METHOD FOR PREPARING GLUTARYL-BRIDGED BIS-BIOGENIC GUANIDINE CHELATE AND METHOD FOR PREPARING POLYBUTYLENE SUCCINATE

Abstract

A method for preparing glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2 including contacting biogenic guanidine (G) with glutaryl chloride in DMSO solvent for an acylation reaction, to yield glutaryl-bridged bis-biogenic guanidine GbG (G-b-G), and mixing the glutaryl-bridged bis-biogenic guanidine GbG as a chelating ligand and a non-toxic metal salt MX.sub.2 in an amphiphilic mixed solvent DMSO-H.sub.2O for a ligand addition reaction, to yield glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2. The biogenic guanidine (G) is selected from arginine (Arg), guanidine acetic acid (Gaa), creatine (Cra), and creatinine (Cran). M represents Fe.sup.2+, Mg.sup.2+, or Zn.sup.2+; and X represents CI.sup., AcO.sup.(CH.sub.3COO.sup.), LaO.sup.(CH.sub.3CH(OH)COO.sup.). The glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2 can be used as a catalyst for production of polybutylene succinate (PBS) using succinic anhydride (SAn) and BDO as monomers through a batch process or a continuous process. The catalyst of (GbG)MX.sub.2 of the disclosure is non-toxic, and the PBS synthesized features excellent environmental and biological safety.

Claims

1. A method for preparing glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, the method comprising: 1) contacting biogenic guanidine (G) with glutaryl chloride, to yield glutaryl-bridged bis-biogenic guanidine GbG (G-b-G), with a reaction formula as follows: ##STR00004## wherein, biogenic guanidine (G) is selected from arginine (Arg), guanidine acetic acid (Gaa), creatine (Cra), and creatinine (Cran); DMSO is dimethyl sulfoxide; operations in 1) comprise: adding DMSO to a first reactor, and adding biogenic guanidine (G) and glutaryl chloride to the first reactor, and stirring a first mixture in the first reactor under nitrogen protection; recycling DMSO from the first mixture through vacuum distillation and obtaining a resulting first solid; transferring the first solid to Buchner funnel, washing the first solid with deionized water and ethanol in sequence, removing the water and ethanol through filtration under reduced pressure, vacuum drying, to yield glutaryl-bridged bis-biogenic guanidine GbG, with a yield of 98%; 2) mixing the glutaryl-bridged bis-biogenic guanidine GbG as a chelating ligand and a non-toxic metal salt MX.sub.2 in an amphiphilic mixed solvent DMSO-H.sub.2O for a ligand addition reaction, to yield glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, with a reaction formula as follows: ##STR00005## wherein, M represents Fe.sup.2+, Mg.sup.2+, or Zn.sup.2+; and X represents CI.sup., AcO.sup.(CH.sub.3COO.sup.), LaO.sup.(CH.sub.3CH(OH)COO.sup.); operations in 2) comprise: adding the amphiphilic mixed solvent DMSO-H.sub.2O to a second reactor, and adding the glutaryl-bridged bis-biogenic guanidine GbG and the non-toxic metal salt MX.sub.2 to the second reactor, stirring a second mixture in the second reactor under nitrogen protection; recycling the amphiphilic mixed solvent from the second mixture through vacuum distillation and collecting a resulting second solid; transferring the second solid in a Buchner funnel, washing the second solid with deionized water and ethanol in turn, decompression draining to remove residual ethanol, vacuum drying, to yield glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, with a yield of 99%.

2. The method of claim 1, wherein in 1), a molar ratio of biogenic guanidine (G) to glutaryl chloride is 2:1; the first mixture is stirred in the first reactor at 25-95 C. for 4-12 hours; and in 2), a molar ratio of the glutaryl-bridged bis-biogenic guanidine GbG to the non-toxic metal salt MX.sub.2 is 1:1; the second mixture is stirred in the second reactor at 25-80 C. for 4-8 hours.

3. The method of claim 1, wherein in 2), a volume ratio of DMSO to water in the amphiphilic mixed solvent DMSO-H.sub.2O is 1:1.

4. The method of claim 1, wherein the vacuum drying in 1) and 2) is carried out at 40-60 C. for 12-24 hours.

5. A method for preparing poly(butylene succinate) (PBS) with the glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2 prepared according to the method of claim 1, poly(butylene succinate) (PBS) being prepared through a catalytic ring opening esterification-polycondensation reaction (ROE-PC) with a reaction formula as follows: ##STR00006## wherein, MHBS is monohydroxybutyl succinate, and n represent an average degree of polymerization: 1.1110.sup.3-1.510.sup.3; the method comprises a batch process or a continuous process; 1) the batch process comprises: starting a stirrer of a polymerization reactor; adding a first half of a predetermined molar quantity of 1,4-butanediol (BDO) to the polymerization reactor; evenly mixing the glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, a heat stabilizer, and succinic anhydride (SAn), and adding a resulting mixture to the polymerization reactor; adding a second half of 1,4-butanediol to the polymerization reactor; purging air in the polymerization reactor with nitrogen, and heating the polymerization reactor under atmospheric pressure and nitrogen protection to 1602 C. and holding for 90-100 min for ring opening esterification, reducing a pressure in the polymerization reactor to 800.2 kPa, continuously heating the polymerization reactor to 1702 C. and holding for 25-30 min; gradually reducing the pressure in the polymerization reactor to 500.2 kPa and holding a temperature of 1752 C. for 25-30 min for secondary esterification reaction; reducing the pressure in the polymerization reactor to 300.2 kPa and holding a temperature of 1802 C. for 25-30 min, and gradually reducing the pressure in the polymerization reactor to 100.2 kPa and holding a temperature of 2002 C. for 25-30 min for pre-polycondensation (pre-PC); reducing the pressure in the polymerization reactor to 603 Pa and holding a temperature of 2355 C. for 90-100 min for polycondensation reaction; terminating the polycondensation reaction, discharging a resulting product under nitrogen pressure, pelletizing the product under water-cooling, and drying, to yield poly(butylene succinate) (PBS); 2) the continuous process is performed with a 400 ton/year continuous device and comprises: 2.1) raw material formulating: heating and melting 1,4-butanediol (BDO), pumping the 1,4-butanediol into a raw material tank through a pneumatic pump, and then pumping the 1,4-butanediol into a slurry preparation tank through a raw material delivery pump and a flowmeter; evenly mixing the glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, a heat stabilizer, and SAn, and manually adding a resulting mixture through a feeding inlet to the slurry preparation tank; controlling a temperature in the slurry preparation tank at 602 C.; introducing prepared reaction materials in the slurry preparation tank to a slurry product tank through static pressure difference, and controlling a temperature in the slurry product tank at 602 C., a liquid level of 10%-80%; conveying the reaction materials from a top inlet into a ring opening esterification reactor through a slurry conveying pump at a conveying rate of 61.50.5 kg/h; 2.2) ring opening esterification and secondary esterification: heating the ring opening esterification reactor to 1702 C., maintaining a pressure in the ring opening esterification reactor at 800.2 kPa and a liquid level of 552% for ring opening esterification (ROE); introducing a product from the ring opening esterification reactor to a secondary esterification reactor at a delivery rate of 61.50.5 kg/h, controlling a temperature of the secondary esterification reactor at 1752 C. and a pressure of 500.2 kPa for secondary esterification reaction, a liquid level of 402%; wherein, the ring opening esterification reactor and the secondary esterification reactor share one recovery tower to absorb water produced by esterification reaction, a small amount of by-product tetrahydrofuran, and recycle unreacted BDO, and the recovery tower operates under negative pressure; 2.3) pre-polycondensation reaction: introducing a product from the secondary esterification reactor to a pre-polycondensation reactor at a delivery rate of 560.5 kg/h, controlling a temperature in an upper chamber of the pre-polycondensation reactor at 1752 C., a pressure of 300.2 kPa, and a liquid level of 352 kg, and a temperature in a lower chamber of the pre-polycondensation reactor at 2005 C., a pressure of 100.2 kPa, and a liquid level of 552 kg for pre-polycondensation reaction; 2.4) polycondensation reaction: introducing a product from the pre-polycondensation reactor to a polycondensation reactor at a delivery rate of 500.5 kg/h, controlling a temperature of the polycondensation reactor at 2355 C., a pressure of 603 kPa, and a liquid level of 302% to conduct polycondensation; introducing a product from the polycondensation reactor to a pelletizing section at a delivery rate of 500.5 kg/h, pelletizing under water-cooling conditions, and drying, to yield poly(butylene succinate) (PBS) products.

6. The method of claim 5, wherein a molar ratio of the BDO to the SAn is between 1.05:1 and 1.17:1.

7. The method of claim 5, wherein a molar amount of (GbG)MX.sub.2 accounts for 610.sup.5-1.310.sup.4 of that of the SAn.

8. The method of claim 5, wherein the heat stabilizer is titanium phosphate (TP), and a molar amount of titanium phosphate accounts for 810.sup.5-1.710.sup.4 of that of the SAn.

9. The method of claim 5, wherein the poly(butylene succinate) (PBS) products have a weight average molecular weight Mw 1.910.sup.5-2.610.sup.5, a molecular weight distribution index PDI 1.68-1.82; a melting point MP 115-117 C., and a thermal decomposition temperature Td.sub.10 387-391 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] The invention is described hereinbelow with reference to accompanying drawings, in which the sole FIGURE is a process flow diagram of a 400 tons/year PBS continuous production device.

DETAILED DESCRIPTION

[0044] To further illustrate the disclosure, embodiments detailing a method for preparing glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2 are described below. It should be noted that the following embodiments are intended to describe and not to limit the disclosure.

Example 1

Preparation of Bridged Bis-Biogenic Guanidine Chelate (Arg-b-Arg)FeCl.SUB.2

(1) Preparation of Bridged Bis-Biogenic Guanidine Arg-b-Arg

[0045] To a first reactor equipped with an electro-mechanical stirrer, thermometer, reflux condenser and nitrogen inlet, 250 mL of DMSO, 0.02 mole (3.4840 g) of Arg, and 0.01 mole (1.6901 g) of glutaralyl chloride were added. The stirrer of the first reactor was started, nitrogen was introduced to replace the air in the first reactor thoroughly, and the mixture in the first reactor was continuously stirred at 251 C. for 12 h under nitrogen protection. A solvent was distilled under reduced pressure (recycled for use), and a first solid was collected and transferred to a Buchner funnel, and washed with deionized water and ethanol in turn. After the washing solvent was removed under reduced pressure, the first solid was put into a vacuum drying box and dried under vacuum at 60 C. for 24 h, to yield 4.3773 g of a finished product of bridged bis-biogenic guanidine Arg-b-Arg, with a yield of 98.5%.

(2) Preparation of Bridged Bis-Biogenic Guanidine Chelate (Arg-b-Arg)FeCl.SUB.2

[0046] 300 mL of DMSO-H.sub.2O mixed solvent (DMSO:H.sub.2O=1:1, v/v), 2.2220 g (0.005 mole) of bridged bis-biogenic guanidine Arg-b-Arg, 0.6638 g (0.005 mole) of FeCl.sub.2 were added into a second reactor, and nitrogen was introduced to replace the air in the second reactor thoroughly, and the mixture in the second reactor was continuously stirred at 251 C. for 8 h under nitrogen protection. A solvent was distilled under reduced pressure (recycled for use), and a second solid was collected and transferred to a Buchner funnel, and washed with deionized water and ethanol in turn. The second solid was drained under reduced pressure, and dried under vacuum at 60 C. for 24 h, to yield 2.8272 g of a finished product of bridged bis-biogenic guanidine chelate (Arg-b-Arg)FeCl.sub.2, with a yield of 99.0%.

Example 2

Preparation of Bridged Bis-Biogenic Guanidine Chelate (Gaa-b-Gaa)Mg(OLa).SUB.2

(1) Preparation of Bridged Bis-Biogenic Guanidine Gaa-b-Gaa

[0047] To a first reactor which was the same as that in Example 1, 0.02 mole (2.3422 g) of Gaa and 0.01 mole (1.6901 g) of glutaryl chloride were added for reaction at 451 C. for 10 h. The other reaction conditions and operations were the same as that in Example 1. 3.2626 g of a finished product of bridged bis-biogenic guanidine Gaa-b-Gaa was obtained, with a yield of 98.8%.

(2) Preparation of Bridged Bis-Biogenic Guanidine Chelate (Gaa-b-Gaa)Mg(OLa).SUB.2

[0048] To a second reactor, 0.005 mole (1.6511 g) of Gaa-b-Gaa and 0.005 mole (1.0123 g) of Mg(OLa).sub.2 were added for reaction at 401 C. for 6 h. The other reaction conditions and operations were the same as that in Example 1. 2.6393 g of a finished product of bridged bis-biogenic guanidine chelate (Gaa-b-Gaa)Mg(OLa).sub.2 was obtained, with a yield of 99.1%.

Example 3

Preparation of Bridged Bis-Biogenic Guanidine Chelate (Cra-b-Cra)Zn(0Ac).SUB.2

(1) Preparation of Bridged Bis-Biogenic Guanidine Cra-b-Cra

[0049] To a first reactor which was the same as that in Example 1, 0.02 mole (2.6226 g) of Cra and 0.01 mole (1.6901 g) of glutaryl chloride were added for reaction at 951 C. for 4 h. The other reaction conditions and operations were the same as that in Example 1. 3.5324 g of a finished product of bridged bis-biogenic guanidine Cra-b-Cra was obtained, with a yield of 98.6%.

(2) Preparation of Bridged Bis-Biogenic Guanidine Chelate (Cra-b-Cra)Zn(0Ac).SUB.2

[0050] To a second reactor, 0.005 mole (1.7913 g) of Cra-b-Cra and 0.005 mole (0.9174 g) of Zn(0Ac).sub.2 were added for reaction at 801 C. for 4 h. The other reaction conditions and operations were the same as that in Example 1. 2.6952 g of a finished product of bridged bis-biogenic guanidine chelate (Cra-b-Cra)Zn(0Ac).sub.2 was obtained, with a yield of 99.5%.

Example 4

Preparation of PBS with Bridged Bis-Biogenic Guanidine Chelate (Arg-b-Arg)FeCl.SUB.2

1. Batch Process

[0051] Reaction materials: BDO: 73.5 mol (6.624 kg, SAn: 70.0 mol (7.005 kg); catalyst (Arg-b-Arg) FeCl.sub.2: 4.210.sup.3 mole (2.3988 g); and heat stabilizer TP: 5.610.sup.3 mole (2.9315 g).

[0052] Synthesis process: starting a stirrer of a polymerization reactor; adding a first half of a predetermined molar quantity of the 1,4-butanediol (BDO) to the polymerization reactor; evenly mixing the glutaryl-bridged bis-biogenic guanidine chelate (GbG)MX.sub.2, the heat stabilizer, and SAn, and adding a resulting mixture to the polymerization reactor; adding a second half of 1,4-butanediol to the polymerization reactor; purging air in the polymerization reactor with nitrogen, and heating the polymerization reactor under atmospheric pressure and nitrogen protection to 160-2 C. and holding for 90-100 min for ring opening esterification, reducing the pressure in the polymerization reactor to 800.2 kPa, slowly heating the polymerization reactor to 1702 C. and holding for 25-30 min; gradually reducing the pressure in the polymerization reactor to 500.2 kPa and holding a temperature of 1752 C. for 25-30 min for secondary esterification reaction; reducing the pressure in the polymerization reactor to 300.2 kPa and holding a temperature of 1802 C. for 25-30 min, and gradually reducing the pressure in the polymerization reactor to 100.2 kPa and holding a temperature of 2002 C. for 25-30 min for pre-polycondensation (pre-PC); reducing the pressure in the polymerization reactor to 603 Pa and holding a temperature of 2355 C. for 90-100 min for polycondensation reaction; terminating the polycondensation reaction, discharging a resulting product under nitrogen pressure, pelletizing the product under water-cooling, and drying, to yield poly(butylene succinate) (PBS); the performance parameters of the final product: Mw 2.6110.sup.5, PDI 1.82, MP 117 C., Td.sub.10 390 C.

2. Continuous Process

[0053] Reaction materials: monomers BDO: 84 kg (932.09 mol, SAn: 80 kg (799.44 mol); BDO/SAN=1.166 (molar ratio); catalyst (Arg-b-Arg) FeCl.sub.2: 27.4152 g (4.810.sup.2 moles); heat stabilizer TP: 33.5034 g (6.410.sup.2 mole).

[0054] Synthesis process: the reaction conditions and operations follow the description in aforesaid Method 2 of Technical Solution 2, and are carried out with a 400 t/y PBS continuous production device as shown in the sole FIGURE. The specifications and models of each component in the FIGURE are shown in Table 1.

TABLE-US-00001 TABLE 1 Device Device Device Device Device Number Name Number Device Name Number Device Name Number Device Name 101- BDO raw 103- Recovery tower 105- Spray condenser 107- Spray condenser V01A material C01 E01 for E01 for tank precondensation polycondensation 101- Pneumatic 103- Esterification 105- Liquid sealing 107- Sealing tank for P01 pump V01 water collection V01 tank for V01 polycondensation tank precondensation 102- Slurry 103- Ring-opening 105- Vacuum 107- Vacuum V01 preparation P02 esterification P03 circulation pump P03 circulation pump tank product delivery for for pump precondensation polycondensation 102- Slurry 103- Secondary 105- Vacuum BDO 107- Vacuum BDO V02 product tank R21 esterification E03 cooler for E03 cooler for reactor precondensation polycondensation 102- Slurry 103- Secondary 105- Conveying pump 108- PBS conveying P01 conveying P22 esterification P02 for P02 pump pump product transfer precondensation pump product 103- Ring 105- Precondensation 107- Polycondensation R01 opening R01 reactor R01 reactor esterification reactor

[0055] The performance parameters of the final product: Mw 2.5610.sup.5, PDI 1.81, MP 117 C., Td.sub.10 391 C.

Example 5

Preparation of PBS with Bridged Bis-Biogenic Guanidine Chelate (Gaa-b-Gaa)Mg(OLa).SUB.2

1. Batch Process

[0056] Reaction materials: monomers BDO: 77.0 mole (6.939 kg, SAn: 70.0 mole (7.005 kg); catalyst (Gaa-b-Gaa)Mg(OLa).sub.2: 6.310.sup.3 mole (3.3558 g); heat stabilizer TP: 8.410.sup.3 mole (4.3973 g).

[0057] The synthesis process is the same as that in Example 4. The performance parameters of the final product: Mw 2.2810.sup.5, PDI 1.79, MP 116 C., Td.sub.10 389 C.

2. Continuous Process

[0058] Reaction materials: monomers BDO: 84 kg; SAn: 80 kg, catalyst (Gaa-b-Gaa)Mg(OLa).sub.2: 7.1910.sup.2 mole (38.2983 g); heat stabilizer TP: 9.610.sup.2 mole (50.2550 g).

[0059] Synthesis process: the reaction conditions and operations follow the description in aforesaid Method 2) of Technical Solution 2. The performance parameters of the final product: Mw 2.2010.sup.5, PDI 1.78, MP 116 C., Td.sub.10 388 C.

Example 6

Preparation of PBS with Bridged Bis-Biogenic Guanidine Chelate (Cra-b-Cra)Zn(0Ac).SUB.2

1. Batch Process

[0060] Reaction materials: monomers BDO: 81.9 mole (7.381 kg, SAn: 70.0 mole (7.005 kg); catalyst (Cra-b-Cra)Zn(0Ac).sub.2: 9.110.sup.3 mole (4.9298 g); heat stabilizer TP: 1.210.sup.2 mole (6.2819 g).

[0061] The synthesis process is the same as that in Example 4. The performance parameters of the final product: Mw 1.9810.sup.5, PDI 1.68, MP 115 C., Td.sub.10 388 C.

2. Continuous Process

[0062] Reaction materials: monomers BDO: 84 kg, SAn: 80 kg; catalyst (Cra-b-Cra)Zn(0Ac).sub.2: 1.0410.sup.1 mole (56.3410 g); heat stabilizer TP: 1.3610.sup.1 mole (71.1946 g).

[0063] Synthesis process: the reaction conditions and operations follow the description in aforesaid Method 2) of Technical Solution 2. The performance parameters of the final product: Mw 1.9610.sup.5, PDI 1.70, MP 115 C., Td.sub.10 387 C.

[0064] It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications.