阅读说明：本技术 用于或用作烯烃聚合催化剂的过渡金属络合物 (Transition metal complexes for use in or as catalysts for olefin polymerization ) 是由 N·H·弗来德里驰斯 M·A·祖德维尔德 P·凯尼恩 S·麦克林 于 2018-05-18 设计创作，主要内容包括：一种用于烯烃聚合的催化剂,其含有至少一种金属络合物,该金属络合物包含至少一个连接到与金属键合的配体上的-SF<Sub>5</Sub>基团。本发明进一步涉及催化剂、制造聚烯烃的方法和UHMWPE的分散体。(A catalyst for the polymerization of olefins comprising at least one metal complex comprising at least one-SF linked to a ligand bonded to a metal 5 A group. The invention further relates to a catalyst, a process for producing a polyolefin and a dispersion of UHMWPE.)

1. A catalyst for the polymerization of olefins comprising at least one metal complex comprising at least one-SF linked to a ligand bonded to a metal₅A group.

2. Transition metal complex suitable for use in a catalyst for olefin polymerization, wherein the metal complex comprises at least one-SF linked to a metal-bonded ligand₅A group.

3. The transition metal complex according to claim 2, wherein the complex is a catalyst or compound having the general structure 12:

wherein the substituents and subscripts have the following meanings:

m is a transition metal of groups 3 to 10 of the periodic Table of the elements,

·L₁representing neutral Lewis bases, e.g. phosphanes (R)¹⁹)_xPH_3-xOr amines (R)¹⁶)_xNH_3-xHaving identical or different radicals R¹⁶Ethers (R)¹⁶)₂O，H₂O, alcohol (R)¹⁶) OH, pyridine, formula C₅H_5-x(R¹⁶)_xPyridine derivatives of N, CO, C₁-C₁₂Alkyl nitriles, C₆-C₁₄An arylnitrile or an ethylenically unsaturated double bond system, and wherein x represents an integer from 0 to 3;

·L₂represents a halogen ion, an amide ion (R)¹⁶)_hNH_2-hH represents an integer of 0 to 2, and C₁-C₆Alkyl anions, allyl anions, benzyl anions or aryl anions, L₁And L₂May be linked to each other by one or more covalent bonds;

x is CR or a nitrogen atom (N), wherein R is hydrogen, C₁-C₆Alkyl radical, C₇-C₁₃Aralkyl or C₆-C₁₄Aryl, which is unsubstituted or substituted by one or more C₁-C₁₂Alkyl, halogen, monohalogenated or polyhalogenated C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, siloxy OSiR¹¹R¹²R¹³Amino group NR¹⁴R¹⁵Or C₁-C₁₂Thioether group substitution;

y is an OH group, oxygen, sulfur, N-R¹⁰Or P-R¹⁰；

A is 1 or 2; b is 0 or 1; c is 0 or 1, and wherein a + b + c is equal to the valence of the transition metal M, and wherein b + c is 1 or 2;

·R¹-R⁹independently of one another are:

hydrogen;

οC₁-C₁₂alkyl, which may be branched or unbranched, identically or differently selected from C₁-C₁₂Alkyl, halogen, C₁-C₁₂Alkoxy and C₁-C₁₂C substituted one or more times by sulfide group substituents₁-C₁₂An alkyl group; c₇-C₁₃Aralkyl group;

οC₃-C₁₂a cycloalkyl group;

is the same or different from C₁-C₁₂Alkyl, halogen, C₁-C₁₂Alkoxy and C₁-C₁₂C substituted one or more times by sulfide group substituents₃-C₁₂A cycloalkyl group;

οC₆-C₁₄aryl, which is optionally identical or different, selected from one or more C₁-C₁₂Alkyl, halogen, monohalogenated or polyhalogenated C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, siloxy OSiR¹¹R¹²R¹³Amino group NR¹⁴R¹⁵And C₁-C₁₂Substituent of thioether group;

οC₁-C₁₂an alkoxy group;

omicron siloxy OSiR¹¹R¹²R¹³；

O halogen;

οNO₂radicals or amino radicals NR¹⁴R¹⁵(ii) a Or

ο-SF₅A group or a group of the following formula 14, wherein n is an integer of 1 to 5;

in each case two adjacent radicals R¹-R⁹May form a saturated or unsaturated 5-to 8-membered ring with each other;

·R¹⁰-R¹⁶independently of one another are hydrogen, C₁-C₂₀Alkyl, which may in turn be substituted by O (C)₁-C₆Alkyl) or N (C)₁-C₆Alkyl radical)₂Radical substitution, C₃-C₁₂Cycloalkyl radical, C₇-C₁₃Aralkyl radical, C₇-C₁₃Substituted aralkyl radicals, C₆-C₁₄Aryl or substituted C₆-C₁₄An aryl group;

·R¹⁹may be C₁-C₂₀Alkyl radical, C₃-C₁₂Cycloalkyl radical, C₇-C₁₃Aralkyl radical, C₆-C₁₄Aryl, the alkyl, cycloalkyl, aralkyl and aryl groups may be in turn substituted by O (C)₁-C₆Alkyl) or N (C)₁-C₆Alkyl radical)₂Salt substitution of a group, a sulfonate group, or a sulfonate group;

wherein the radical R¹-R⁹Must be-SF₅Radical or radical of the formula 14

Wherein n is an integer from 1 to 5.

4. A transition metal complex according to claim 3, wherein the metal M is an early transition metal from groups 3-6 of the periodic table and a is 2, which means that the transition metal comprises 2 ligands.

5. The transition metal complex according to claim 2, having one of the structures according to:

6. the transition metal complex according to claim 2, wherein the complex has a structure according to formula 13,

and wherein the substituents and subscripts have the meanings defined above.

7. The transition metal complex according to claim 3 or 6, wherein Y is an-OH group or oxygen.

8. The transition metal complex according to any one of claims 3 to 7, wherein formula (R)¹⁹)_xPH_3-xThe phosphane of (a) is selected from salts of mono-, di-and tri-sulfonated triphenylphosphanes, preferably sodium salts of mono-, di-and tri-sulfonated triphenylphosphanes, most preferably TPPTS (3, 3' -phosphanetriyltris (benzenesulfonic acid) trisodium salt.

9. The transition metal complex according to any one of claims 6 to 8, wherein the complex is of formula 15

Wherein R is⁵、R⁷、R⁹Independently selected from H, methyl, isopropyl, NO₂And

wherein R is¹And R³Independently selected from H, methyl, isopropyl, NO₂I (iodine) and

wherein n is an integer from 1 to 5;

with the proviso that R¹、R³、R⁵、R⁷And R⁹At least one of which isWherein n is an integer from 1 to 5.

10. The transition metal complex according to any one of claims 3 to 9, which comprises-SF₅The group (14) of (A) is a 3, 5-difluorosulfanylphenyl group.

11. The transition metal complex according to any one of claims 6 to 10, wherein the complex is of formula 13₁-13₅Any one of the above-mentioned (a) and (b),

wherein R is⁵And R⁹Independently selected from H, -CH₃Or isopropyl, and

wherein R is¹And R³Independently selected from H, CH₃Isopropyl, phenyl, naphthyl, anthracenyl, -NO₂And

wherein L is₁Selected from pyridine or TPPTS and wherein L₂Is methyl.

12. The transition metal complex according to any one of claims 2 to 11, wherein L₁Selected from pyridine or TPPTS, L₂Is methyl, R¹And R³Independently selected from H, CH₃Isopropyl, phenyl, naphthyl, anthracenyl, NO₂And are and

13. a catalyst for the polymerization of olefins comprising a transition metal complex according to any of claims 2 to 12 and optionally a cocatalyst.

14. A process for the (co) polymerisation of olefin monomers by polymerising one or more olefin monomers in the presence of a catalyst as defined in claim 13 wherein an activator is present and the molar ratio of activator to catalyst is in the range 0.1 to 10, preferably 0.2 to 5, more preferably 0.5 to 2.

15. A copolymer of two or more olefins or a dispersion of a polyolefin obtained in the process according to claim 14, preferably wherein the polyolefin is an UHMwPE having a number average molecular weight Mn above 500.000 g/mol.

Examples

Determination of molecular weight

The molecular weight (weight average molecular weight (Mw) and number average molecular weight (Mn)) of the polyethylene obtained was 1mLmin at 160 ℃ in 1,2, 4-trichlorobenzene by HT-GPC^-1Measured at flow rate on a Polymer Laboratories 220 instrument equipped with an Olexis column with a refractive index detector, a viscosity detector and a light scattering detector. Mw and Mn were measured according to the method of ASTM D6474-12.

Polymerization in toluene

The polymerization of ethylene in toluene was carried out in a 300mL stainless steel mechanically stirred pressure reactor equipped with a heating/cooling jacket supplied by a thermocouple-controlled thermostat immersed in the polymerization mixture. The reactor was placed under vacuum and backfilled with argon, and the process was repeated three times at a temperature above 60 ℃ to ensure complete degassing of the reactor before cooling to 5 ℃ below the desired temperature. Then 100mL of distilled and degassed toluene were transferred in a cannula to the cooled reactor and stirred at 500 rpm. Then 5 μmol of the appropriate procatalyst was dissolved in minimal toluene and transferred to the reactor via syringe. The stirring speed was increased to 1000rpm and the reactor was pressurized to a constant pressure of 40bar of ethylene while warming to the desired value. The ethylene flow to the reactor was stopped after 40 minutes and the reactor was carefully vented. The bulk polymer was precipitated in methanol, filtered, washed thoroughly with methanol and dried overnight in a vacuum oven (50 ℃, 30 mBar).

Polymerization in aqueous dispersions

Ethylene polymerization in aqueous medium was carried out in a 300mL stainless steel mechanically stirred pressure reactor equipped with a heating/cooling jacket supplied by a thermocouple-controlled thermostat immersed in the polymerization mixture. The reactor was placed under vacuum and backfilled with argon, and the process was repeated three times at a temperature above 60 ℃ to ensure complete degassing of the reactor before cooling to 10 ℃. In a 250mL Schlenk type glass vessel, SDS (sodium dodecyl sulfate) (1.5 or 3g) and CsOH (512mg, if necessary) were dissolved in 100mL distilled and degassed water, then 90mL of the resulting homogeneous solution was transferred to a cooled reactor with a cannula and stirred at 500 rpm. Then 5 μmol of the appropriate procatalyst was dissolved in the remaining 10mL of aqueous solution and transferred via syringe into the reactor. The stirring speed was increased to 1000rpm and the reactor was pressurized to a constant pressure of 40bar of ethylene while warming to the desired value. The ethylene flow to the reactor was stopped after an appropriate time (30 or 60 minutes) and the reactor was carefully vented. The resulting dispersion was filtered on cotton wool (cottonwood) and the solids content was determined by precipitating a 20g aliquot with 150mL methanol. The bulk polymer obtained was then filtered, washed thoroughly (with water and methanol) and dried overnight in a vacuum oven (50 ℃, 30 mBar).

Examples with group 7-10 transition metals.

-SF₅Synthesis of substituted Compounds

desired-SF₅The synthesis of the substituted ligand is simple and requires only a few steps. Commercially available 1-bromo-3, 5-bis (pentafluorosulfanyl) benzene uses Pd (dppf) Cl₂It is readily converted to the pinacol-protected boronate ester (3). GC showed a conversion of starting material to product after 4.5 hours of>95% and the pure product can be isolated in 76% yield.

Scheme 2-containing SF₅The brominated compound of (a) is catalytically converted to the boronic ester.

From the boronic esters, the desired aniline (4, 6) is synthesized by Suzuki coupling or with 2, 6-dibromo-or 2,4, 6-tribromoaniline. Salicylaldimines (5, 7) are then synthesized by catalytic condensation of these anilines with the appropriate salicylic acid. Procatalyst (1-SF)₅/Py，2-SF₅/Py) was obtained in near quantitative yield by reaction with (TMEDA) NiMe2 in the presence of pyridine (scheme 1).

Synthesis of the Water-soluble Complex by introducing TPPTS (3, 3' -phosphanetriyltris (benzenesulfonic acid) trisodium salt) as a ligand into the intermediate ComplexIt is stabilized by the labile neutral ligand DMF. DMF complete exchange of TPPTS was unsuccessful, but the water-soluble complex 1-SF was isolated by washing away the lipophilic intermediate catalyst₅A crude procatalyst mixture of/TPPTS, free TPPTS and residual DMF. The relative ratios of these compounds can be determined from 1H NMR, which allows calculation of approximate molecular weights. This raw mixture can then be used to obtain a stable polyethylene dispersion by direct polymerization.

Scheme 3 Synthesis of Water soluble Ni (II) procatalyst 1-SF₅/TPPTS。

Scheme 1 Synthesis of-SF₅Substituted ligand and complexation to obtain Ni (II) procatalyst, 1-SF₅Py and 2-SF₅Py and 2-SF₅/Py。

Two additional catalysts according to the following structure have been prepared (1-SF)₅TPPTS and 2-SF₅/TPPTS)：

Comparative example:

using CF as the nickel catalyst₃Preparation of the substituents (as comparative example) and catalytic Properties with-SF according to the invention₅Catalysts for the substituents were compared.

Comparative example (CF)₃Substituent group)

Polymerisation

The initial polymerization was carried out in toluene over a wide temperature range (30-70 ℃ C.) to evaluate the substituents on the catalyst performanceAnd the influence of both polymer properties. When similar CF₃-SF in toluene for comparison of-complexes₅The substituted complexes exhibit reduced productivity, (shown in FIG. 2), particularly at 2-SF₅Py at 30 ℃ (Table 1, entry 7).

TABLE 1 use of the complex 1-SF₅/Py、2-SF₅Py and CF₃-analog (1-CF)₃/Py、2-CF₃Py) as a result of ethylene polymerization of the procatalyst in toluene. a is

^aPolymerization conditions: 5. mu. mol procatalyst, 100mL toluene, 40bar C₂H₄，40min。^b10⁴×mol[C₂H₄]×mol^-1[Ni]×h^-1。^cMeasured by GPC at 160 ℃.^dMeasured by DSC.^eBy passing¹³C NMR spectroscopy.^fComprising 1.1 ethyl branches and<0.5 n-propyl branch.

Although the loss of activity may appear to be the use of-SF₅Defects of the complex, but this is relatively small and in 1-SF₅In the case of/Py, the switching frequency (TOF) is comparable. There are also several known methods for enhancing the activity of these neutral ni (ii) salicylaldimine complexes. They include destabilization of the quiescent state by ligand design, use of less strongly coordinating ligands and removal of neutral ligands via phase transfer or addition of appropriate scavengers. the-SF₅The increase in β -hydrogen elimination with increasing polymerization temperature leads to a decrease in polymer melt temperature with increasing branching (and decreasing molecular weight)₃This reduction in melting temperature is significantly reduced compared to polymers produced by the analogue, which can be a significant advantage in certain polymer applications. Although the melting temperatures of the polymers produced at 30 ℃ are comparable, use is made of-SF₅Poly(s) of the complex produced at 70 ℃Melting temperature ratio of the compound by CF₃Those produced by the analogues were 7 ℃ and 8 ℃ higher. by-SF₅By branching of substituted catalysts¹³C NMR showed only methyl branching, indicating that chain travel was restricted even after β -hydrogen elimination, and that subsequent insertion was rapid₅Substituted complexes, with a significant decrease in branching at higher temperatures. Different from CF₃-analog, 1-SF₅Py and 2-SF₅the/Py showed very similar degree of branching despite the significantly different catalyst structure. Comparative 1-SF₅Py and 1-CF₃Py, there was a significant increase in molecular weight at all temperatures. Polymerization at 50 deg.C (Table 1, entries 2 and 5) is probably due to the introduction of-SF which results in a tripling of the molecular weight₅The most obvious example of how such simple substitution can be made. Using 2-SF₅Py and 2-CF₃A similar trend was seen for/Py, and when 2-SF was used₅In the case of/Py, polymerization at higher temperatures (50 ℃ C., 70 ℃ C.) gives polymers having higher molecular weights. In conclusion, it is clear that the introduction of-SF₅The substituents result in a significant improvement in polymer properties despite a slight decrease in productivity.

Using water-soluble catalyst 1-SF₅the/TPPTS is polymerized to give a dispersion of high molecular weight, linear polyethylene. Unlike polymerization in toluene, it appears that in aqueous medium-SF₅Substituted and CF₃There was no significant difference in productivity between the substituted complexes. CsOH was added (to inhibit hydrolysis), and 1-CF was added₃Increase in productivity of/TPPTS to 1-SF₅Point where the production rate of TPPTS is higher. Indicating the absence of hydrolysis, 1-CF₃The productivity of/TPPTS would be higher as can be expected from the results in toluene. However, it can also be obtained from 1-SF stabilizing the catalyst₅The bulk of free ligand present in the crude mixture of TPPTS.

TABLE 2 use of the complex 1-SF₅TPPTS and CF thereof₃-analog, 1-CF₃the/TPPTS is the result of ethylene polymerization as a procatalyst in water. a is

^aPolymerization conditions: 5 μmol procatalyst, 100mL H₂O, 15 ℃, 1.5g SDS, 40bar C₂H₄，30min。^b100mL H₂O，15℃，3g SDS，512mg CsOH.H₂O，60min。^c10⁴×mol[C₂H₄]×mol^-1[Ni]。^dMeasured by GPC at 160 ℃.^e1 st/2 nd heating by DSC measurement. f was determined by DLS, volume average.^gBy passing¹³C NMR spectroscopy.

Different from CF₃-analogue, complex 1-SF₅the/TPPTS yields polyethylene dispersions having the characteristic melting properties of linear Ultra High Molecular Weight Polyethylene (UHMWPE), i.e. an exaggerated first melting temperature in the region of 140 ℃, while all subsequent melting achieves a melting temperature of ≈ 135 ℃. Dispersions with these melting properties have been obtained beforehand as "ideal polyethylene nanocrystals", which however require a lower polymerization temperature of 10 ℃ to limit branching and have an Mn of not more than 420.000 g/mol. Polymerization at 10 ℃ is undesirable because at this temperature, ethylene hydrate formation can lead to large temperature changes and destabilization of the polyethylene dispersion. By using additives that can suppress the formation of ethylene hydrates (e.g. PEG), polymerization at 10 ℃ is only possible for short reaction times. Complex 1-SF₅The productivity of the/TPPTS is also significantly greater than the catalyst used to produce the ideal polyethylene nanocrystals, which at half the catalyst loading yields a dispersion with higher polymer content. Although the previously synthesized "ideal polyethylene nanocrystals" exhibited melting behavior similar to linear UHMWPE. Their molecular weight (Mn. about.420 kgmol-1) and UHMWPE (Mn)>500kgmol-1) is relatively low. This difference in melting behavior and molecular weight is achieved by using the complex 1-SF₅the/TPPTS is reduced. Using this catalyst it is possible to obtain polyethylenes having a molecular weight (as Mn) in excess of 1000kgmol-1 and, using suitable additives, it is possible to obtain polyethylenes higher than those of the prior art previouslyThe molecular weight of 1000kgmol-1 increased (Table 2, entry 2). Polyethylene is produced in a highly organized crystalline form, as are other dispersions produced using this polymerization process. Although the crystals produced by the catalyst are large: (<250nm) and less uniform in size, but retains a high degree of crystallinity (< 75%) and the polyethylene is disentangled, as evidenced by the fact that no exaggerated first melting temperature is observed when a slow melting rate is used.

Examples with Ti as transition metal

A Ti-catalyst having the following procatalyst structure has been prepared.

Procatalyst construction:

having CF₃The group catalyst is a comparative catalyst and has-SF₅The catalyst of the group is a catalyst according to the invention.

Synthesizing a TMS-ligand:

synthesis of-SF₅-FI ligand:

aminophenylthiopentafluoride (1.096g, 5mmol) and 3-tert-butylsalicylaldehyde (0.893g, 5mmol) were dissolved in TsOH.H₂O-acidified toluene (6 mL). The mixture was stirred at 70 ℃ overnight. After stirring overnight the solvent was removed to give an oily yellow solid which was washed with methanol (2 × 5mL) and the yellow powder was dried under high vacuum (1.49g, 3.9mmol, 79%).

1H NMR(400MHz，CDCl₃)：δ13.04(br s，1H)OH，8.50(s，1H)5，7.91(dd，J＝8.4，1.3Hz，1H)1，7.59(td，J＝7.7，1.4Hz，1H)3，7.49(dd，J＝7.7，1.7Hz，1H)8，7.37(t，J＝7.9Hz，1H)2，7.30(dd，J＝7.7，1.8Hz，1H)6，7.10(m，1H)4，6.93(t，J＝7.7Hz，1H)7，1.52(s，9H)9。

Synthesis of TMS-SF₅-FI ligand:

mixing SF₅-FI ligand (1.25g, 3.3mmol) was dissolved in abs.THF (12mL) and added to Schlenk containing NaH (450 mg). It was then stirred at 50 ℃ for 3 hours, then excess TMSCl (2.1mL) was added. The resulting decolorized mixture was stirred for 2 hours, and then the solvent was removed. The solid was resuspended in pentane (15mL) and filtered. Removal of pentane gave the product as a white solid (810mg, 1.8mmol, 54%).

1H NMR(400MHz，CDCl₃)：δ8.65(s，1H)5，8.03(dd，J＝7.7，1.9Hz，1H)6，7.87(dd，J＝8.4，1.3Hz，1H)1，7.52(m，2H)3，8，7.28(t，J＝7.9Hz，1H)2，7.07(t，J＝7.7Hz，1H)7，6.94(d，J＝7.9Hz，1H)4，1.47(s，9H)9，0.31(s，9H)10。

Synthesis of (tBu _ SF) via dehalogenation silylation₅_SA)₂TiCl₂：

Mixing TMS-SF₅The FI ligand (271mg, 0.6mmol) was dissolved in toluene (3mL) and TiCl in toluene (1mL) was added₄(57mg, 0.3mmol) in water. The solution turned red immediately and was left to stir for 3.5 hours. The solvent was removed in vacuo to give an oily red solid which was washed with pentane (2 × 5mL) to give a red/orange powder (85mg, 0.1mmol, 33%).

1H NMR(400MHz，C₆D₆)：δ7.85(s，2H)，7.47(d，J＝8.6Hz，2H)7.30(d，J＝7.9Hz，4H)6.87(t，J＝7.73Hz，2H)，6.74(d，J＝7.5Hz，2H)，6.66(m，4H)，1.46(s，18H)。

The loading of the catalyst is as follows: 1 μmol, Al: Ti 750: 1.

Polymerisation procedure

Ethylene polymerization in toluene using a titanium catalyst was carried out in a 300mL stainless steel mechanically stirred pressure reactor equipped with a heating/cooling jacket supplied by a thermocouple-controlled thermostat immersed in the polymerization mixture. The reactor was placed under vacuum and backfilled with argon, and the process was repeated three times at a temperature above 60 ℃ to ensure complete degassing of the reactor before cooling to the desired temperature. Then 100mL of distilled and degassed toluene was transferred to the cooled reactor with a cannula and stirred at 500 rpm. Then 0.5mL of MAO-10T (750. mu. mol) was added to the reactor via syringe and allowed to stir. Then 1. mu. mol of the appropriate procatalyst was added via syringe. The stirring speed was increased to 1000rpm and the reactor was pressurized to a constant pressure of ethylene of 6 bar. The ethylene flow to the reactor was stopped after 10 minutes and the reactor was carefully vented. The polymer was collected in methanol (acidified with HCl) and stirred, filtered, washed thoroughly with methanol and dried in a vacuum oven (50 ℃, 30mBar) overnight.