Metal-conjugated microporous polymers

Abstract

A catalyst which can catalyze ring-addition reaction of CO.sub.2 and an alkylene oxide at 0˜180° C. under 0.1˜8.0 MPa to produce a corresponding cyclic carbonate, and the preparation thereof. The catalyst is a conjugated microporous macromolecule polymer complexed with cobalt, chromium, zinc, copper or aluminium, and by using the macromolecule catalyst complexed with different metals to catalyze the reaction of CO.sub.2 and alkylene oxide at normal temperature and normal pressure, a yield of the corresponding cyclic carbonate of 35%˜90% can be obtained. The catalyst is easy to recover and the re-use of the catalyst has no influence on the yield; additionally, the yield can reach over 90% by controlling the reaction conditions.

Claims

1. A metal-conjugated microporous polymer having one of the following structures: ##STR00009## ##STR00010## ##STR00011## ##STR00012## wherein, R.sub.1=—H, -.sup.tBu, -.sup.iBu, —NO.sub.2, —Cl, —CH.sub.2NEt.sub.2, —CH.sub.2N(Bn)Et.sub.2Br, —CH.sub.2N(CH.sub.3).sub.2CH.sub.2Ph, ##STR00013## X=—OAc or —Cl or —Br or —I or -Et or —OMe or —OEt or —OCH.sub.2CH.sub.2(OCH.sub.2CH).sub.2Cl, n represents degree of polymerization of the metal-conjugated microporous polymer and is in the range of 30˜100.

2. The metal-conjugated microporous polymer of claim 1 having a chemical structure of CMP-2-1, CMP-2-2, or CMP-2-3 as shown in claim 1.

3. The metal-conjugated microporous polymer of claim 1 having a chemical structure of CMP-2-1, CMP-3-1, CMP-4-1, or CMP-5-1 as shown in claim 1.

4. The metal-conjugated microporous polymer of claim 1 having a chemical structure of CMP-1-2 or CMP-1-3 as shown in claim 1.

5. A method for preparing the metal-conjugated microporous polymer of claim 1 wherein the metal-conjugated microporous polymer has a chemical structure of CMP-1-2, CMP-1-3, CMP-2-1, CMP-2-2, CMP-2-3, CMP-3-1, CMP-32, CMP-3-3, CMP-4-1, CMP-4-2, or CMP-4-3 as shown in claim 1, and the method comprises: synthesis of Salen: stirring a mixture solution of R.sub.1-substituted salicylaldehyde and 1,2-diaminocyclohexane with a mole ratio of 1:1˜30 in methanol or ethanol as a solvent for 3˜15 hours at 0˜150°C. to obtain a Salen compound; synthesis of Salen-M-X or Salen-M: reacting the Salen compound with a M-containing compound to obtain the Salen-M or reacting a M-X compound with the Salen compound to obtain the Salen-M-X compound; and synthesis of the metal-conjugated microporous polymer: with anhydrous toluene and triethylamine (TEA) as solvent (volume ratio=3˜4:1), CuI and tetrakis-(triphenylphosphine)palladium(0) as catalyst, a mixture solution of alkynyl benzene A and Salen-M-X or Salen-M (mole ratio=1˜4:1) is stirred under argon for 60˜90 hours at 25˜100° C., affording the metal-conjugated microporous polymer, wherein the mole ratio of CuI and alkynyl benzene A is 1:5˜10 and, the mole ratio of tetrakis-(triphenylphosphine)palladium(0) and alkynyl benzene A is 1:20˜30, M is Co, Cr, Zn, or Cu, and alkynyl benzene A is 1,3,5-triethynylbenzene, 1,4-diethynylbenzene or tetrakis(4-ethynylphenyl)methane.

6. The method of claim 5 wherein: the amount of anhydrous toluene required by each 1 mmol Salen-M-X , or Salen-M is 30˜50 ml.

7. A method for preparing the metal-conjugated microporous polymer of claim 1, wherein the metal-conjugated microporous polymer has a chemical structure of CMP-5-1, CMP-5-2, CMP-5-3 as shown in claim 1, and the method comprises: 1) synthesis of Salen: stirring a mixture solution of R1-substituted salicylaldehyde and 1,2-diaminocyclohexane with a mole ratio of 1:1˜30 in methanol or ethanol as a solvent for 1˜15 hours at 0˜150°C. to obtain a Salen compound: 2) synthesis of a conjugated microporous polymer (CMP): with anhydrous toluene and triethylamine (TEA) as solvent (volume ratio=3˜4:1), tetrakis-(triphenylphosphine)palladium(0) and CuI as catalyst, a mixture solution of alkynyl benzene A and Salen (mole ratio=1:1˜5) is stirred under argon for 60˜90 hours at 20˜150° C., affording the CMP, wherein, the mole ratio of CuI and alkynyl benzene A is 1:10˜40, and the mole ratio of or tetrakis-(triphenylphosphine)palladium(0) and alkynyl benzene A is 1:12˜50; 3) synthesis of the metal-conjugated microporous polymer: with anhydrous toluene as a solvent, a mixture solution of an aluminum compound and CMP (mass ratio=1:1˜6) is stirred for 8˜15 hours at 90˜130° C., affording the metal aluminum-conjugated microporous polymer, wherein, the aluminum compound is AlCl.sub.3, AlBr.sub.3, AlEt.sub.3, Al(OMe).sub.3, Al(OMe).sub.3, or Al(OCH.sub.2CH.sub.2(OCH.sub.2CH).sub.2Cl).sub.3, wherein alkynyl benzene A is 1,3,5-triethynylbenzene, 1,4-diethynylbenzene or tetrakis(4-ethynylphenyl)methane.

8. The method of claim 7 wherein: the mole ratio of alkynyl benzene A and Salen in step 1) is 1:1˜3; the mole ratio of tetrakis-(triphenylphosphine)palladium(0) or CuI and 1,3,5-triethynylbenzene in step 1) is 1:12˜28, and 1:10˜25 respectively; the mass ratio of aluminum compound and CMP in step 2) is 1:1˜2.5.

9. The method of claim 7 wherein: the amount of anhydrous toluene required by each 1 mmol Salen in step 1) is 20˜25 ml; and the amount of anhydrous toluene required by each 1 g CMP in step 2) is 15˜20 ml.

10. A method of making a cyclic carbonate comprising coupling CO.sub.2 and an epoxide in the presence of the metal-conjugated microporous polymer of claim 1 as a catalyst at 0˜180° C. and 0.1˜8.0 MPa CO.sub.2 pressure.

11. The method of claim 10, wherein: general procedure for the catalytic reaction of CO.sub.2 and epoxides at ambient pressure and temperature: in the presence of an amine compound, a mixture solution of the metal-conjugated microporous polymer, and the epoxide (mass ratio=1:10˜50) is stirred for 12˜72 hours at ambient pressure and temperature, affording the corresponding cyclic carbonate, wherein, the mole ratio of the amine compound and epoxide is 1:10˜100, and M is not Al.

12. The method of claim 10, wherein: general procedure for the catalytic reaction of CO.sub.2 and epoxide at a wide range of temperature and pressure: in the presence of a amine compound, a mixture solution of the metal-conjugated microporous polymer and the epoxide (mass ratio=1:10˜50) is stirred for 1˜6 hours at 50˜160° C. and 2˜8 MPa CO.sub.2 pressure, affording the corresponding cyclic carbonate, wherein, the mole ratio of the amine compound and epoxide is 1:10˜100, and M is not Al.

13. The method of claim 10, wherein: M is Al, general procedure to catalyze reaction of CO.sub.2 and the epoxide: in the presence of an amine compound, a mixture solution of the metal-conjugated microporous polymer and epoxide (mass ratio=1:1˜25) is stirred for 3˜80 hours at 0˜160° C., affording the corresponding cyclic carbonate, wherein, the mole ratio of the amine compound and epoxide is 1:5˜1000.

14. The method claim 13, wherein, the mole ratio of the amine compound and epoxide is 1:900.

15. The method of claim 12, wherein the reaction is conducted in the presence of an amine compound selected from the group consisting of quaternary ammonium salts, triethylamine (TEA), dimethylaminopyridine (DMAP), and mixtures thereof.

16. The method of claim 10, wherein the epoxide is selected from the group consisting of propylene oxide, epichlorohydrin, 2-ethyloxirane, 2-butyloxirane, 2-phenyloxirane, and mixtures thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Description of the figures is provided below:

(2) FIG. 1: .sup.1H NMR of the Salen [N,N-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane as an example] (CDCl.sub.3, measured under 400 MHz NMR equipment);

(3) FIG. 2: .sup.1H NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(4) FIG. 3: .sup.13C NMR of the 4-Methyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(5) FIG. 4: .sup.1H NMR of the 4-Choloro-[1,3]dioxolan-2-one (measured under CDCl.sub.3, 400 MHz NMR equipment);

(6) FIG. 5: .sup.13C NMR of the 4-Choloro-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(7) FIG. 6: .sup.1H NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(8) FIG. 7: .sup.13C NMR of the 4-Ethyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(9) FIG. 8: .sup.1H NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(10) FIG. 9: .sup.13C NMR of the 4-Butyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(11) FIG. 10. .sup.1H NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(12) FIG. 11: .sup.13C NMR of the 4-Phenyl-[1,3]dioxolan-2-one (CDCl.sub.3, measured under 400 MHz NMR equipment);

(13) FIG. 12: The FT-IR spectra of CMP-1-1;

(14) FIG. 13: The FT-IR spectra of CMP-1-2;

(15) FIG. 14: The FT-IR spectra of CMP-2-1;

(16) FIG. 15: The FT-IR spectra of CMP-3-1;

(17) FIG. 16: Solid-state NMR spectra for the CMP-5-1;

(18) FIG. 17: Solid-state NMR spectra for the CMP-1-1;

(19) FIG. 18: Solid-state NMR spectra for the CMP-1-2;

(20) FIG. 19: Solid-state NMR spectra for the CMP-2-1;

(21) FIG. 20: Solid-state NMR spectra for the CMP-3-1;

(22) FIG. 21: Solid-state NMR spectra for the CMP-4-1.

DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS

(23) The invention is not limited by the embodiments described above which are presented as examples only but can be modified in various ways within the scope of protection defined by the appended patent claims.

(24) The technological invention embodiment is not limited in the specific examples below, including the any combination of these detailed implementation programs.

EXAMPLE 1

(25) 1. Synthesis of Salen-Co: A solution of Co(OAc).sub.2 (1 mmol) in CH.sub.3OH (10 ml) was added to a solution of the Salen (0.75 mmol) in 10 mL anhydrous toluene (10 ml) via a syringe. The reaction mixture was refluxed for 5 hours at 80° C., yielding the target Salen-Co;

(26) 2. Synthesis of Salen-Co—OAc: The acetic acid (6.5 mmol) was added to a solution of the Salen-Co (0.65 mmol) in toluene (6 ml) and CH.sub.2Cl.sub.2 (18 ml) via a syringe under argon. The mixture was stirred for 5 hours at 25° C., yielding the target Salen-Co—OAc, and its NMR spectrum was shown in FIG. 2.

(27) 3. Synthesis of CMP-1-1: Salen-Co—OAc (0.45 mmol), 1,3,5-triethynylbenzene (1.35 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). Then the reaction mixture was refluxed at 85° C. for 72 hours. After post-processing, CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG. 17, respectively.

(28) 4. Catalyzing for the coupling reaction of CO.sub.2 and epoxides:

(29) 1) A mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours at ambient pressure and temperature, and the yield of the propylene carbonate is 87.5%;

(30) 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 6 hours at 45° C., and the yield of the propylene carbonate is 94.5%. The .sup.1H and .sup.13C NMR for the propylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 2

(31) 1. Synthesis of Salen-Co: A solution of Co(OAc).sub.2 (1 mmol) in CH.sub.3OH (10 ml) was added to a solution of the Salen (0.6 mmol) anhydrous toluene (10 ml) via a syringe. Then the reaction mixture was refluxed for 5 hours at 80° C., yielding the target Salen-Co;

(32) 2. Synthesis of Salen-Co—OAc: The acetic acid (5 mmol) was added to a solution of the Salen-Co (0.5 mmol) in toluene (5 ml) and CH.sub.2Cl.sub.2 (15 ml) via a syringe under argon. Then the mixture was stirred for 5 hours at 25° C., yielding the target Salen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

(33) 3. Synthesis of CMP-1-1: Salen-Co—OAc (0.6 mmol), 1,3,5-triethynylbenzene (2.4 mmol), copper(I) iodide (60 mg) and tetrakis-(triphenylphosphine)palladium(0) (100 mg) were dissolved in a mixture of toluene (16 ml) and triethylamine (6 ml). Then the reaction mixture was refluxed at 85° C. for 72 hours. After post-processing, CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG. 17, respectively.

(34) 4. Catalyzing the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-1-1, 400 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours at ambient pressure and temperature, and the yield of the propylene carbonate is 80.5%; 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 4 hours at 60° C., and the yield of the propylene carbonate is 98.5%. The .sup.1H and .sup.13C NMR for the propylene carbonate were shown in FIG. 3 and FIG. 4; 3) A mixture of 100 mg CMP-1-1, 200 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at the ambient pressure and temperature, and the yield of the propylene carbonate is 56.5%; 4) With 5.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 12 hours at 30° C., and the yield of the propylene carbonate is 94.0%. The .sup.1H and .sup.13C NMR for the propylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 3

(35) 1. Synthesis of Salen-Co: A solution of Co(OAc).sub.2 (1 mmol) in CH.sub.3OH (8 ml) was added to a solution of the Salen (0.5 mmol) in 8 mL anhydrous toluene (10 ml) via a syringe. The reaction mixture was refluxed for 5 hours at 80° C., yielding the target Salen-Co;

(36) 2. Synthesis of Salen-Co—OAc: The acetic acid (9 mmol) was added to a solution of Salen-Co (0.65 mmol) in toluene (5 ml) and CH.sub.2Cl.sub.2 (15 ml) via a syringe under argon. The mixture was stirred for 6 hours at 25° C., yielding the target Salen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

(37) 3. Synthesis of CMP-1-1: Salen-Co—OAc (0.6 mmol), 1,3,5-triethynylbenzene (2.0 mmol), copper(I) iodide (50 mg) and tetrakis-(triphenylphosphine)palladium(0) (100 mg) were dissolved in a mixture of toluene (16 ml) and triethylamine (5 ml). Then the reaction mixture was refluxed at 85° C. for 72 hours. After post-processing, CMP-1-1 was obtained. The FT-IR spectra and the Solid-state NMR spectra of the CMP-1-1 were shown in FIG. 12 and FIG. 17 respectively.

(38) 4. Catalyzing the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-1, 400 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 96.5%; 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 3 hours at 70° C., and the yield of the propylene carbonate is 97%; 3) A mixture of 100 mg CMP-1, 200 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at the ambient pressure and temperature, and the yield of the propylene carbonate is 66.5%; 4) With 5.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 12 hours at 30° C., and the yield of the propylene carbonate is 94.0%; 5) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 60 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 91.5%; 6) A mixture of 100 mg CMP-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 36 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 76.5%.

EXAMPLE 4

(39) 1. Synthesis of Salen-Co: A solution of Co(OAc).sub.2 (1 mmol) in CH.sub.3OH (10 ml) was added to a solution of the Salen (0.6 mmol) in 10 ml anhydrous toluene via a syringe. The reaction mixture was refluxed for 5 hours at 80° C., yielding the target Salen-Co.

(40) 2. Synthesis of Salen-Co—OAc: The acetic acid (5 mmol) was added to a solution of the Salen-Co (0.5 mmol) in toluene (5 ml) and CH.sub.2Cl.sub.2 (15 ml) via a syringe under argon. The mixture was stirred for 5 hours at 25° C., yielding the target Salen-Co—OAc, and the NMR spectrum was shown in FIG. 2.

(41) 3. Synthesis of CMP-1-2: Salen-Co—OAc (0.6 mmol), 1,4-diacetylenebenzene (1.2 mmol), copper(I) iodide (50 mg) and tetrakis-(triphenylphosphine)palladium(0) (90 mg) were dissolved in a mixture of toluene (16 ml) and triethylamine (6 ml). Then the reaction mixture was refluxed at 85° C. for 72 hours. After post-processing, CMP-1-2 was obtained. The FT-IR spectra and the Solid-state NMR spectra of the CMP-1-2 were shown in FIG. 13 and FIG. 18, respectively.

(42) 4. Catalyzing for the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 66.5%; 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 2 hours at 90° C., and the yield of the propylene carbonate is 85.9%; 3) With 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide in the mixture, the reaction mixture was stirred for 24 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 52.5%; 4) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 2 hours at 110° C., and the yield of the propylene carbonate is 91.1%; 5) With 4.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-1-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 1 hour at 120° C., and the yield of the propylene carbonate is 64.2%. The .sup.1H and .sup.13C NMR spectrums for the propylene carbonate were shown in FIG. 3 and FIG. 4.

EXAMPLE 5

(43) 1. Synthesis of Salen-Cr—Cl: The chromium (II) chloride (0.8 mmol) and Salen (N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.6 mmol) were dissolved in dried THF (12 mL). The mixture was stirred under argon at 25 oC for 24 hours and for another 24 hours in the air. After that the compound Salen-Cr—Cl was obtained.

(44) 2. Synthesis of CMP-2: 1) Synthesis of CMP-2-1: Salen-Cr—Cl (0.4 mmol), 1,3,5-triethynylbenzene (1.2 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (12 ml) and triethylamine (4 ml). The reaction mixture was refluxed at 80° C. for 72 hours, yielding the needed compound CMP-2-1. The FT-IR spectra and the Solid-state NMR spectra of the CMP-2-1 were shown in FIG. 14 and FIG. 19, respectively; 2) Synthesis of CMP-2-2: Salen-Cr—Cl (0.45 mmol), 1,4-diethynylbenzene (1.35 mmol), copper(I) iodide (30 mg) and tetrakis-(triphenylphosphine)palladium(0) (60 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). The reaction mixture was refluxed at 80° C. for 72 hours, yielding the needed compound CMP-2-2; 3) Synthesis of CMP-2-3: Salen-Cr—Cl (0.4 mmol), tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). The reaction mixture was refluxed at 85° C. for 72 hours, yielding the needed compound CMP-2-3.

(45) 3. Catalyzing for the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-2-1, 500 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 67.7%; 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and the yield of the propylene carbonate is 98.5%. The NMR spectrums for the product were shown in FIG. 2 and FIG. 3; 3) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-1, 600 mg TBAB and 1.96 ml epichlorohydrin was stirred for 1 hour at 100° C., and the yield of the corresponding cyclic carbonate is 99.1%. The NMR spectrums for the product were shown in FIG. 4 and FIG. 5; 4) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-1, 600 mg TBAB and 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 96.0%. The NMR spectrums for the product were shown in FIG. 6 and FIG. 7; 5) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-1, 600 mg TBAB and 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 96.7%. The NMR spectrums for the product were shown in FIG. 8 and FIG. 9; 6) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-1, 600 mg TBAB and 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 96.3%. The NMR spectrums for the product were shown in FIG. 10 and FIG. 11; 7) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-2-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 86.5%.

EXAMPLE 6

(46) 1. Synthesis of Salen-Zn: The Et.sub.2Zn (0.4 ml, 1.0 M in hexane) and Salen (N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane (0.4 mmol) and were dissolved in dried THF (20 ml). The mixture was stirred under argon at 25° C. for 24 hours. After that the compound Salen-Zn was obtained.

(47) 2. Synthesis of CMP-3: 1) Synthesis of CMP-3-1: Salen-Zn (0.35 mmol), 1,3,5-triethynylbenzene (1.05 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in a mixture of toluene (12 ml) and triethylamine (4 ml). The reaction mixture was refluxed at 85° C. for 72 hours, yielding the needed compound CMP-3-1. The FT-IR spectra and the Solid-state NMR spectra of the CMP-3-1 were shown in FIG. 15 and FIG. 20, respectively. 2) Synthesis of CMP-3-2: Salen-Zn (0.4 mmol), 1,4-diethynylbenzene (1.2 mmol), copper(I) iodide (35 mg) and tetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). The reaction mixture was refluxed at 85° C. for 72 hours, yielding the needed compound CMP-3-2. 3) Synthesis of CMP-3-3: Salen-Zn (0.4 mmol), tetrakis(4-ethynylphenyl)methane (1.2 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (12 ml) and triethylamine (4 ml). The reaction mixture was refluxed at 85° C. for 72 hours, yielding the needed compound CMP-3-3.

(48) 3. Catalyzing the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-3-1, 500 mg TBAB and 1.75 ml propylene oxide was stirred 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 85.1%; 2) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and the yield of the propylene carbonate is 95.2%; 3) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-1, 600 mg TBAB and 1.96 ml epichlorohydrin was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 99.6%; 4) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-1, 600mg TBAB and 2.146 ml 1,2-epoxybutane was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 96.5%; 5) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-1, 600 mg TBAB and 3.01 ml 1,2-epoxyhexane was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 98.3%; 6) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-1, 600 mg TBAB and 2.85 ml styrene oxide was stirred for 2 hours at 100° C., and the yield of the corresponding cyclic carbonate is 96.6%; 7) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-3-2, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 1 hour at 100° C., and the yield of the corresponding cyclic carbonate is 88.7%.

EXAMPLE 7

(49) 1. Synthesis of Salen-Cu: The Cu(OAc).sub.2 (0.5 mmol) and Salen (N′N′-bis(3-tert-butyl-5-bromo-salicylidene)-1,2-diaminocyclohexane, 0.5 mmol) and were dissolved in dried ethanol (20 mL). The mixture was stirred at 80° C. for 24 hours. After that the compound Salen-Cu was obtained.

(50) 2. Synthesis of CMP-4: 1) Synthesis of CMP-4-1: Salen-Cu (0.46 mmol), 1,3,5-triethynylbenzene (1.32 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). The reaction mixture was refluxed at 80° C. for 72 hours, yielding the needed compound CMP-4-1. The Solid-state NMR spectra of the CMP-4-1 were shown in FIG. 21. 2) Synthesis of CMP-4-2: Salen-Cu (0.4 mmol), 1,4-diethynylbenzene (1.2 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (70 mg) were dissolved in a mixture of toluene (12 ml) and triethylamine (4 ml). The reaction mixture was refluxed at 80° C. for 72 hours, yielding the needed compound CMP-4-2. 3) Synthesis of CMP-4-3: Salen-Cu (0.45 mmol), tetrakis(4-ethynylphenyl)methane (1.35 mmol), copper(I) iodide (40 mg) and tetrakis-(triphenylphosphine)palladium(0) (80 mg) were dissolved in a mixture of toluene (15 ml) and triethylamine (5 ml). The reaction mixture was refluxed at 85° C. for 72 hours, yielding the needed compound CMP-4-3.

(51) 3. Catalyzing for the coupling reaction of CO.sub.2 and epoxides: 1) A mixture of 100 mg CMP-4-1, 400 mg TBAB and 1.75 ml propylene oxide was stirred for 72 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 58.5%; 2) A mixture of 100 mg CMP-4-1, 500 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 51.3%; 3) A mixture of 100 mg CMP-4-1, 200 mg TBAB and 1.75 ml propylene oxide was stirred for 48 hours in CO.sub.2 at ambient pressure and temperature, and the yield of the propylene carbonate is 42.7%; 4) With 3.0 MPa CO.sub.2 introduced, a mixture of 100 mg CMP-4-1, 600 mg TBAB and 1.75 ml propylene oxide was stirred for 2 hours at 100° C., and the yield of the propylene carbonate is 52.7%.

EXAMPLE 8

(52) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with methanol as solvent, a mixture of salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 40° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and AlEt.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 2 hours, the yield of the propylene carbonate is 30%.

EXAMPLE 9

(53) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with methanol as solvent, a mixture of salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 40° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and AlCl.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-Al. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 5 hours, the yield of the propylene carbonate is 39.8%.

EXAMPLE 10

(54) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with propanol as solvent, a mixture of .sup.tBu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 50° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and AlBr.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-Al. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 10 hours, the yield of the propylene carbonate is 52.1%.

EXAMPLE 11

(55) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with methanol as solvent, a mixture of Cl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and AlEt.sub.3 (20 mg) was stirred and refluxed at 140° C. for 8 hours, yielding the target catalyst CMP-5-1; 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 20 hours, the yield of the propylene carbonate is 63.4%.

EXAMPLE 12

(56) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with methanol as solvent, a mixture of Cl-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and AlCl.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1; 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 10° C. for 6 hours, the yield of the propylene carbonate is 40.3%.

EXAMPLE 13

(57) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with methanol as solvent, a mixture of NO.sub.2-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 50° C. for 10 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (100 mg) and AlEt.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst CMP-5-1; 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 5 hours, the yield of the propylene carbonate is 53.5%.

EXAMPLE 14

(58) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with i-propanol as solvent, a mixture of .sup.iBu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (100 mg) and AlBr.sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-5-1. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 10 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 15° C. for 20 hours, the yield of the propylene carbonate is 83.7%.

EXAMPLE 15

(59) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with i-propanol as solvent, a mixture of .sup.iBu-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 70° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and Al(OEt).sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst CMP-5-1. 4) Catalyzation for the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 30 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:10) was stirred at 0° C. for 5 hours, the yield of the propylene carbonate is 68.2%.

EXAMPLE 16

(60) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with hexanol as solvent, a mixture of CH.sub.2N(CH.sub.3).sub.2CH.sub.2Ph-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 80° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and Al(OMe).sub.3 (20 mg) was stirred and refluxed at 90° C. for 8 hours, yielding the target catalyst compound CMP-Al. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 30 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5) was stirred at 0° C. for 13 hours, the yield of the propylene carbonate is 89.6%.

EXAMPLE 17

(61) Synthesis of CMP-5-1 and its catalyzation for the coupling reaction of CO.sub.2 and epoxides: 1) Synthesis of Salen: with butanol as solvent, a mixture of CH.sub.2N(Bn)Et.sub.2Br-substituted salicylaldehyde (6.0 mmol) and 1,2-diaminocyclohexane (7.0 mmol) was stirred at 25° C. for 5 hours, yielding the Salen compound; 2) A mixture of salen (3.0 mmol), 1,3,5-triethynylbenzene (1.0 mmol), copper(I) iodide (10 mg) and tetrakis-(triphenylphosphine)palladium(0) (10 mg) was stirred at 30° C. for 60 hours, yielding the target polymer CMP; 3) A mixture of CMP (20 mg) and Al(OMe).sub.3 (20 mg) was stirred and refluxed at 100° C. for 10 hours, yielding the target catalyst CMP-5-1. 4) Catalyzing the coupling reaction of CO.sub.2 and epoxides: With sufficient CO.sub.2 introduced, a mixture of 10 mg CMP-5-1 and 30 mg propylene oxide (mole ratio of ammonium salt and propylene oxide=1:5), was stirred at 0° C. for 20 hours, the yield of the propylene carbonate is 93.5%.

(62) Using the polymers as catalysts to catalyze the coupling reaction of CO2 and epoxides, the yields of the cyclic carbonates were in the range of 35˜90%. The catalysts can be reused for several times without reducing the yields which can reach to 90% above at high pressure (2˜8 MPa) and the temperature of 50˜120 oC for 1˜3 hours. The procedure is a breakthrough for overcoming the limitation of this reaction which can only occur at high pressure and temperature catalyzed by other catalysts. Meanwhile the reuse of the catalysts can figure out the troubles caused by the low efficiency of the other catalysts.