WO2010136544A1

WO2010136544A1 - Process for catalytic ring-opening polymerization of cyclic monomers

Info

Publication number: WO2010136544A1
Application number: PCT/EP2010/057360
Authority: WO
Inventors: Carsten Strohmann; Sonja Herres-Pawlis; Viktoria Gessner; Janna Börner; Prisca Eckert; Klaus Jurkschat; Gerrit BRADTMÖLLER; Markus SCHÜRMANN; Michael Gock
Original assignee: Technische Universität Dortmund
Priority date: 2009-05-28
Filing date: 2010-05-27
Publication date: 2010-12-02

Abstract

The present invention relates to a process for catalytic ring-opening polymerization of cyclic monomers by means of diamine-zinc complexes and/or polynuclear aminoethoxide-zinc complexes, and to processes for preparing suitable diamine-zinc complexes and polynuclear aminoethoxide-zinc complexes. The polymerization process according to the invention is suitable for providing polymers with an optimized polydispersity.

Description

Process for the catalytic ring-opening polymerization of cyclic

monomers

The present invention relates to a process for the catalytic ring-opening polymerization of cyclic monomers with diam in-zinc complexes and / or polynuclear aminoethanolate-zinc complexes and to processes for preparing suitable diamine-zinc complexes and polynuclear aminoethanolate-zinc complexes.

The ring-opening polymerization is capable of producing a variety of different polymers starting from cyclic monomers. Thus, for example, polylactides can be prepared starting from lactide. Polylactides (PLA) are thermoplastics that find industrial application in a variety of ways. The properties of PLA depend, as with all polymers, primarily on the degree of polymerization and the associated molecular weight and degree of crystallinity. In addition, the polydispersity, which is a measure of the width of the molecular weight distribution, has an influence on the physical, mechanical and rheological properties of the corresponding polymer. Furthermore, any copolymers can have a lasting effect on the properties of the polymer. At higher molecular weight, the glass transition temperatures and the melting temperatures of the polymer material, as well as its tensile strength and modulus of elasticity increase. The elongation at break as a value on the flexibility of the polymer, however, decreases with increasing molecular weight.

Other cyclic monomers, such as lactams, such as caprolactam, can be polymerized by ring-opening polymerization to form polyamides (PA). Similarly, lactols or thiolactones can be converted to corresponding polymers by means of ring-opening polymerization reactions.

One of the objectives in the polymerization of monomers is to achieve as narrow as possible a molecular weight distribution, ie a polydispersity close to 1, in order to ensure the most homogeneous molecular weight distribution of the polymer and the associated properties. The object of the present invention is to provide a process for the polymerization of cyclic monomers, with which polymers having an optimized polydispersity are obtained.

Moreover, it is the object of the present invention to provide a process for the preparation of suitable catalysts for the catalytic ring-opening polymerization of cyclic monomers.

This problem is solved with reference to the polymerization process by a process according to claim 1. With regard to the process for the preparation of suitable catalysts, the object is achieved by a process according to claim 7.

Thus, according to the invention, a process is disclosed for the catalytic ring-opening polymerization of cyclic monomers, which is characterized in that the polymerization catalyst used is at least one compound of the group consisting of diamine-zinc complexes and polynuclear aminoethanolate-zinc complexes.

Cyclic monomers such as lactones, lactams, lactimes, lactols, lactides, thiolactones or thiolactides can be converted into corresponding polymers by means of catalytic ring-opening polymerization with the abovementioned polynuclear aminoethanolate-zinc complexes or diamine-zinc complexes.

Polynuclear in the present case is to be understood that the corresponding aminoethanolate-zinc complexes have at least three central atoms (Zin katome), preferably more than four central atoms.

Suitable polymerization catalysts for use in the process according to the invention are, for example, ZnX ₂ * (R, R) -TMCDA, ZnX ₂ * (R, R) -TECDA, (RcRcRN ₁ RN) - [ZnX ₂ -DEDMC DA] (R _c, Rc, RΛ /) - [ZnX ₂ ETMCDA], (R _C, RC, R N) - [ZnX ₂ PTMCDA] ₁ [Zn (TEMCDA) X _2], [(Zn) ₆ (OCH ₂ CH ₂ ) ₂ NMe) ₄ ((HIGH ₂ CH ₂ ) ₂ NMe) ₂ ] X ₂ • H ₂ O, [MeN (CH ₂ C (CH ₂ ) ₂ O) ₂ Zn] ₆ - H ₂ O with X = Cl or Br. The polymerization catalysts according to the invention can be used in the process in a molar ratio to m cyclic monomer between 1: 5000 to 1: 50, preferably between 1: 2000 to 1: 100, more preferably between 1: 1000 and 1: 250.

The process can be carried out in a temperature range between 80 ^° C. and 250 ^° C., preferably 100 ^° C. and 200 ^° C.

In addition, the method is suitable both for bulk polymerization, ie for the catalytic conversion of the monomers in the absence of a solvent, as well as for solution polymerization in appropriate solvents.

Surprisingly, it has been found that with the process according to the invention an optimized polydispersity of the polymers obtained can be achieved. This is in a range between about 2.2 and about 1.45 and thus shows a high homogeneity of the molecular weights obtained.

With regard to the process for preparing a catalyst for the ring-opening polymerization of cyclic monomers, the invention proposes a process which is characterized in that a divalent zinc compound is selected from the group consisting of (1R, 2R) -Λ /, Λ / , Λ / ^' , Λ / ^' - tetramethylcyclohexane-1,2-diamine, (1R.2R) - Λ /, Λ /, Λ / ^' , Λ / ^' - tetraethylcyclohexane-1,2-diamine, (1R, 2R) -N, N, N ^' , N ^' - diethyldimethylcyclohexane-1,2-diamine, (1R, 2R) -Λ /, Λ /, Λ / ^' , Λ / ^' -Thethylmethylcyclohexan-1, 2-diamine, (1R, 2R) -Λ /, Λ /, Λ / ^' , Λ / ^' -Ethylthmethylcyclohexan-1, 2-diamine, (1 R.2R) - Λ /, Λ /, Λ / ^' , Λ / ^' - Pentylthmethylcyclohexan-1, 2-diamine, (NaOC ₂ H ₄ J ₂ N-CH ₃ , and / V-methyl-2,2 ^* -Bis (dimethyl) -diethanolamin is reacted.

The divalent zinc compound may be selected from the group consisting of ZnX ₂ with X = Br or Cl, R ₂ Zn with R = Me or Et, Zn (OR) ₂ with R = AlIIyI and Zn (NR ₂ ) ₂ with R = Alkyl, thorganosilyl or aryl. - A -

Embodiments of the invention will become apparent from the dependent claims and the following examples.

1 shows a general representation of the diamine-zinc invention

complex;

Fig. 2 shows the synthetic route of ZnBr ₂ (RR) -TMCDA;

Fig. 3 shows the molecular structure of ZnBr ₂ (RR) -TMCDA;

Fig. 4 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of ZnBr ₂ - (RR) -TMCDA in the crystal;

Fig. 5 shows the synthetic route of ZnBr ₂ (R ₁ R) -TECDA;

Fig. 6 shows the molecular structure of ZnBr ₂ (RR) TECDA;

Figure 7 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of ZnBr ₂ - (RR) TECDA in the crystal.

8 shows the ring-opening polymerization of lactide with diamine-zinc

complex;

Fig. 9 shows the molecular structure of ZnCl ₂ - (R ₁ R) -TMCDA;

. _[2 ZnCl -DEDMCDA] - Figure 10 shows the molecular structure of (Rc, Rc, R _N, R _N ')

Figure 11 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of (R _C R _C R _N , R _N ) - [ZnCl ₂ -DEDMCDA] in the crystal;

. _[2 ZnBr -DEDMCDA] - Figure 12 shows the molecular structure of (R RcRcR _N1 _N)

Figure 13 shows thermal deflection ellipsoids (50% probability of residence) of the molecular structure of (R _C R _C R _N , R _N ) - [ZnBr ₂ DEDMCDA] in the crystal;

Fig. 14 shows the molecular structure of (RcRcRw) - [ZnBr ₂ -ETMCDA];

Figure 15 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of {Rc, R _C R _N ) - [ZnBr ₂ -ETMCDA] in the crystal;

Fig. 16 shows the molecular structure of (RcRcR _N ) - [ZnCl ₂ -PTMCDA];

Figure 17 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of (R _C R _C R _N ) - [ZnCl ₂ -PTMCDA] in the crystal; FIG. 18 shows structural motifs of aminoethanolate-zinc according to the invention

complex;

Fig. 19 shows the synthetic route of

[(Zn) 6 (OCH ₂ CH 2) 2 NMe) ₄ ((HIGH ₂ CH 2) 2 NMe) 2] Cl ₂ ^• H ₂ O;

Fig. 20 shows molecular structure of [(Zn) 6 (OCH ₂ CH 2) 2 NMe) ₄ ((HOCH ₂ CH 2) 2 NMe) 2] Cl ₂ ^• H ₂ O;

Figure 21 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of [(Zn) ₆ (OCH ₂ CH ₂ ) ₂ NMe) ₄ ((HIGH ₂ CH ₂ ) ₂ NMe) ₂ ] CI ₂ • H ₂ O in the crystal ;

Fig. 22 shows molecular structure of [MeN (CH ₂ C (CH ₂ ) ₂ O) ₂ Zn] ₆ * H ₂ O;

Figure 23 shows the thermal deflection ellipsoids (50% probability of residence) of the molecular structure of [MeN (CH ₂ C (CH ₂ ) ₂ O) ₂ Zn] ₆ 'H ₂ O in the crystal.

Synthesis of the diamine-zinc complexes

The preparation of the diamine-zinc complexes according to the invention, as shown generally in FIG. 1, was carried out by dissolving the chiral / achiral amine and one equivalent of the corresponding zinc (II) salt (bromide, chloride, or acetate). in acetone, diethyl ether or dichloromethane or a mixture of the solvents. Preferably, neutral tetrasubstituted diamines will be used for the complexes.

After slow reduction of the solvent at room temperature, colorless crystals of each Zinksalzaddu formed ktes. The diamine-zinc complexes according to the invention described below were isolated as monocrystalline solids and their structure determined by means of single-crystal X-ray structure analysis.

The amine compounds used as starting materials are commercially available or were prepared on the basis of literature procedures (F. Larrox, EN Jacobsen, J. Org. Chem., 1994, 59, 1939, J.-C. Kizirian, N. Cabello, L. Pinchard, Cork, A. Alexakis, Tetrahedron 2005, 61, 8939, AP CoIe, V. Mahadevan, LM Mirica, X. Ottenwaelder, TDP Stack, Inorg Chem, 2005, 44, 7345, C. Strohmann, VH Gessner, Angew Chem 2007, 119, 8429-8432, Angew Chem Chem Int Ed 2007, 46, 8281-8283; G. Fraenkel, J. Gallucci, HS Rosenzweig, J. Org. Chem. 1989, 54, 681-683). Racemic and chiral compounds were synthesized analogously.

Example 1: Preparation of ZnBr ₂ (R ₅ R) -TMCDA

The preparation of (R ₁ R) -TMCDA was based on literature starting from a mixture of isomers of cyclohexanediamine. Resolution with L-tartaric acid and Eschweiler-Clark methylation gave the enantiopure (1R, 2R) -Λ /, Λ /, Λ / ', Λ /' - tetramethylcyclohexane-1,2-diamine. The enantiomeric purity determination of the chiral compounds was carried out according to the literature (C. Strohmann, VH Gessner, J. Am. Chem. Soc., 2008, 130, 11719; SC Benson, P. Cai, M. Colon, MA Haiza, M. Tokles, JK Snyder , J. Org. Chem. 1988, 53, 5335).

As shown in FIG. 2, 132 mg (0.59 mmol) of zinc (II) bromide and 100 mg (0.59 mmol) of (R ₁ R) -TMCDA were dissolved in 5 ml of acetone to prepare the zinc salt complex. After slow evaporation of the solvent at room temperature, colorless single crystals of the adduct were formed (yield: 183 mg, 46 mmol, 78%).

The product obtained showed the following N M R spectroscopic and elemental analytical properties:

¹ H-NMR: (500.1 MHz, CDCl ₃ , CDCl ₃ ): δ = 1.16-1.34 (m, 4H, CH ₂ -cyclohexyl),

1.84-1.89 (m, 2H, CH ₂ cyclohexyl), 2:01 to 2:05 (m, 2H; CH ₂ - cyclohexyl), 2:42 [s, 6H; N (CH ₃₎ _2, D1], 2.57-2.60 (m, 2H, CHN), 2.63 [s, 6H; N (CH ₃ ) ₂ , D ₂ ].

{1 H) ¹³ C-NMR (125.8 MHz, CDCl _3, CDCl _3): δ = 22.3 + 24.2 (CH ₂ cyclohexyl) 41.1 + 47.1 [N (CHs) _2, D1 and D2], (64.5 CHN).

Elemental analysis: measured: C 30.50 H 5.55 N 7.10 calculated: C 30.37 H 5.61 N 7.08

For the resulting complex, the structural data given in Tables 1 and 2 below were obtained. Table 1: List of crystallographic data of compound ZnBr ₂ - (R ₁ R) - TMCDA

Table 2: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² x 10 ³ ) for ZnBr ₂ - (RR) -TMCDA. U (eq) is calculated as one third of the trace of the

Example 2: Preparation of ZnCl ₂ (R ₅ R) -TMCDA

In accordance with the synthetic route described in Example 1 also ZnC ^ - (RR) -TMCDA was shown, wherein as a divalent zinc compound, a corresponding amount of zinc (II) chlohd was used.

For the resulting complex, the structural data given in Table 3 below. ZeI I constant ZnCl ₂ (RR) -TMCDA:

Space group Fλ \

Cell volume: 1402.08 (9) Ä ³

Table 3: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² χ 10 ³ ) for ZnCl ₂ - (RR) -TMCDA. U (eq) is calculated as one third of the trace of the

Example 3: Preparation of ZnBr ₂ (R ₅ R) -TECDA

The preparation of (R ₁ R) -TECDA was carried out according to literature also starting from a mixture of isomers of cyclohexanediamine. Resolution with L-tartaric acid and subsequent release of the amine with aqueous KOH solution gave the enantiomerically pure (1 R, 2R) -cyclohexanediamine, which was reacted with diethyl sulfate to TECDA.

As shown in FIG. 3, 99 mg (0.44 mmol) of zinc (II) bromide and 100 mg (0.44 mmol) of (R ₁ R) -TECDA were dissolved in 5 ml of acetone to prepare the zinc salt complex. After evaporation of the solvent at room temperature, colorless needles of the monomeric compound were formed (185 mg, 0.41 mmol, 93%). The product obtained showed the following NM R spectroscopic and elemental analytical properties:

¹ H-NMR: (400.1 MHz, CDCl ₃ , CDCl ₃ ): δ = 1.19-1.31 (m, 2H, CH ₂ ), 1.27 (t, 6H,

³ JHH = 7.0 Hz; _CH3 D1), 1.27 (t, 6H, ³ J _HH = 7.0 Hz; _CH3 D2), 1:38 to 1:51 (m, 2H, CH _2), 1.81 -1.87 (m, 2H, CH _2), 2.11, -2.20 (m, 2H, CH ₂ ), 2.82-2.93 (m, 4H, CH ₂ N, D1), 2.93-2.98 (m, 2H, CHN), 3.20-3.30 (m, 4H, CH ₂ N D2).

( ¹ H) ¹³ C-NMR (100.6 MHz, CDCl ₃ , CDCl ₃ ): δ = 10.7 + 12.5 (CH ₃ , D 1 + D ₂ ), 25.3 + 28.7 (CH ₂ cyclohexyl), 41.2 + 48.5 (CH ₂ N, D1 + D2), 66.6 (CHN).

Elemental analysis: measured: C 37.35 H 6.55 N 6.25

Calculated: C 37.24 H 6.70 N 6.20

The molecular structure of the resulting complex is shown in FIG. 4. Selected bond lengths (A) and angles [°] were as follows: Br (1) -Zn (1) 2.3691 (7), Br (2) -Zn (1) 2.3451 (10), Br (3) -Zn (2) 2.3682 (7), Br (4) -Zn (2) 2.3416 (10), N (1) -Zn (1) 2.087 (5), N (2) -Zn (1) 2,112 (4), N (3) -Zn (2) 2.105 (4), N (4) -Zn (2) 2.076 (4); N (1) -Zn (1) -N (2) 86.74 (18), N (1) -Zn (1) -Br (2) 117.35 (13), N (2) - Zn (1) -Br ( 2) 113.61 (14), N (1) -Zn (1) -Br (1) 107.17 (11), N (2) -Zn (1) -Br (1) 111.81 (11), Br (2) - Zn (1) -Br (1) 116.45 (3), N (4) -Zn (2) -N (3) 86.72 (16), N (4) -Zn (2) -Br (4) 120.32 (13 ), N (3) -Zn (2) -Br (4) 112.01 (13), N (4) -Zn (2) -Br (3) 105.78 (11), N (3) -Zn (2) - Br (3) 113.10 (11), Br (4) -Zn (2) -Br (3) 115.58 (3).

The measurement of the A crystal was carried out on the devices Bru ker APEX-CCD (D8 three-circuit goniometer) from Bruker Analytical X-Ray Systems and CrysAlis CCD from Oxford Diffraction Ltd. The implemented programs were used to collect and process the data. The solution of the single-crystal X-ray structure analyzes was done with the program SHELXS90 [7] with direct methods, the structure refinement with the program SHELXL97 [8]. All non- Hydrogen atoms were refined anisotropically. U _eq is defined as one third of the trace of the orthogonalized tensor U _1J . For the hydrogen atoms the standard values of the SHELXL program were used with L / _IS0 (H) = -1.2 U _eq (C) for CH ₂ , CH and CHarom and with L / _IS0 (H) = -1.5 U _eq (C) for CH ₃ . The exponent of the anisotropic excursion factor has the form: -2π ² [h ² -a ^* -2U ¹¹ + ... + 2 h ka ^* b ^* U ¹² ].

For the resulting complex, the structural data given in Tables 4 to 6 below were obtained.

Cell constants ZnBr ₂ (RR) -TECDA:

Space group:

a = 7.7904 (3) Ä b = 14.2265 (5) Ä c = 16.4885 (7) Ä ß = 102.060 (4) Ä

Cell volume: 1787.09 (12) Ä ³

Table 4: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters ((AA ²² Xx 1100 ³³ )) for ZZnnBBrr ₂₂ - ((RR ₁₁ RR)) - TECDA. U (eq) is calculated as one-third of the trace of the orthogonal UÜ tensor

X y Z U (eq)

Br (1) 12030 (1) 1105 (1) 5336 (1) 33 (1)

Br (2) 8411 (1) 2978 (1) 4271 (1) 25 (1)

Br (3) 12167 (1) 3588 (1) 376 (1) 30 (1)

Br (4) 8846 (1) 1622 (1) -734 (1) 25 (1)

C (1) 8791 (7) 320 (4) 3366 (4) 27 (2)

C (2) 8412 (6) -186 (5) 4105 (4) 22 (2)

C (3) 4514 (6) 72 (4) 3660 (3) 23 (2)

C (4) 5790 (5) 767 (4) 4184 (3) 15 (1)

C (5) 7551 (5) -75 (3) 5452 (3) 12 (1)

C (6) 6439 (6) -971 (4) 5396 (4) 19 (2)

C (7) 6694 (6) -1464 (3) 6226 (3) 21 (1)

C (8) 6226 (6) -804 (4) 6872 (3) 19 (1)

C (9) 7286 (6) 105 (4) 6940 (4) 19 (2)

C (10) 7052 (6) 602 (3) 6087 (3) 12 (1)

C (11) 9489 (5) 1642 (5) 6849 (3) 19 (1)

C (12) 10457 (6) 2577 (4) 6858 (4) 24 (2) C (13) 6679 (6) 2321 (4) 6086 (4) 16 (1)

C (14) 5799 (6) 2394 (4) 6828 (4) 25 (2)

C (15) 4451 (6) 4264 (4) -1471 (4) 26 (2)

C (16) 5897 (5) 3607 (4) -1040 (3) 17 (1)

C (17) 9081 (6) 4326 (4) -1556 (4) 26 (2)

C (18) 8373 (6) 4749 (5) -839 (4) 19 (2)

C (19) 6750 (5) 4437 (3) 308 (3) 10 (1)

C (20) 6477 (6) 5504 (4) 285 (4) 20 (2)

C (21) 5747 (6) 5834 (3) 1016 (3) 29 (2)

C (22) 6949 (6) 5546 (4) 1822 (4) 27 (2)

C (23) 7149 (6) 4487 (4) 1850 (4) 19 (2)

C (24) 7932 (5) 4142 (3) 1129 (3) 14 (1)

C (25) 6781 (5) 2454 (4) 1078 (4) 20 (2)

C (26) 6115 (6) 2247 (4) 1870 (4) 30 (2)

C (27) 9741 (5) 2879 (5) 1867 (3) 22 (2)

C (28) 10489 (6) 1899 (4) 1829 (4) 32 (2)

N (1) 7531 (5) 412 (3) 4645 (3) 12 (1)

N (2) 7969 (4) 1556 (4) 6118 (3) 12 (1)

N (3) 7394 (5) 4043 (3) -435 (3) 10 (1)

N (4) 8323 (4) 3108 (3) 1140 (3) 10 (1)

Zn (1) 9058 (1) 1595 (1) 5048 (1) 14 (1)

Zn (2) 9255 (1) 3007 (1) 52 (1) 15 (1)

Table 5: Anisotropic excursion parameters (A x 10) for ZnBr ₂ (RR) TECDA. The exponent of the anisotropic excursion factor has the form: -2ττ ² [h ² a * ² U ¹¹ + ... + 2 hka ^* b ^* U ¹² ]

I Ji 1 _l | 22 ,, 33 ,, 23 ,, 13 l | 12

Br (1) 12 (1) 50 (1) 38 (1) -4 (1) 5 (1) 4 (1)

Br (2) 31 (1) 20 (1) 25 (1) 8 (1) 5 (1) -3 (1)

Br (3) 12 (1) 42 (1) 36 (1) 1 (1) 5 (1) -6 (1)

Br (4) 23 (1) 21 (1) 28 (1) -10 (1) 3 (1) 5 (1)

C (1) 39 (3) 25 (4) 19 (4) -1 (3) 13 (3) 4 (3)

C (2) 31 (3) 21 (4) 17 (4) -1 (3) 14 (3) 9 (3)

C (3) 23 (3) 22 (4) 15 (3) 3 (3) -15 (2) 1 (2)

C (4) 12 (2) 23 (3) 7 (3) 8 (3) -2 (2) 2 (2)

C (5) 13 (2) 17 (3) 7 (3) 8 (2) 4 (2) 6 (2)

C (6) 25 (3) 12 (4) 21 (4) -7 (3) 9 (3) -2 (2)

C (7) 22 (3) 17 (3) 26 (3) 13 (3) 8 (2) -1 (2)

C (8) 20 (3) 20 (3) 17 (3) 15 (3) 5 (3) 1 (2) C (9) 24 (3) 21 (4) 15 (4) 7 (3) 10 (3) 2 (3)

C (10) 10 (2) 10 (3) 18 (3) 2 (2) 4 (2) -2 (2)

C (11) 19 (2) 24 (3) 14 (4) 1 (3) 5 (2) -7 (3)

C (12) 34 (3) 25 (4) 11 (4) 0 (3) -3 (3) -8 (3)

C (13) 22 (3) 13 (3) 14 (4) -4 (3) 6 (3) 3 (2)

C (14) 27 (3) 28 (4) 21 (4) -13 (3) 9 (3) 5 (3)

C (15) 24 (3) 26 (4) 24 (4) -6 (3) -2 (3) -2 (3)

C (16) 22 (2) 18 (3) 9 (3) -12 (3) -3 (2) -7 (2)

C (17) 30 (3) 36 (4) 17 (4) 6 (3) 16 (3) -1 (3)

C (18) 17 (3) 12 (4) 27 (5) 2 (3) 6 (3) 1 (3)

C (19) 11 (2) 8 (3) 13 (3) -7 (2) 4 (2) -4 (2)

C (20) 16 (3) 19 (4) 20 (4) -9 (3) -6 (3) 5 (3)

C (21) 29 (3) 8 (3) 49 (4) -11 (3) 5 (3) 12 (2)

C (22) 27 (3) 34 (4) 23 (4) -13 (3) 10 (3) 0 (3)

C (23) 25 (3) 26 (4) 8 (4) -4 (3) 5 (3) 5 (3)

C (24) 16 (2) 14 (3) 10 (3) -1 (2) 1 (2) 1 (2)

C (25) 15 (3) 15 (3) 31 (4) -3 (3) 4 (3) 1 (2)

C (26) 28 (3) 24 (4) 41 (5) 1 (3) 16 (3) 3 (3)

C (27) 21 (2) 29 (4) 13 (4) 6 (3) 1 (2) 3 (3)

C (28) 35 (3) 32 (4) 29 (5) 13 (3) 8 (3) 20 (3)

N (1) 12 (2) 14 (3) 9 (3) -3 (2) 1 (2) 2 (2)

N (2) 11 (2) 17 (3) 9 (3) -1 (3) 1 (2) -3 (2)

N (3) 13 (2) 8 (2) 8 (3) -4 (2) 2 (2) -6 (2)

N (4) 12 (2) 5 (3) 14 (3) 3 (2) 4 (2) -1 (2)

Zn (1) 13 (1) 17 (1) 13 (1) 1 (1) 3 (1) -2 (1)

Zn (2) 12 (1) 16 (1) 16 (1) -2 (1) 3 (1) 1 (1)

Table 6: Hydrogen Coordinates (x 10 ⁴ ) and Isotropic Displacement Parameters (A ² X 10 ³ ) for ZnBr ₂ (RR) TECDA

X y Z U (eq)

H (1A) 7684 499 2997 40

H (1B) 9455-94 306840

H (1C) 9483 885 3549 40

H (2A) 7652-734 3911 26

H (2B) 9528 -427 4441 26

H (3A) 5076-216 3242 34

H (3B) 3453 406 3384 34

H (3C) 4199 -419 4020 34

H (4A) 6015 1278 3812 18

H (4B) 5182 1052 4594 18 H (5) 8794-269 5676 14

H (6A) 5185-807 5205 23

H (6B) 6771 -1402 4983 23

H (7A) 7932-1667 6402 25

H (7B) 5940-2030 6175 25

H (8A) 6454-1123 7418 23

H (8B) 4959-653 6721 23

H (9A) 8544-38 7151 23

H (9B) 6898 531 7341 23

H (10) 5767 727 5900 15

H (11A) 10323 1121 6833 23

H (11B) 9048 1582 7368 23

H (12A) 10696 2698 6308 37

H (12B) 11567 2548 7267 37

H (12C) 9728 3084 7006 37

H (13A) 5752 2238 5580 19

H (13B) 7275 2924 6030 19

H (14A) 5049 1843 6842 37

H (14B) 5084 2966 6780 37

H (14C) 6701 2419 7341 37

H (15A) 3898 4566 -1057 39

H (15B) 3568 3904 -1859 39

H (15C) 4955 4747 -1776 39

H (16A) 5356 3122 -743 21

H (16B) 6385 3281 -1472 21

H (17A) 9631 3718 -1386 39

H (17B) 9953 4752 -1706 39

H (17C) 8113 4237 -2035 39

H (18A) 9364 5001 -419 22

H (18B) 7580 5278 -1049 22

H (19) 5574 4148 295 12

H (20A) 7612 5821 293 24

H (20B) 5657 5680 -237 24

H (21A) 5623 6527 998 35

H (21B) 4569 5557 985 35

H (22A) 6453 5760 2296 33

H (22B) 8113 5844 1866 33

H (23A) 7922 4300 2381 23

H (23B) 5987 4192 1820 23

H (24) 9075 4477 1169 17

H (25A) 7098 1847 854 24

H (25B) 5792 2719 665 24 H (26A) 7064 1969 2285 45

H (26B) 5129 1806 1744 45

H (26C) 5726 2833 2087 45

H (27A) 9272 2937 2379 26

H (27B) 10700 3344 1902 26

H (28A) 9548 1434 1794 48

H (28B) 11392 1783 2330 48

H (28C) 11011 1846 1339 48

Example 4: Preparation of (Rc, Rc R _N , R _{N '} ) - [ZnCl ₂ DEDMCDA] and (Rc Rc R _N5 R _N ) - [ZnBr ₂ DEDMCDA]

In an analogous manner to Examples 1 to 3, the complexes _(C R _C R RN, RN) - are detailed [ZnBr ₂ DEDMCDA] - [ZnCl ₂ DEDMCDA] and (RcRcR _N1 R _N).

For the complexes obtained, the structural data given in Table 7 and 8 below were obtained.

ZeI I constant (RcRcR _N1 R _N ) - [ZnCl ₂ DEDMCDA]:

Crystal system orthorhombic space group P2 ₁ 2i2 ₁ (19)

Cell dimension [A] a = 10.2752 (11) b = 14.4299 (16) c = 21,668 (3) cell volume [A ³ ] 3212.8 (6)

Table 7: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A x 10) for (RcRcR _N1 R _N ) - [ZnCI ₂ -DEDMCDA]. U (eq) is calculated as one-third of the trace of the orthogonal UÜ tensor

X y Z U (eq)

C (1) 5462 (2) 4633 (2) 9097 (1) 36 (1)

C (2) 6529 (2) 4648 (2) 8087 (1) 35 (1)

C (3) 7488 (3) 5389 (2) 8287 (1) 50 (1)

C (4) 5128 (2) 3332 (2) 8356 (1) 27 (1)

C (5) 3769 (2) 3727 (2) 8221 (1) 37 (1)

C (6) 2860 (3) 3000 (2) 7958 (1) 45 (1)

C (7) 2745 (3) 2190 (2) 8406 (1) 44 (1)

C (8) 4087 (2) 1777 (2) 8532 (1) 34 (1)

C (9) 5030 (2) 2497 (2) 8795 (1) 26 (1)

CMO) 6839 (3) 1478 (2) 8454 (1) 41 (1) C (11) 6335 (3) 1625 (2) 9545 (1) 41 (1)

C (12) 7657 (3) 1229 (2) 9723 (1) 55 (1)

C (13) 7759 (3) 6184 (2) 381 (1) 48 (1)

C (14) 9086 (3) 6048 (2) 1310 (2) 52 (1)

C (15) 10349 (3) 6232 (2) 960 (2) 67 (1)

C (16) 6741 (2) 6329 (2) 1419 (1) 33 (1)

C (17) 6248 (3) 5329 (2) 1382 (2) 52 (1)

C (18) 5059 (3) 5185 (2) 1790 (2) 56 (1)

C (19) 3985 (3) 5833 (2) 1590 (1) 49 (1)

C (20) 4447 (2) 6842 (2) 1646 (1) 40 (1)

C (21) 5670 (2) 7021 (2) 1262 (1) 29 (1)

C (22) 6074 (3) 8386 (2) 1946 (1) 38 (1)

C (23) 5418 (3) 8605 (2) 872 (1) 41 (1)

C (24) 5843 (3) 9624 (2) 901 (2) 63 (1)

Cl (1) 9242 (1) 3140 (1) 8342 (1) 51 (1)

Cl (2) 7967 (1) 3713 (1) 9943 (1) 52 (1)

Cl (3) 9377 (1) 8296 (1) 1856 (1) 47 (1)

Cl (4) 8624 (1) 8509 (1) 138 (1) 43 (1)

N (1) 6060 (2) 4049 (1) 8606 (1) 27 (1)

N (2) 6359 (2) 2116 (1) 8942 (1) 28 (1)

N (3) 7929 (2) 6502 (1) 1029 (1) 33 (1)

N (4) 6167 (2) 8005 (1) 1308 (1) 29 (1)

Zn (1) 7575 (1) 3274 (1) 8984 (1) 29 (1)

Zn (2) 8129 (1) 7930 (1) 1053 (1) 28 (1)

H (1A) 6142 4995 9303 53

H (1B) 5029 4233 9400 53

H (1C) 4824 5053 8912 53

H (2A) 5770 4951 7891 42

H (2B) 6949 4250 7772 42

H (3A) 7050 5830 8561 75

H (3B) 7817 5716 7923 75

H (3C) 8215 5099 8507 75

H (4) 5493 3102 7957 32

H (5A) 3393 3978 8607 44

H (5B) 3850 4245 7923 44

H (6A) 3199 2777 7557 54

H (6B) 1990 3275 7887 54

H (7A) 2169 1709 8228 52

H (7B) 2354 2406 8798 52

H (8A) 4447 1525 8143 41

H (8B) 4000 1259 8828 41

H (9) 4648 2727 9190 31

H (IOA) 7774 1374 8510 62

H (IOB) 6682 1755 8048 62

H (IOC) 6376 886 8483 62

H (11A) 5693 1114 9524 50 H (11B) 6046 2061 9870 50

H (12A) 7868 708 9451 83

H (12B) 7629 1013 10151 83

H (12C) 8323 1710 9681 83

H (13A) 7824 5507 365 72

H (13B) 8438 6459 122 72

H (13C) 6902 6378 230 72

H (14A) 8934 5371 1327 62

H (14B) 9184 6273 1739 62

H (15A) 10317 5920 559 101

H (15B) 11085 5993 1199 101

H (15C) 10454 6900 898 101

H (16) 6997 6444 1857 39

H (17A) 6021 5180 949 62

H (17B) 6949 4901 1514 62

H (18A) 4758 4535 1758 67

H (18B) 5289 5308 2226 67

H (19A) 3208 5737 1853 59

H (19B) 3740 5700 1157 59

H (20A) 3744 7261 1507 47

H (20B) 4632 6982 2085 47

H (21) 5430 6915 820 35

H (22A) 5158 8495 2049 58

H (22B) 6554 8972 1968 58

H (22C) 6448 7942 2238 58

H (23A) 4479 8563 972 49

H (23B) 5540 8372 446 49

H (24A) 5710 9861 1321 95

H (24B) 5324 9989 610 95

H (24C) 6766 9672 792 95

ZeI I constant (RcRcR _N1 R _N ) - [ZnBr ₂ DEDMCDA]:

Crystal system orthorhombic

Room group P2 ₁ 2 ₁ 2 ₁ (19)

Cell dimension [A] a = 9.9604 (15) b = 12.2299 (18) c = 13,610 (2) Cell volume [A ³ ] 1657.9 (4) Table 8: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² χ 10 ³ ) for (RcRcR _N1 R _N ) - [ZnBr ₂ -DEDMCDA]. U (eq) is calculated as one-third of the trace of the orthogonal UÜ tensor

X y Z U (eq)

Br (1) -2392 (1) 10498 (1) 2007 (1) 42 (1)

Br (2) -2597 (1) 7215 (1) 1937 (1) 47 (1)

C (1) 108 (9) 9813 (6) 3719 (5) 50 (2)

C (2) -90 (9) 7842 (6) 3867 (5) 54 (2)

C (3) -1405 (10) 7968 (7) 4425 (6) 80 (3)

C (4) 1485 (6) 8574 (5) 2651 (4) 33 (2)

C (5) 2721 (7) 8916 (7) 3259 (5) 54 (2)

C (6) 4025 (7) 8690 (7) 2704 (6) 61 (2)

C (7) 4028 (8) 9289 (7) 1740 (7) 67 (3)

C (8) 2845 (7) 8937 (7) 1127 (6) 47 (2)

C (9) 1499 (6) 9123 (5) 1646 (4) 29 (2)

C (10) 498 (7) 7650 (5) 648 (5) 43 (2)

C (11) 82 (8) 9569 (6) 228 (5) 41 (2)

C (12) -1121 (9) 9291 (7) -392 (5) 68 (3)

N (1) 155 (5) 8754 (5) 3163 (3) 32 (1)

N (2) 317 (5) 8777 (5) 1040 (3) 30 (1)

Zn -1265 (1) 8804 (1) 2043 (1) 28 (1)

H (1A) -813 9951 3940 75

H (1B) 402 10410 3290 75

H (1C) 704 9768 4291 75

H (2A) 660 7811 4344 65

H (2B) -104 7142 3502 65

H (3A) -1298 8521 4940 120

H (3B) -1649 7267 4726 120

H (3C) -2114 8195 3970 120

H (4) 1567 7770 2533 39

H (5A) 2662 9705 3414 65

H (5B) 2726 8507 3887 65

H (6A) 4799 8931 3105 74

H (6B) 4115 7895 2584 74

H (7A) 4871 9131 1383 81

H (7B) 3982 10086 1860 81

H (8A) 2937 8151 967 57

H (8B) 2851 9350 501 57

H (9) 1411 9927 1759 35

H (10A) 1144 7664 106 64

H (10B) -366 7373 410 64

H (10C) 834 7173 1172 64

H (11A) 888 9592 -197 49

H (11B) -44 10307 512 49 H (12A) -935 8628 -773 101

H (12B) -1312 9898 -841 101

H (12C) -1899 9166 34 101

Example 5: Preparation of (RcRcRN) - [ZnBr ₂ -ETMCDA] and (R _C , R _C , R _N ) - [ZnCl ₂ PTMCDA]

Analogously to Examples 1 to 3, the complexes (RcRcRw) - [Zn Br ₂ - ETMCDA] and (RcRcRN) - [ZnCl ₂ -PTMCDA] were prepared.

For the complexes obtained, the structural data given in Table 9 and 10 below were obtained.

ZeI I constant (RcRcRw) - [ZnBr ₂ ETMCDA]:

Orthorhombic Crystal System Space Group P2i2i2i (19) Cell Dimension [A] a = 8.2219 (9) b = 13.2393 (15) c = 14.1127 (16)

Cell volume [A ³ ] 1536.2 (3)

Table 9: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² χ 10 ³ ) for (RcRcRw) - [ZnBr ₂ -ETMCDA]. U (eq) is calculated as one-third of the trace of the orthogonal UÜ tensor

X y Z U (eq)

Br (1) 13180 (1) 8680 (1) 7393 (1) 50 (1)

Br (2) 11019 (1) 6809 (1) 9228 (1) 42 (1)

C (1) 10815 (4) 9133 (2) 10510 (2) 41 (1)

C (2) 12805 (3) 10057 (2) 9615 (2) 42 (1)

C (3) 9930 (3) 10312 (2) 9223 (2) 25 (1)

C (4) 9446 (3) 11087 (2) 9983 (2) 34 (1)

C (5) 6685 (3) 11265 (2) 9272 (2) 44 (1)

C (6) 7151 (3) 10521 (2) 8490 (2) 34 (1)

C (7) 8433 (3) 9764 (2) 8837 (2) 25 (1)

C (8) 9093 (4) 9450 (2) 7150 (2) 40 (1)

C (9) 7644 (4) 8174 (2) 8084 (2) 41 (1)

C (10) 7942 (5) 7361 (3) 7384 (3) 64 (1)

C (19) 8186 (4) 11829 (2) 9611 (2) 41 (1)

N (1) 11194 (3) 9572 (2) 9566 (2) 29 (1)

N (2) 8911 (3) 8991 (1) 8102 (1) 27 (1) Zn (2) 11161 (1) 8432 (1) 8551 (1) 26 (1)

H (1A) 10879 9663 10994 62

H (1B) 11601 8599 10657 62

H (1C) 9715 8848 10502 62

H (2A) 12804 10566 10119 63

H (2B) 13048 10382 9007 63

H (2C) 13634 9545 9751 63

H (3) 10421 10697 8685 30

H (4A) 8999 10729 10541 41

H (4B) 10425 11463 10190 41

H (5A) 5874 11752 9028 53

H (5B) 6190 10894 9809 53

H (6A) 7586 10898 7940 41

H (6B) 6170 10150 8279 41

H (7) 7939 9386 9378 30

H (8A) 8025 9667 6918 60

H (8B) 9554 8952 6713 60

H (8C) 9819 10036 7191 60

H (9A) 7577 7868 8723 49

H (9B) 6576 8486 7945 49

H (IOA) 7928 7646 6743 95

H (IOB) 7090 6847 7440 95

H (IOC) 9005 7053 7506 95

H (19A) 7879 12307 10120 49

H (19B) 8654 12222 9081 49

ZeI I constant (RcRcR _N ) - [ZnCl ₂ PTMCDA]:

Space group P2i (4) Cell dimension [A] a = 12.3903 (18) b = 12.8524 (19) c = 12.6936 (19) ß = 1 16.785 (2) °

Cell volume [A ³ ] 1804.5 (5)

Table 10: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² x 10 ³ ) for (RcRcR _N ) - [ZnCl ₂ -PTMCDA]. U (eq) is calculated as one third of the trace of the orthogonal UÜ tensor xyz U (eq)

C (1) 10029 (2) 5552 (2) 446 (2) 34 (1)

C (2) 9661 (2) 4816 (2) 2023 (2) 35 (1)

C (3) 10965 (2) 4929 (2) 2954 (2) 37 (1) C (4) 11149 (2) 4517 (2) 4147 (2) 37 (1)

C (5) 12416 (2) 4662 (2) 5125 (2) 40 (1)

C (6) 12532 (2) 4352 (2) 6325 (2) 46 (1)

C (7) 7947 (2) 5560 (2) 277 (2) 25 (1)

C (8) 7612 (2) 4682 (2) -633 (2) 37 (1)

C (9) 6260 (2) 4636 (2) -1450 (2) 49 (1)

C (10) 5829 (2) 5671 (2) -2070 (2) 47 (1)

C (11) 6110 (2) 6531 (2) -1164 (2) 37 (1)

C (12) 7461 (2) 6601 (2) -338 (2) 26 (1)

C (13) 6912 (2) 7569 (2) 1047 (2) 49 (1)

C (14) 7837 (3) 8479 (2) 4 (2) 52 (1)

C (15) 7168 (2) 3187 (2) 5049 (2) 34 (1)

C (16) 7837 (2) 3579 (2) 3554 (2) 30 (1)

C (17) 7211 (2) 2641 (2) 2794 (2) 34 (1)

C (18) 7596 (2) 2510 (2) 1816 (2) 35 (1)

C (19) 7025 (2) 1597 (2) 998 (2) 38 (1)

C (20) 7463 (3) 1483 (2) 75 (2) 51 (1)

C (21) 7865 (2) 4975 (2) 4883 (2) 26 (1)

C (22) 9057 (2) 4751 (2) 5990 (2) 35 (1)

C (23) 9682 (2) 5747 (2) 6622 (2) 40 (1)

C (24) 8842 (2) 6374 (2) 6946 (2) 45 (1)

C (25) 7686 (2) 6636 (2) 5849 (2) 39 (1)

C (26) 7033 (2) 5653 (2) 5187 (2) 28 (1)

C (27) 5966 (2) 6763 (2) 3400 (2) 45 (1)

C (28) 4885 (2) 6104 (2) 4435 (2) 50 (1)

Cl (1) 9439 (1) 7007 (1) 3607 (1) 35 (1)

Cl (2) 10940 (1) 7951 (1) 1706 (1) 45 (1)

Cl (3) 5384 (1) 4833 (1) 1326 (1) 40 (1)

Cl (4) 4075 (1) 3608 (1) 3272 (1) 39 (1)

N (1) 9277 (2) 5629 (1) 1087 (2) 26 (1)

N (2) 7783 (2) 7470 (1) 548 (2) 31 (1)

N (3) 7225 (2) 4002 (1) 4241 (1) 25 (1)

N (4) 5865 (2) 5878 (2) 4105 (2) 31 (1)

Zn (1) 9482 (1) 7088 (1) 1874 (1) 26 (1)

Zn (2) 5504 (1) 4520 (1) 3097 (1) 25 (1)

H (1A) 10877 5688 995 52

H (1B) 9751 6065 -193 52

H (1C) 9955 4851 115 52

H (2A) 9555 4123 1649 41

H (2B) 9126 4849 2412 41

H (3A) 11198 5672 3032 44

H (3B) 11498 4544 2698 44

H (4A) 10576 4874 4372 44

H (4B) 10951 3766 4069 44

H (5A) 12652 5401 5150 48

H (5B) 12983 4239 4948 48 H (6A) 12069 4838 6559 69

H (6B) 13385 4373 6908 69

H (6C) 12218 3646 6283 69

H (7) 7533 5410 778 30

H (8A) 8051 4785-1111 44

H (8B) 7876 4010-214 44

H (9A) 6091 4078 -2042 58

H (9B) 5818 4471-986 58

H (IOA) 4947 5642 -2587 56

H (IOB) 6237 5817 -2569 56

H (11A) 5667 6397-694 44

H (11B) 5826 7204 -1576 44

H (12) 7876 6749 -839 32

H (13A) 7234 8053 1715 74

H (13B) 6786 6886 1317 74

H (13C) 6140 7834 439 74

H (14A) 7042 8637-646 78

H (14B) 8436 8436 -300 78

H (14C) 8069 9031 598 78

H (15A) 6612 2635 4584 51

H (15B) 6881 3497 5581 51

H (15C) 7976 2892 5513 51

H (16A) 8674 3382 4111 36

H (16B) 7884 4137 3038 36

H (17A) 6324 2734 2441 40

H (17B) 7425 2007 3290 40

H (18A) 7391 3155 1339 42

H (18B) 8486 2429 2183 42

H (19A) 7209 951 1471 46

H (19B) 6136 1688 602 46

H (20A) 7280 2119 -400 76

H (20B) 7056 890-437 76

H (20C) 8338 1364 460 76

H (21) 8072 5384 4329 31

H (22A) 8889 4310 6538 42

H (22B) 9605 4360 5758 42

H (23A) 10426 5571 7345 48

H (23B) 9917 6164 6103 48

H (24A) 9250 7025 7345 54

H (24B) 8645 5971 7501 54

H (25A) 7882 7077 5320 47

H (25B) 7143 7037 6079 47

H (26) 6823 5241 5738 34

H (27A) 5238 6795 2641 67

H (27B) 6677 6664 3263 67

H (27C) 6050 7415 3832 67

H (28A) 5071 6747 4899 75 Ring-opening polymerization of lactide with diamine-zinc complexes and / or polynuclear aminoethanolate-zinc complexes

The ring-opening polymerization of lactide to polylactide was carried out according to literature procedures, as shown in FIG. 8 (Börner, S. Herres-Pawlis, U. Flörke, K. Huber, Eur. J. Inorg. Chem. 2007, 5645 B. J. Börner, U. Flunk, K. Huber, A. Döring, D. Kuckling, S. Herres-Pawlis, Chem. Eur. J. 2009, 15, 2362-2376). For the polymerization, apart from the diamine-zinc complexes, no further initiators are needed.

bulk

The lactide (25 mmol) and the catalyst (0.05 mmol) are added to a 50 ml

Balance piston weighed. The flask is purged with argon and sealed with a stopper with metal clip. The reaction mixture is adjusted to the desired

Reaction temperature heated.

After the reaction time, the residue is dissolved in 25 ml of dichloromethane and the

Polymer in 350 ml of cold ethanol with stirring. The polymer is in the

High vacuum dried at about 50 ⁰ C.

solution

The lactide (25 mmol) is weighed into a 50 ml round bottom flask. The flask is closed with a septum, purged with argon and mixed in an argon countercurrent with the absolute solvent. The reaction mixture is heated with stirring to the desired reaction temperature. When this is achieved, a solution of the catalyst (0.05 mmol) in the solvent used for the polymerization is added by means of a syringe.

Polymer in 350 ml of cold ethanol with stirring. The polymer is in the

High vacuum dried at about 50 ⁰ C.

Example 6: Ring-opening polymerization with ZnCl ₂ - (R ₅ R) -TMCDA

At a reaction time of 24 h at 150 ^° C., a polylactide with a molecular mass M _w of 38000 g / mol and a polydispersity of 1.6 is obtained in 27% yield. Example 7: Ring-opening polymerization with ZnCl ₂ (f?, F?) - DEDMCDA

At a reaction time of 24 h at 150 ⁰ C is obtained in 41% yield, a polylactide having a molecular weight M _w of 40000 g / mol and a polydispersity of 1, 5. After 48 h, the yield is 56%, the molecular weight M _w 52000 g / mol with a polydispersity of 1, 6.

Example 8: Ring-opening polymerization with ZnBr ₂ (R ₅ R) -TECDA

At a reaction time of 24 h at 150 ⁰ C 9 is obtained in 92% yield, a polylactide having a molecular mass M _w of 133000 g / mol and a polydispersity of 1,. After 48 h, the yield is 91%, the molar mass M _w 113000 g / mol with a polydispersity of 1, 9.

Table 11: Results of the catalytic ring-opening polymerisation

Synthesis of aminoethanolate-zinc complexes

The representation of the aminoethanolate-zinc complexes according to the invention, as shown as structural motifs in FIG. 18, was performed by reaction of the Sodium salts of ethanolamines with zinc (II) salts ZnX ₂ (X eg halogen, acetate, phenolate, triflate) and by reacting ethanolamines with diorganozinc compounds ZnR ₂ (R = alkyl, aryl).

It should be emphasized that aliphatic ethanolamines having different substitution patterns are preferably used for the complexes according to the invention. The amine compounds are z.T. commercially available. Racemic and chiral compounds were synthesized analogously.

The polynuclear aminotehanolate-zinc complexes according to the invention can generally be obtained by means of different synthetic routes.

a) Synthesis via R ₂ Zn

A solution consisting of the ligand (n mmol) in toluene or n-hexane (5 ml / mmol) is added under reflux to an equimolar solution of R ₂ Zn (R = Me, Et) in toluene or n-hexane (1 ml / mmol). After completion of the gas evolution, the solvent is removed in vacuo and the product can be isolated as a colorless solid. Colorless crystals suitable for X-ray structure analysis could be obtained by recrystallization from n-hexane in air.

b) Synthesis via ZnCl ₂

A Nathum-methanolate solution prepared by reacting sodium (2n mmol) with methanol was added dropwise with the ligand (n mmol). This solution was refluxed for 1 h before the methanol was removed in vacuo. The resulting colorless solid is taken up in THF and added dropwise to a solution of anhydrous zinc dichloride (n mmol) in THF (2 ml / mmol). After 12 h stirring at room temperature the THF, the remaining solid with CH ₂ Cl ₂ was distilled off in vacuo, and NaCl through diatomaceous earth (Celite 535 ^®) was filtered off. The now clear filtrate was concentrated to dryness in vacuo and the product can be isolated as a colorless solid. Colorless crystals suitable for X-ray structure analysis could be obtained by recrystallization from a 3/2 mixture of CH ₂ Cl ₂ and n-hexane in air. c) Synthesis via Zn (OR) ₂ (R = alkyl)

Equimolar amounts of the zinc dialcoholate and the N-organodiethanolamine are dissolved in toluene and the reaction mixture is refluxed for 30 minutes. Subsequently, the alcohol formed and the toluene are distilled off in vacuo. The product is obtained as a colorless solid.

d) Synthesis via Zn (NR ₂ J ₂ (R = alkyl, triorganosilyl, aryl)

Equimolar amounts of the zinc diamine and N-organodiethanolamine are dissolved in toluene and the reaction mixture is refluxed for 30 minutes. Subsequently, the volatile components are distilled off in vacuo. The product is obtained as a colorless solid.

Example 9: Preparation of [(Zn) ₆ (OCH ₂ CH ₂ ) ₂ NMe) 4 ((HIGH ₂ CH ₂ ) ₂ NMe) ₂ ] Cl ₂ • H ₂ O

The reaction provided this compound as a colorless powder that is well soluble in organic polar solvents such as CH ₂ Cb.

A Nathum-methanolate solution prepared by a reaction of sodium (1.69 g, 73.36 mmol) with methanol (100 mL) was added dropwise with N-methyldiethanolamine (4.21 mL, 36.68 mmol). This solution was heated at reflux for 1 h. Subsequently, the methanol was distilled off in vacuo, the colorless solid obtained was taken up in THF (100 ml) and added dropwise to a solution of anhydrous zinc dichloride (5.14 g, 36.68 mmol) in THF (25 ml). After 12 h stirring at room temperature the THF, the remaining solid with CH ₂ CI was distilled off in vacuo, added ₂ (50 ml) and NaCl on diatomaceous earth (Celite 535 ^®) was filtered off. The now clear filtrate was concentrated to dryness in vacuo. Thus, 5.8 g were (37.77 mmol, 87% d. Th.) 6-N-methyl-1, 3,2-dioxazinkocan, having a melting point of 338-341 ⁰ C (Zs.), Are obtained.

The product obtained showed the following NMR spectroscopic properties:

¹ H-NMR (300.13 MHz, CDCl ₃ ): δ (ppm) = 2.38 (s, broad signal Wi _{// 2} = 134 Hz, CH ₃ -N and CH ₂ -N, 7 H), 3.82 (s, broad Signal Wi _{/ 2} = 127 Hz, CH ₂ -O, 4H).

¹³ C ( ¹ H) NMR (75.5 MHz, CDCl ₃ ): δ (ppm) = 42.8 (s, N-Me), 48.8 (s, N-Me), 55.6 (s, CH ₂ -N), 60.0 (wide signal Wi _{/ 2} = 250 Hz, CH ₂ -O), 62.3 (s), 63.6 (s), 64.7 (s). Melting point 338 ° C-341 ° C (Zs.)

Crystals suitable for single-crystal X-ray diffraction analysis (Figure 21) could be obtained from CH ₂ Cb and n-hexane by slow evaporation of the solvent. Elemental analysis of these crystals indicates that these with [(Zn) 6 (OCH2CH2) 2NMe) ₄ ((HOCH ₂ CH 2) 2NMe) 2] Cl2 ^• H ₂ O correspond (C: 30.4%, H 5.1%, N 7.1%) ,

The compound crystallizes triklin in space group P1 with four molecules per unit cell. Also included are two molecules of water per unit cell. This compound is a hexanuclear zinc cluster that is formally a hexamer of zinc cocaine. This consists of a

Zinc-oxane four-membered ring Zn2A-O4A-Zn2-O4, where each of the two zinc atoms in it is coordinated by two other zinc cocans. Thus, the zinc atoms Zn (2) and Zn (2A) are distorted octahedrally in the above-mentioned four-membered ring. The remaining four zinc atoms of the cluster are distorted trigonal bipyramidally coordinated. Each of the six zinc atoms contained carries an N-methyldiethanolamine as a ligand. Also, two chloride ions Cl (1) and CI (IA) are contained in the compound. These form the counterions to the doubly positively charged cluster.

For the resulting complex, the structural data given in Tables 11 and 12 below were obtained.

Table 11: Selected bond lengths (A) in [(Zn) 6 (OCH2CH2) 2NMe) ₄ ((HIGH ₂ CH2) 2NMe) 2] Cl2 ^• H ₂ O

Zn (2) -O (4) 2.2813 (1) Zn (2) -Zn (3A) 3.1301 (1)

Zn (3) -O (4A) 2.0700 (1) Zn (3) -Zn (3A) 2.2149 (1)

Zn (3) -O (5A) 1.9781 (1) Zn (2) -Zn (3) 3.1498 (1)

Zn (2) -O (5) 2.0179 (1) Zn (I) -N (I) 2.2702 (1)

Zn (2) -O (2) 2.0063 (1) Zn (I) -CI (I) 2.2649 (1)

Zn (1) -O (2) 1.9895 (1) CI (1) -H (2L) 2.4403 (1)

Zn (I) -O (I) 2.1233 (1) O (3) -H (2L) 3.1929 (1)

Zn (3) -O (1) 1.9852 (1) O (3) -H (1L) 2.2125 (1)

Zn (3) -O (6A) 2.0238 (1) CI (1) -H (1L) 3.1632 (1)

Zn (2) -O (1) 2.3806 (1) Zn (1) -O (3) 2.0384 (1)

Zn (2) -O (4A) 2.0356 (1) Zn (1) Zn (2) 3.2406 (1) Zn (2) -N (2) 2.1761 (1)

Single-crystal X-ray diffraction analysis was performed on a Bruker AXS SMART CCD device with Mo-K _α radiation (0.71073 A) at 173 (1) K. To solve the structures, the direct method SHELXS97 ^{[4] followed} by successive differential Fourier synthesis was used. For refinement, the least squares method SHELXL97 ^{[5] was used} . Atom scattering factors for neutral atoms and real and imaginary parts of the dispersion were taken from the International Tables for X-Ray Crystallography ^[6] . The pictures were created with the program SHELXTlJ ⁷¹ and Diamond 3.0.

Table 12: List of the crystallographic data of the compound [(Zn) 6 (OCH2CH2) 2NMe) ₄ ((HOCH ₂ CH 2) 2NMe) 2] Cl2 ^• H ₂ O

[(Zn) ₆ (OCH ₂ CH ₂ ) ₂ NMe) ₄ ((HIGH ₂ CH ₂ ) ₂ NMe) ₂ ] Cl2

- H ₂ O

Molecular formula C ₃₀ H ₆₆ N ₆ O ₁₂ Cl ₂ Zn ₆ H ₂ O

Molecular weight / g / mol 1166

Crystal system triklin

Crystal size 0.15 x 0.29 x 0.32

Space group P -1 a / A 9.6846 (4) b / A 10.6787 (5) c / A 11.7943 (6) α / ° 84.9 β / ° 79.42 γ / ° 68.05

V / A ³ 1111.81 (7)

Z 1

Pberechnet / g / m ³ 1.741 μ / mm ^"1 3.36

F (OOO) 598

Θ angle / ° 2-28

-12 <h <12 h, k, I values -14 <k <13

-15 <l <15

Measured reflexes 19363

Completeness of θ _max - independent Reflexes 5283 /0.0221

Reflexes with (l> 2σ (l)) 4482 Refinement parameter 293

GooF (F ² ) 1.072 R1 (F) (l> 2σ (l)) 0.0223 wR2 (F ² ) 0.0597

Maximum / minimum

0.64 / -0.49 difference peak e / A ³

Example 10: Preparation of Vnn [MeN (CH ₂ C (CH ₂ H ₂ ) ₂ Zn] ₆ * H ₂ O

A solution of / V-methyl-2,2 ^* -bis (dimethyl) -diethanolamine (5.5 mmol, 0.96 g) in toluene (25 ml) was added at room temperature to a solution of Et ₂ Zn (5.5 mmol, 1M in n-). Hexane) in toluene (55 ml) and then heated at reflux for one hour. After removal of the solvent in vacuo, 1.30 g (5.44 mmol, 99% of theory) of 4-Λ / -methyl-2,7-bis (dimethyl) -2,8,4-dioxazazincocane were obtained as a colorless solid. Colorless crystals suitable for X-ray structure analysis could be obtained by recrystallization from n-hexane in air.

For the complex obtained, the structural data given in Table 13 below were obtained.

ZeI I constant [MeN (CH ₂ C (CH ₂ ) ₂ O) ₂ Zn] ₆ - H ₂ O:

Room group Triklin, P1

Cell dimension [A] a = 11.6421 (7) b = 11.6518 (6) c = 15.1304 (8) β = 77.604 (5) ° cell volume [A ³ ] 1684.47 (16)

Table 13: Atomic coordinates (x 10 ⁴ ) and equivalent isotropic displacement parameters (A ² x 10 ³ ) for [MeN (CH ₂ C (CHs) ₂ O) ₂ Zn] ₆ * calculated as one-third of the trace of the orthogonal UÜ tensor

U (eq)

Zn (I) 6155 (1) 137 (1) 967 (1) 13 (1)

Zn (2) 4210 (1) -424 (1) 2528 (1) 16 (1) Zn (3) 5375 (1) -2024 (1) 1105 (1) 13 (1)

0 (1) 4440 (2) -1 (2) 1141 (1) 13 (1)

0 (11) 5991 (2) -523 (2) 2390 (1) 15 (1)

0 (17) 5603 (2) 1837 (2) -111 (1) 13 (1)

0 (21) 2769 (2) 796 (2) 3131 (1) 24 (1)

0 (27) 2539 (2) 3329 (2) 2564 (2) 33 (1)

0 (31) 4667 (2) -2300 (2) 2470 (1) 16 (1)

0 (37) 6879 (2) -1514 (2) 442 (1) 14 (1)

N (14) 7263 (2) 1018 (2) 1324 (2) 17 (1)

N (24) 504 (2) 2878 (2) 4036 (2) 22 (1)

N (34) 7161 (2) -3988 (2) 1724 (2) 16 (1)

C (Il) 7917 (2) -1414 (3) 3231 (2) 24 (1)

C (12) 6593 (2) -173 (3) 2913 (2) 17 (1)

C (13) 6720 (3) 1093 (3) 2294 (2) 20 (1)

C (14) 8734 (2) 338 (3) 1273 (2) 27 (1)

C (15) 6766 (3) 2386 (3) 663 (2) 19 (1)

C (16) 6479 (2) 2421 (3) -290 (2) 15 (1)

C (17) 5710 (3) 230 (3) 3776 (2) 25 (1)

C (18) 5767 (3) 3917 (3) -811 (2) 22 (1)

C (19) 7699 (2) 1666 (3) -881 (2) 23 (1)

C (21) 1305 (3) -86 (3) 3044 (2) 33 (1)

C (22) 1633 (3) 645 (3) 3555 (2) 21 (1)

C (23) 450 (2) 2097 (3) 3477 (2) 22 (1)

C (24) -421 (3) 2985 (3) 4858 (2) 29 (1)

C (25) 478 (3) 4187 (3) 3515 (2) 26 (1)

C (26) 1827 (3) 4138 (3) 3219 (2) 23 (1)

C (27) 1858 (3) -123 (3) 4571 (2) 29 (1)

C (28) 2630 (3) 3570 (3) 4067 (2) 30 (1)

C (29) 1630 (3) 5570 (3) 2706 (2) 32 (1)

C (31) 5385 (3) -3208 (3) 4052 (2) 25 (1)

C (32) 5457 (3) -3508 (3) 3120 (2) 19 (1)

C (33) 6926 (2) -4024 (3) 2739 (2) 20 (1)

C (34) 7414 (3) -5291 (3) 1587 (2) 26 (1)

C (35) 8314 (2) -3720 (3) 1312 (2) 18 (1)

C (36) 8090 (2) -2695 (3) 350 (2) 16 (1)

C (37) 4955 (3) -4569 (3) 3334 (2) 26 (1)

C (38) 7979 (3) -3239 (3) -409 (2) 23 (1)

C (39) 9250 (2) -2361 (3) 79 (2) 23 (1)

H (IO) 3970 (20) 460 (30) 785 (19) 16

H (270) 2620 (30) 2580 (30) 2770 (20) 39

H (ILA) 8415 -1787 2709 35

H (IIB) 7749-2096 3713 35

H (IlC) 8414-1136 346935

H (13A) 5851 1880 2272 23

H (13B) 7287 1240 2583 23

H (14A) 9027 813 1511 40

H (14B) 9070 352 63440

H (14C) 9057-591 1640 40

H (15A) 7417 2711 567 23

H (15B) 5959 3010 943 23

H (17A) 4856 965 3590 37

H (17B) 6109 519 4097 37

H (17C) 5607 -540 4186 37

H (18A) 5613 3982 -1427 34

H (18B) 6305 4349-855 34

H (18C) 4935 4363 -478 34

H (19A) 7447 1821 -1489 34

H (19B) 8090 706-584 34

H (19C) 8330 1994 -943 34

H (21A) 2030-984 3068 49

H (21B) 1161 424 2404 49

H (21C) 519-157 3340 49

H (23A) 408 2606 2827 26

H (23B) -362 2016 3664 26 H (24A) -311 2091 5203 44

H (24B) -1312 3548 4667 44

H (24C) -250 3386 5246 44

H (25A) -14 4833 3898 31

H (25B) 0 4530 2959 31

H (27B) 2055 359 4876 44

H (27C) 2588-1021 4608 44

H (27D) 1074-195 4873 44

H (28A) 2747 2662 4374 45

H (28B) 2168 4143 4493 45

H (28C) 3481 3545 3870 45

H (29A) 1146 5892 2164 48

H (29B) 2477 5556 2517 48

H (29C) 1140 6169 3114 48

H (31A) 4498-2923 4335 38

H (31B) 5628-2494 3941 38

H (31C) 5985-4018 4463 38

H (33A) 7263-3472 2849 24

H (33B) 7433-4956 3091 24

H (34A) 8190-6019 1896 39

H (34B) 7550 -5246 931 39

H (34C) 6666 -5458 1846 39

H (35A) 9084-4575 1254 21

H (35B) 8507-3375 1737 21

H (37A) 4050 -4193 3583 38

H (37B) 5491-5371 3783 38

H (37C) 5011 -4806 2769 38

H (38A) 7932 -2601 1006 35

H (38B) 7193-3355-272 35

H (38C) 8742 -4102 -424 35

H (39A) 9133 -1722 -524 34

H (39B) 10061-3183 54 34

H (39C) 9286 -1969 535 34

Example 11: ring-opening polymerization with [(Zn) 6 (OCH2CH2) 2NMe) 4 ((HOCH ₂ CH 2) 2NMe) 2] Cl2 ^• H ₂ O

Under the conditions of the mass or solution polymerization described above was conducted at a reaction time of 24 h at 150 ⁰ C in 91% yield, a polylactide having a molecular mass M _w of 98500 g / mol and a polydispersity of 1 obtained 82nd After 48 h, the yield was 92%, the molecular weight M _w 88200 g / mol with a polydispersity of 1.85.

Claims

claims

1. A process for the catalytic ring-opening polymerization of cyclic monomers, characterized in that at least one compound of the group consisting of diamine-zinc complexes and polynuclear aminoethanolate-zinc complexes is used as the polymerization catalyst.

2. The method according to claim 1, wherein the cyclic monomer is a lactone, lactam, lactim, lactol, lactide, thiolactone or thiolactide.

3. The method according to any one of the preceding claims, wherein as a polymerization catalyst a compound of the group consisting of ZnX ₂ * (R, R) -TMCDA, ZnX ₂ ^ RR) -TECDA ₁ _(N1 RcRcR R _N) - _[2 ZnX DEDMCDA] (R _C R _C R _A z) - [Zn X ₂ ETMCDA] ₁ (Rc Rc ₁ R _N ) - [Zn X ₂ PTMCDA] ₁ [Zn (TEMCDA) X ₂ ], [(Zn) ₆ (OCH ₂ CH ₂ ) ₂ NMe) ₄ ((HIGH ₂ CH ₂ ) ₂ NMe) ₂ ] X ₂ • H ₂ O, [MeN (CH ₂ C (CH ₃ ) ₂ O) ₂ Zn] ₆ * H ₂ O with X = Cl or Br becomes.

4. The method according to any one of the preceding claims, wherein the polymerization catalyst in a molar ratio between 1: 5000 to 1: 50, preferably between 1: 2000 to 1: 100, more preferably between

1: 1000 and 1: 250 to the cyclic monomer is used.

5. The method according to any one of the preceding claims, wherein the polymerization at a temperature between 80 ⁰ C and 250 ⁰ C, preferably 100 ⁰ C and 200 ⁰ C is performed.

6. The method according to any one of the preceding claims, wherein the polymerization is carried out as a bulk polymerization or solution polymerization.

7. A process for producing a catalyst for ring-opening polymerization of cyclic monomers according to any one of claims 1 to 6, characterized in that a divalent zinc compound with a compound selected from the group consisting of (1R, 2R) -Λ /, Λ /, Λ / ^' , Λ / ^' - tetramethylcyclohexane-1,2-diamine, (1R, 2R) -Λ /, Λ /, Λ / ^' , Λ / ^' -Tetraethylcyclohexane-1,2-diamine, (1R, 2R) -Λ /, Λ /, Λ / ^' , Λ / ^' -diethyldimethylcyclohexane-1,2-diamine, (1R, 2R) - Λ /, Λ /, Λ / ^' , Λ / ^' - thymethylcyclohexane-1,2-diamine, (1R, 2R) -N, N, N ^' , N ^' - ethylthymethylcyclohexane-1,2-diamine, (1R , 2R) -N, N, N ^', ^N' - Pentyltrimethylcyclohexan-1, 2-diamine, (NaOC _{2 H} ₄₎ ₂ N-CH 3, and N-methyl \ -2, T- implemented H bis (dimethyl) -diethanolamine becomes.

8. The method according to claim 7, characterized in that the divalent zinc compound from the group consisting of ZnX ₂ with X = Br or Cl, R ₂ Zn with R = Me or Et, Zn (OR) ₂ with R = AIIyI and Zn ( NR ₂ ) ₂ with R = alkyl, thorganosilyl or aryl.

9. Use of a diamine-zinc complexes and / or a polynuclear aminoethanolate-zinc complexes for the catalytic ring-opening polymerization of cyclic monomers.

10. Use according to claim 9, wherein the cyclic monomer is a lactone, lactam, lactim, lactol, lactide, thiolactone or thiolactide.