sub.n, determined by gel permeation chromatography, of 500 to 100,000.

37: The process according to claim 19, wherein the at least one organic compound (II) comprises at least one oxygen atom with at least one lone electron pair.

38: The process according to claim 19, 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, organic compounds with at least one keto function, and organic compounds with at least one nitrogen containing heterocyclic ring.

Description

EXAMPLES

Example 1: Formation of Liquid Complexes

[0215] The following combinations of phosphorus containing electron donors according to formula (II) with Lewis acids were briefly tested in terms of possibility to prepare LCCs:

TABLE-US-00001 TABLE 1 Lewis acid χ (LA) P.sub.888O PPh.sub.3O AlCl.sub.3 0.6 yellow liquid viscous black liquid FeCl.sub.3 0.6 dark-brown liquid with black solid the finely dispersed precipitate TiCl.sub.4 0.6 viscous bright yellow orange solid liquid

[0216] The liquid complexes listed in Table 1 were further investigated in the polymerization of isobutene.

Example 2

[0217] According to the general procedure outlined above isobutylene was polymerized in the presence of PPh.sub.3O—AlCl.sub.3 as catalyst in n-hexane. Further to the conditions mentioned in Table 2 the polymerization was carried out as follows:

[0218] Mole fraction χ(AlCl3)=0.6; [IB]=5.2 M; T=0° C.; reaction time=30 min.

TABLE-US-00002 [LCC] Ether conv. M.sub.n End group distribution (%) run mM (mM) (%) (g mol.sup.−1) Ð exo endo + tri tetra PIBCI coupled 1.sup.b 22 — 81 1300 7.7 5 6 28 0 0 2 22 .sup.iPr.sub.2O (11) 32 2300 5.1 11 55 34 0 0 3 33 .sup.iPr.sub.2O (11) 89 1000 5.1 5 66 29 5 0 4 33 .sup.iPr.sub.2O (22) 30 4900 3.2 36 35 27 2 0 5 33 CE (22) 100 5000 3.3 57 24 18 1 0 6 33 CEE (22) 95 1400 2.1 70 15 9 0 6 .sup.btime = 10 min.

Example 3

[0219] According to the general procedure outlined above isobutylene was polymerized in the presence of P.sub.888O—AlCl.sub.3 as catalyst in n-hexane. Further to the conditions mentioned in Table 3 the polymerization was carried out as follows:

TABLE-US-00003 conv. M.sub.n End group distribution (%) run ether T, ° C. (%) (g mol.sup.−1) Ð exo endo + tri tetra PIBCI coupled 1.sup.b — 0 72 5200 4.0 0 68 32 0 0 2.sup.b .sup.iPr.sub.2O 0 15 3600 2.7 71 1 1 27 0 3 .sup.iPr.sub.2O 0 37 6500 3.1 48 25 13 14 0 4 .sup.iPr.sub.2O 10 44 6000 3.2 23 42 19 16 0 5 .sup.iPr.sub.2O 20 84 3600 2.3 2 69 30 0 0 6 CEE 0 40 5000 3.9 67 1 1 27 0 7 CEE 10 46 4200 2.9 67 25 13 14 0 8 CEE 20 56 2000 3.5 65 23 11 1 0 9 CE 0 100 6900 2.2 81 0 0 19 0 .sup.b[P.sub.888O—AlCl.sub.3] = 22 mM.

Example 4

[0220] According to the general procedure outlined above isobutylene was polymerized in the presence of P.sub.888O—FeCl.sub.3 as catalyst in n-hexane at 0° C. Further to the conditions mentioned in Table 4 the polymerization was carried out as follows:

[0221] Mole fraction χ(FeCl.sub.3)=0.6; [P.sub.888O—FeCl.sub.3]=22 mM; [IB]=5.2 M

TABLE-US-00004 [R.sub.2O] Time conv. M.sub.n End group distribution (%) run [R.sub.2O] [LCC] (min) (%) (g mol.sup.−1) Ð exo endo + tri tetra PIBCI coupled 1 — — 20 90 1800 7.0 25 35 36 0 4 2 .sup.iPr.sub.2O 1 20 26 2100 2.8 91 3 3 3 0 3 .sup.iPr.sub.2O 0.66 20 52 1400 2.3 97 2 0 0 1 4 .sup.iPr.sub.2O 0.5 20 100 1500 2.1 91 3 1 0 5 5 CEE 0.5 15 100 1000 2.2 80 10 4 0 6 6 CE 0.5 10 100 1300 3.1 41 29 24 0 6

Example 5

[0222] To have a deeper insight into the polymerization mechanism, the kinetics of isobutylene polymerization with the P.sub.888O—FeCl.sub.3/.sup.iPr.sub.2O initiating system at [.sup.iPr.sub.2O]/[P.sub.888O—FeCl.sub.3]=0.5 was briefly investigated.

[0223] The result was shown in FIG. 3.

[0224] It can easily be seen that the reaction according to the invention yields much higher conversion rates than the reaction with [emim]Cl—FeCl.sub.3 (2) according to Polymer, 145 (2018) 382-390, shown in FIG. 2.

[0225] The complex P.sub.888O—FeCl.sub.3/.sup.iPr.sub.2O does not only leads to higher conversion of isobutene in shorter time than the system [emim]Cl—FeCl.sub.3.

[0226] Simultaneously, the exo-selectivity at a certain conversion is higher for the complexes according to the invention than for those used for the reaction according to FIG. 2.

Example 6

[0227] The polymerization reaction was carried out in steel vessel equipped with a cold finger condenser under inert atmosphere at −20° C. Polymerization was initiated by adding of isobutylene (25.20 g, 45.0×10.sup.−2 mol) to a mixture of a total volume 150.02 mL consisting of 0.02 mL of MeOH, 10.00 mL of P.sub.888O—BF.sub.3 (χ(BF.sub.3)=0.58) and n-hexane (140.00 mL). After 1 h, 5 mL of MeOH was poured into the steel vessel to terminate the polymerization. The quenched reaction mixture was diluted by n-hexane and washed 3 times with MeOH. The solvent was evaporated under reduced pressure at 190° C. to give the product polymer. Monomer conversion was determined gravimetrically.

TABLE-US-00005 conv. M.sub.n End group distribution (%) run (%) (g mol.sup.−1) Ð exo endo + tri tetra coupled 1 86 920 1.2 35 60 4 1