Highly Active Double Metal Cyanide Compounds

Abstract

The present invention is directed to supported catalyst having utility in the polymerization and co-polymerization of epoxide monomers, said supported catalyst having the general Formula (I):

[DMCC]*b Supp  (I) wherein: [DMCC] denotes a double metal cyanide complex which comprises a double metal cyanide (DMC) compound, at least one organic complexing agent and a metal salt; Supp denotes a hydrophobic support material; and, b represents the average proportion by weight of said support material, based on the total weight of [DMCC] and Supp, and is preferably in the range 1 wt. %≤b≤99 wt. %.

Claims

1. A supported catalyst having the general Formula (I):
[DMCC]*b Supp  (I) wherein: [DMCC] denotes a double metal cyanide complex which comprises a double metal cyanide (DMC) compound, at least one organic complexing agent and a metal salt; Supp denotes a hydrophobic support material; and, b represents the average proportion by weight of said support material, based on the total weight of [DMCC] and Supp; wherein the hydrophobic support material is selected from the group consisting of hydrophobic materials having a methanol wettability value of at least 30 vol. %; carbonaceous inorganic solid materials; and inorganic solid materials which are isoelectronic with carbon.

2. The supported catalyst according to claim 1, wherein b is in the range of 10 wt. %≤b≤70 wt. %.

3. The supported catalyst according to claim 1, wherein said double metal cyanide complex [DMCC] is represented either by the general Formula (II-A)
M.sup.1.sub.d[M.sup.2(CN).sub.e].sub.f*xM.sup.3(X).sub.g*yH2O*ωL  (II-A); or
by general Formula (II):
M.sup.1.sub.d[M.sup.2(CN).sub.e].sub.f*xM.sup.3(X).sub.g*yH2O*zL.sup.1*aL.sup.2  (II) wherein: M.sup.1 is a Zn, Fe, Co, Ni, Mn, Cu, Sn or Pb ion; M.sup.2 is a Fe, Co, Mn, Cr, Ir, Rh, Ru or V ion; M.sup.3 is a Zn, Fe, Co, Ni, Mn, Cu, Sn, Pb, Cr, Ir, Rh, Ru or V ion; X is an anion; L is an organic complexing agent; L.sup.1 and L.sup.2 are distinct from one another and represent respectively first and second organic complexing agents; d, e, f and g are each integers >0 but have values such that the complex M.sup.1.sub.d[M.sup.2(CN).sub.e].sub.f*xM.sup.3(X).sub.g is electrically neutral; 0.1≤x≤5; 0.1≤y≤1; 0.0001≤ω≤6; 0.0001≤z≤1; and, 0.0001≤a≤5.

4. The supported catalyst according to claim 3, wherein said double metal cyanide complex [DMCC] is represented by Formula (II-A) and further meets at least one of the following conditions: i) M.sup.1 is equal to M.sup.3; ii) X is an anion selected from the group consisting of halide, hydroxide, sulphate, carbonate, cyanide, thiocyanide, carboxylate, nitrate, borate and antimonite; and, iii) L is selected from the group consisting of aliphatic C.sub.1 to C.sub.24 alcohols, monoglyme, diglyme, 1,4-dioxane, furan, polypropyleneglycol (PPG) homopolymers, polypropyleneglycol (PPG) copolymers and mixtures of two or more thereof.

5. The supported catalyst according to claim 3, wherein said double metal cyanide complex [DMCC] is represented by Formula (II) and further meets at least one of the following conditions: i) M.sup.1 is equal to M.sup.3; ii) X is an anion selected from the group consisting of halide, hydroxide, sulphate, carbonate, cyanide, thiocyanide, carboxylate, nitrate, borate and antimonite; and, iii) L.sup.1 and L.sup.2 are independently selected from the group consisting of aliphatic C.sub.1 to C.sub.24 alcohols, monoglyme, diglyme, 1,4-dioxane, furan, polypropyleneglycol (PPG) homopolymers, polypropyleneglycol (PPG) copolymers and mixtures of two or more thereof.

6. The supported catalyst according to claim 3, wherein: i) M.sup.1 is equal to M.sup.3 and is Zn; M.sup.2 is Co; and, ii) X is a halide.

7. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) has a methanol wettability value of from 30 to 80 vol. %.

8. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) is selected from the group consisting of hydrophobically modified inorganic oxide or hydroxide, hydrophobically modified calcium carbonate, and clay.

9. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) is selected from hydrophobically modified silica or hydrophobically modified calcium carbonate.

10. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) is selected from carbonaceous inorganic solid materials or inorganic solid materials which are isoelectronic with carbon.

11. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) is selected from activated charcoal, carbon black, carbon nanotubes, fullerene, graphene or boron nitride.

12. The supported catalyst according to claim 1, wherein the hydrophobic support material (Supp) is selected from the group consisting of hydrophobically modified silica, hydrophobically modified fumed silica, hydrophobically modified calcium carbonate, activated charcoal, carbon black and graphene.

13. A method for producing the supported catalyst of Formula (I) as defined in claim 1, comprising the steps of: i) mixing in an aqueous medium a) at least one complexing agent; b) the hydrophobic support (Supp); c) at least one salt of the general formula (IIa);
M.sup.1.sub.dX.sub.g  (IIa) where M.sup.1 is a Zn, Fe, Co, Mn, Cu, Sn, Pb or Ni ion, X is an anion, and d and g are integers >0 and assume values such that the salt M.sup.1.sub.dX.sub.g is electroneutral; and, d) at least one complex of the general formula (IIb)
M.sup.3.sub.h[M.sup.2(CN).sub.e].sub.f  (IIb) where M.sup.3 is an alkali metal ion, M.sup.2 is a Co, Cr, Mn, Ir, Rh, Ru, V or Fe ion and h, e and f are integers >0 and assume values such that the complex M.sup.3.sub.h[M.sup.2(CN).sub.e].sub.f is electroneutral; ii) washing the obtained catalyst with an aqueous solution; iii) drying the washed catalyst.

14. A method for producing the supported catalyst of Formula (I) as defined in claim 1, comprising the steps of: i) mixing in an aqueous medium a) at least one complexing agent; c) at least one salt of the general formula (IIa);
M.sup.1.sub.dX.sub.g  (IIa) where M.sup.1 is a Zn, Fe, Co, Mn, Cu, Sn, Pb or Ni ion, X is an anion, and d and g are integers >0 and assume values such that the salt M.sup.1.sub.dX.sub.g is electroneutral; and, d) at least one complex of the general formula (IIb)
M.sup.3.sub.h[M.sup.2(CN).sub.e].sub.f  (IIb) where M.sup.3 is an alkali metal ion, M.sup.2 is a Co, Cr, Mn, Ir, Rh, Ru, V or Fe ion and h, e and f are integers >0 and assume values such that the complex M.sup.3.sub.h[M.sup.2(CN).sub.e].sub.f is electroneutral; ii) washing the obtained catalyst with an aqueous solution; iii) drying the washed catalyst, wherein b) the hydrophobic support (Supp) is added before or during the washing step ii) or after the drying step iii).

15. A method for producing a functionalized polymer or copolymer, said method comprising the steps of: a) providing an initiator, said initiator comprising or consisting of an active hydrogen-containing compound capable of alkoxylation by an epoxide compound; b) providing a supported catalyst as defined in claim 1; and, in the presence of said initiator and said supported catalyst, performing a ring opening polymerization of at least one epoxide monomer or co-polymerization of carbon dioxide and at least one epoxide monomer.

16. A coating, sealant or adhesive composition based on active hydrogen reactive compounds comprising the functionalized polymer or copolymer of claim 15 as a reactive component.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0210] FIG. 1 appended hereto is a High Angle Annular Dark Field (HAADF) transmission electron micrograph (TEM) of the supported catalyst prepared in accordance with Example A herein below. To prepare the TEM, solid samples of the catalyst were disposed, without any pretreatment, on a holey, carbon-supported Cu-grid (Mesh 300) and transferred to the microscope. The TEM measurements were performed at 200 kV with an aberration-corrected JEM-ARM200F (JEOL, Corrector: CEOS). The microscope is equipped with a JED-2300 (JEOL) energy-dispersive x-ray-spectrometer (EDXS) and an Enfinum ER (GATAN) with DualEELS for chemical analysis. The aberration corrected STEM imaging (HAADF) was performed under the following conditions: spot size of approximately 0.1 nm; a convergence angle of 30-36°; and, collection semi-angles of 90-170 mrad.

[0211] FIG. 2 appended hereto is the expanded insert of FIG. 1.

[0212] FIG. 3 is the corresponding Energy-dispersive X-ray spectra (EDXS) of the highlighted region [001] of FIG. 2.

[0213] FIG. 4 is the corresponding Energy-dispersive X-ray spectra (EDXS) of the highlighted region [002] of FIG. 2.

[0214] FIG. 5 is the corresponding Energy-dispersive X-ray spectra (EDXS) of the highlighted region [003] of FIG. 2.

[0215] FIG. 6 is the corresponding Energy-dispersive X-ray spectra (EDXS) of the highlighted region [004] of FIG. 2.

[0216] FIG. 7 is the corresponding Energy-dispersive X-ray spectra (EDXS) of the highlighted region [005] of FIG. 2.

[0217] FIG. 8 provides a comparison of the first order rate constant for the catalytic system obtained in Example A with the first order rate constants of the catalytic systems of Examples J and K. The rate constants were determined by on-line monitoring of the consumption of propylene oxide (PO).

EXAMPLES

Preparation of DMC Catalysts

[0218] The following commercial products were utilized in the Examples: [0219] i) Eutanol® G is a medium spreading emollient available from BASF SE. The product has a hydroxyl value of 175-190 mg KOH/g, a refractive index (20° C.) of 1.4535-1.4555, and a density (20° C.) of 0.835-0.845 g/cm.sup.3. [0220] ii) Aerosil® 104 is hydrophobic fumed silica available from Evonik Industries. [0221] iii) Aerosil® 150 is hydrophilic fumed silica available from Evonik Industries. [0222] iv) HDK® H20 is hydrophobic fumed silica available from Wacker Chemie AG. [0223] v) HDK® N20 is hydrophilic fumed silica available from Wacker Chemie AG. [0224] vi) Carbital 110S is fine ground calcium carbonate coated with fatty acids available from Imerys. [0225] vii) Carbital 110 is fine ground calcium carbonate available from Imerys. [0226] viii) Hakuenka® CCR-S is a precipitated calcium carbonate coated with fatty acids available from Shiraishi Omya GmbH.
The methanol wettability value (vol. %) of the materials listed in Table 1 below was measured by the following methanol wettability test, which is an analytic test method used for the determination of hydrophobicity of Aerosil® product by Evonik Industries (http://www.aerosil.com/product/aerosil/en/services/downloads/Pages/test-methods.aspx as of August 2014).

Methanol Wettability Test

[0227] Procedure: Into at least 4 transparent centrifugal tubes (each 80 ml) 1.2 g (±0.005 g) of samples are weighed first. 48.0 ml of a certain methanol/water mixture (of 10 percent by volume to 90 percent by volume methanol, in 5 percent steps) are added to each weighed portion. The tubes were closed and shaken for 10 seconds by hand and 30 seconds in a horizontal shaker, level 12 (Rütteltisch F. Gerhardt LS10). The samples are subsequently centrifuged at 2500/min at 23° C. for 5 minutes in a laboratory centrifuge. Evaluation takes place after 5 minutes of recondition.

[0228] Evaluation: The methanol wettability value of each sample (supporting material) was defined by the lowest percentage of methanol (vol. %) in a methanol/water mixture, that shows still a quantitative wetting of all support materials, meaning that 100% of the support material were sedimented (no support material in the solution or on the surface of the solution). The lowest percentage of methanol define and quantify the methanol wettability value in vol. %.

TABLE-US-00001 TABLE 1 quantification of the hydrophobicity of the support material by the methanol wettability test described herein Methanol wettability value Methanol/Water in Support material (vol. %) vol. % Aerosil ® 104 60 60/40 HDK ® H20 65 65/35 HDK ® N20 20 20/80 Aerosil ® 150 20 20/80 Hakuenka ® CCR-S 70 70/30 Carbital 110 S 65 65/35 Carbital 110 10 10/90
Example A: To a solution of 3 g (9 mmol) of potassium hexacyanocobaltate in 150 ml of distilled water, 10 ml tert-butyl alcohol, 0.1 g Eutanol® G and 3 g of Aerosil® R 104 were added under vigorous stirring (20000 rpm). Immediately afterwards, a solution of 20 g (147 mmol) of zinc chloride in 100 ml of distilled water and 20 ml tert-butyl alcohol was added to the Aerosil-mixture with vigorous stirring (20000 rpm). The intensity of stirring was reduced (8000 rpm) but continued for 20 minutes. The obtained solid was isolated by centrifugation. The solid was then stirred (10,000 rpm) for 20 minutes with a mixture of 50 ml of tert-butyl alcohol, 50 ml of distilled water and 0.1 g of Eutanol® G and again isolated by centrifugation. The resultant solid was stirred once again (8000 rpm) for 20 minutes with a mixture of 75 ml tert-butyl alcohol and 0.01 g of Eutanol® G and isolated by centrifugation. Thereafter, the resultant solid was stirred again (8000 rpm) for 20 minutes with a solution of 100 ml tert-butyl alcohol and 0.05 g of Eutanol® G. After filtration, the catalyst was dried to constant weight at 50° C. under vacuum.
Example B: The same procedure was used as described in example A except that Aerosil® 104 was added in the last washing step.
Example C: The same procedure was used as described in example A except that Aerosil® 104 was used without Eutanol® G.
Example D: The same procedure was used as described in example A except that Aerosil® 150 was used instead of Aerosil® 104.
Example E: The same procedure was used as described in example A except that HDK® H.sub.2O was used instead of Aerosil® 104.
Example F: The same procedure was used as described in example A except that HDK® N20 was used instead of Aerosil®104.
Example G: The same procedure was used as described in example A except that Carbital 110 S was used instead of Aerosil®104.
Example H: The same procedure was used as described in example A except that Carbital 110 was used instead of Aerosil®104.
Example I: The same procedure was used as described in example A except that Hakuenka® CCR-S was used instead of Aerosil®104.
Example J: A DMC catalyst using Eutanol® G without a silica-based compound was prepared. 1.5 g of potassium hexacyanocobaltate was dissolved in 50 ml of distilled water in a beaker. A solution of 0.35 mmol of Eutanol® G and 5 ml of tert-butyl alcohol is added thereto (Solution 1). 10 g of zinc chloride is dissolved in 50 ml of distilled water and 10 ml of tert-butyl alcohol (Solution 2). Solutions 1 and 2 were combined using a dispersing system for mixing. After stirring for 20 minutes the mixture was centrifuged. The solid was then stirred (10,000 rpm) for 20 minutes with a mixture of 50 ml of tert-butyl alcohol, 50 ml of distilled water and 0.1 g of Eutanol® G and again isolated by centrifugation. The resultant solid was stirred once again (8000 rpm) for 20 minutes with a mixture of 75 ml tert-butyl alcohol and 0.01 g of Eutanol® G and isolated by centrifugation. Thereafter, the resultant solid was stirred again (8000 rpm) for 20 minutes with a solution of 100 ml tert-butyl alcohol and 0.05 g of Eutanol® G. After filtration, the solid cake was re-suspended in a 100% tert-butyl alcohol washing solution, homogenized for 20 minutes and centrifuged: the resulting precipitate was dried to constant weight under vacuum at 50° C.
Example K: A DMC catalyst according to Example 1 of EP 0700949 A2. 8.0 g potassium hexacyanocobaltate was dissolved in 140 mL deionized water in a beaker (Solution 1). 25 g of zinc chloride 25 g was dissolved in 40 ml of deionized water in a second beaker (Solution 2). A third beaker contains Solution 3: a mixture of deionized water (200 mL), tert-butyl alcohol (2 mL), and polyol (2 g of a 4000 mol. wt. poly(oxypropylene) diol). Solutions 1 and 2 were mixed together using a disperser. Immediately, Solution 4, a 50/50 (by volume) mixture of tert-butyl alcohol and deionized water (200 ml total) was added to the zinc hexacyanocobaltate mixture, and the product was stirred for 10 min. Solution 3 (the polyol/water/tert-butyl alcohol mixture) was added to the aqueous slurry of zinc hexacyanocobaltate, and the product was stirred (700 rpm) for 3 min. The mixture was centrifuged to isolate the solids. The solid cake was reslurried in tert-butyl alcohol (140 ml), deionized water (60 ml), and additional 4000 mol. wt. poly(oxypropylene) diol (2.0 g), the mixture was homogenized for 10 min. and centrifuged as described above. The solid cake is reslurried in tert-butyl alcohol (200 ml) and additional 4000 mol. wt. poly(oxypropylene) diol (1.0 g), homogenized for 10 min., and centrifuged. The resulting solid catalyst was dried under vacuum at 50° C. to constant weight. The yield of dry, powdery catalyst was 12.02 g.
Example L: The same procedure was used as described in example A except that activated charcoal powder from Sigma-Aldrich (Product no. 05105) (Cas no. 7440-44-0) was used instead of Aerosil®104.

General Methods for the Propoxylation Reaction

[0229] a) Synthesis of PPG (Mw 3400 g/Mol) in a 100 ml Steel-Autoclave
27 g of a polypropylene glycol diol (Mw 2000 g/mol) was charged in a 100 ml stirring autoclave together with 0.015 g of the selected (DMC) catalyst. The mixture was stirred for 1 hour at 105° C. under reduced pressure (<10 mbar) to remove moisture and volatile contaminants. Thereafter it was stirred under heating to 120° C. in an Argon atmosphere. After reaching this temperature, propylene oxide (0.1 mol) was added in one portion until the total internal pressure increased to 4.5 bar. An increase of temperature and an accelerated drop in the reactor pressure was soon noted, indicating catalyst activation. The reactor was further stirred until the pressure reached 0.5 bar.
b) Synthesis of PPG (12000 g/Mol) in a 1 L Steel-Autoclave
83 g of a propylene glycol diol (Mw 2000 g/mol) was charged in a 1 L steel autoclave together with 0.015 g of the selected (DMC) catalyst (30 ppm based on the weight of the desired product). The mixture was stirred for 1 hour at 105° C. under reduced pressure (<10 mbar) to remove moisture and volatile contaminants. Thereafter it was stirred under heating to 120° C. in an Argon atmosphere. After reaching this temperature and an initial pressure of 0.5 bar, 10 g propylene oxide (PO) was dosed in order to induce the start of the reaction. The internal pressure increased to 2.8 bar. Further propylene oxide was, however, only added when an accelerated pressure drop was observed in the reactor, indicative of the catalyst having been activated: the remainder of the propylene oxide (420 g) was added continuously.
After addition of all the propylene oxide and following a 1 hour post-reaction period at 120° C., the volatile components were distilled off at 90° C. under reduced pressure (<10 mbar) and the mixture then cooled to room temperature.
The propoxylation reaction was followed by means of a time/conversion curve, specifically propylene oxide consumption [g] versus reaction time [min]. The induction time (t.sub.induction) was determined from the point of interception of the tangent to the steepest point of the time/conversion curve with the extended base line of the curve. Table 2 characterizes the catalysts and the polyether diols obtained therewith in following the above described propoxylation reactions.

TABLE-US-00002 TABLE 2 Catalyst Propoxylation Propoxylation at 1 L scale Characterization at 100 ml scale Polymer Properties DMC Zn Co t.sub.induction Polydispersity Viscosity OH Number Catalyst [%] [%] [min] (PDI) [mPas] [mg KOH/g] Example A 14.47 8.28 6 1.3 8000 11.0 Example B 12.51 7.32 5 1.2 5590 10.3 Example C 16.32 9.18 5 1.5 10480 10.8 Example D 11.27 7.69 47 n/a* n/a* n/a* Example E 11.67 6.77 9 1.3 8240 10.7 Example F 12.62 7.41 19 1.6 17920 10.3 Example G 12.44 7.91 4 1.2 7200 10.2 Example H 14.21 8.30 12 1.5 15630 10.5 Example I 12.88 7.48 7 1.3 7300 10.4 Example J 27.55 14.34 4 1.2 7000 10.0 Example K 16.71 9.16 8 1.3 6180 10.4 Example L 14.43 8.26 5 1.3 7800 10.3 *No product for analytical test was available as the catalyst showed no proper reactivity.

Determination of the Catalyst Activity

[0230] In the above described polymerization process, the propagation reaction is of the form:

##STR00002##

wherein: P* represents a reactive polymer chain; n the number of monomeric units; PO denotes a propylene oxide molecule; and, k.sub.pr the rate constant of the propoxylation reaction.
Considering the rate law

[00001]$r_{\mathrm{pr}}=-\frac{d\left[\mathrm{PO}\right]}{dt}=k^{\prime }.Math.\left[\mathrm{PO}\right]\mathrm{with}{h}^{\prime }=k_{\mathrm{pr}}.Math.\left[P^{\prime }\right]$

and also considering that in an immortal polymerization the number of chain ends (n.sub.P*) stays constant, an integration of the rate law leads to:

In[PO]=k′.Math.t+In[PO].sub.0

The propagation reaction is then treated as pseudo first-order.
For determining the rate constants, a discontinuous feeding method was used, in which the consumption of propylene oxide (PO) was monitored with an in situ infrared (IR) probe upon stepwise addition of PO into a 2 liter stainless steel autoclave reactor equipped with an anchor agitator.
166 g of polypropylene glycol starter was first mixed in the reactor with 5 ppm of the catalyst to be evaluated, in a similar procedure to that described in Example 1. The reactor was heated up to 125° C. and 20.8 g (25 ml) of PO was added to initiate the reaction. After the sudden pressure drop occurred, the stepwise addition of PO was started (10% PO, 1.7 ml, 30 ml/min). After each addition, the concentration of PO showed the expected exponential decrease of 1.sup.st order kinetics.
The propoxylation times, which are critical for catalyst activity, correspond to the period between catalyst activation—the end of the induction period—and the end of propylene oxide addition. The total reaction time is the sum of the induction and propoxylation times.
The rate constant (k′/[P*]) after each feed step was calculated and the change of the rate constant upon dilution of the hydroxyl chain ends—as a consequence of the chain growth—is presented in FIG. 8. A comparison of the rate constants for the evaluated catalysts after the first PO dosing is also presented in Table 3 below.

TABLE-US-00003 TABLE 3 Rate Constants after the first PO dosing for the propoxylation reaction using different catalysts Catalyst Used Rate Constant (k′/[P*]) Example A 9.02E−04 Example J 4.27E−04 Example K 1.24E−04
In view of the foregoing description and examples, it will be apparent to those skilled in the art that equivalent modifications thereof can be made without departing from the scope of the claims.