CN112724384B - Method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by chain extension method - Google Patents
Method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by chain extension method Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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Abstract
The invention provides a method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by a chain extension method, which comprises the following steps: a) mixing the reaction raw materials with a catalyst for reaction to obtain a PPST oligomer; the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propylene glycol; b) mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST; the chain extender comprises a main chain extender and an auxiliary chain extender; the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride. The invention adopts the specific chain extender to carry out chain extension reaction, can effectively improve the molecular weight of the poly terephthalic acid-succinic acid-1, 3-propylene glycol ester (namely PPST), and has good product color, low acid value and low preparation cost.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing biodegradable poly (terephthalic acid) -succinic acid-1, 3-propylene glycol ester by a chain extension method.
Background
The application research and development of the biodegradable polyester material are prosperous, and common biodegradable polyester materials comprise Polycaprolactone (PCL), polyglycolic acid (PGA), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene terephthalate adipate (PBAT) and the like, and can be applied to various fields of packaging, catering, agriculture and the like. However, polyester materials obtained by direct polycondensation generally have a relatively low molecular weight, a high color difference (b value), and a high acid value. Therefore, the development of novel degradable polyester materials and the preparation of high molecular weight polyester materials have become common concerns of domestic and foreign scholars.
The polyester chain extension technology is characterized in that a chain extender is added in the melting process to react with the terminal carboxyl or terminal hydroxyl of polyester, so that the molecular weight is increased, and the chain extension purpose is achieved. The existing chain extender mainly comprises the following components: (1) the bisoxazoline chain extender is an unsaturated heterocyclic substance containing nitrogen and oxygen, can react with hydroxyl, carboxyl, amino, anhydride and the like, is mainly suitable for the chain extension process of a polymer with a carboxyl at the end, and is difficult to popularize and use on a large scale due to overhigh price; (2) the isocyanate chain extender is mainly suitable for the chain extension process of polymer materials with hydroxyl at the tail end, wherein diisocyanate is most common in the chain extension reaction of polylactic acid materials. But is easy to decompose under high temperature condition, generates toxic gas and is not suitable for expanding popularization; (3) epoxy chain extenders, because epoxy groups have higher reactivity with carboxyl and lower reactivity with hydroxyl, and the end groups of polyester are mainly hydroxyl and have fewer carboxyl, the chain extension effect is not obvious; (4) other chain extension methods, including chain extenders such as acid anhydride and acyl halide, and the like, and the branching reaction initiated by ultraviolet light and free radicals, have not made important breakthrough due to respective defects or disadvantages.
The acyl chloride chain extender has little research because of generating small molecules in the chain extension process, and mainly focuses on adipoyl chloride and adipoyl chloride aliphatic acyl chloride chain extenders, CN102604051 reports the chain extension of the adipoyl chloride and the adipoyl chloride to PBS, and although the activities of the adipoyl chloride and the adipoyl chloride are high, the adipoyl chloride and the adipoyl chloride have the following problems: firstly, a gas absorption device is needed in the chain extension process, so that the cost is high; secondly, the synthesized polyester has higher carboxyl end group content, so that the aging speed is accelerated, and the service life is shorter; thirdly, the polyester has poor color (the b value is high), and the downstream application of the product is influenced; finally, fatty acyl chlorides are too reactive to easily cross-link. Therefore, the selection of the chain extender with moderate activity, the reduction of the chain extension cost, the reduction of the acid value and the improvement of the color are inevitable trends in the development of the polyester in the future.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing biodegradable poly (1, 3-trimethylene terephthalate) -succinate by a chain extension method. The poly terephthalic acid-succinic acid-1, 3-propylene glycol ester (PPST) prepared by the invention has high molecular weight, good color, low acid value and low cost.
The invention provides a method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by a chain extension method, which comprises the following steps:
a) mixing the reaction raw materials with a catalyst for reaction to obtain a PPST oligomer;
the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propanediol;
b) mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST;
the chain extender comprises a main chain extender and an auxiliary chain extender;
the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride.
Preferably, the chain-assistant agent is 4-dimethylamino pyridine and metal salt;
the metal salt is a metal carbonate and/or a metal bicarbonate.
Preferably, the mass ratio of the 4-dimethylaminopyridine to the metal salt is 9: 1.
Preferably, the metal carbonate is selected from one or more of sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and barium carbonate;
the metal bicarbonate is selected from one or more of sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
Preferably, the mass ratio of the main chain extender to the PPST oligomer is 0.5-1.5%;
the mass ratio of the chain extender to the PPST oligomer is 1-3%.
Preferably, the catalyst is a bismuth-based composition catalyst;
the bismuth-based composition catalyst comprises bismuth chloride, cerium chloride and zinc chloride;
the mass ratio of the catalyst to the reaction raw material is 0.1-0.5%.
Preferably, the molar ratio of the bismuth chloride to the cerium chloride to the zinc chloride is (0.2-0.4) to (0.1-0.2);
the bismuth-based composition catalyst is prepared by the following method: mixing and dissolving bismuth chloride, cerium chloride, zinc chloride and 1, 3-propylene glycol to obtain a liquid bismuth composition catalyst;
the dissolving temperature is 130-150 ℃.
Preferably, in the reaction raw materials, the molar ratio of terephthalic acid to succinic acid to 1, 3-propanediol is (40-60) to (60-40) to (150-250).
Preferably, in the step a), the temperature of the reaction is 240 ℃;
the number average molecular weight of the PPST oligomer obtained in the step a) is 1.5-3 ten thousand;
in the step b), the reaction temperature is 160-230 ℃.
Preferably, in step b), the reaction is carried out in a co-rotating parallel three-screw extruder;
the length-diameter ratio of the co-rotating parallel three-screw extruder is (36-44) to 1.
The invention provides a method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by a chain extension method, which comprises the following steps: a) mixing the reaction raw materials with a catalyst for reaction to obtain a PPST oligomer; the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propylene glycol; b) mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST; the chain extender comprises a main chain extender and an auxiliary chain extender; the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride. The invention adopts the specific chain extender to carry out chain extension reaction, can effectively improve the molecular weight of the poly terephthalic acid-succinic acid-1, 3-propylene glycol ester (namely PPST), and has good product color, low acid value and low preparation cost.
Detailed Description
The invention provides a method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene succinate by a chain extension method, which comprises the following steps:
a) mixing the reaction raw materials with a catalyst for reaction to obtain a PPST oligomer;
the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propanediol;
b) mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST;
the chain extender comprises a main chain extender and an auxiliary chain extender;
the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride.
With respect to step a): and mixing the reaction raw materials with a catalyst for reaction to obtain the PPST oligomer.
In the invention, the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propanediol. In the invention, the molar ratio of the terephthalic acid to the succinic acid to the 1, 3-propanediol is preferably (40-60) to (60-40) to (150-250).
In the present invention, the catalyst is preferably a bismuth-based composition catalyst. The bismuth-based composition catalyst comprises bismuth chloride, cerium chloride and zinc chloride. In the present invention, the molar ratio of bismuth chloride, cerium chloride and zinc chloride is preferably (0.2 to 0.4): (0.1 to 0.2).
In the present invention, the bismuth-based catalyst is preferably prepared by the following method: mixing and dissolving bismuth chloride, cerium chloride, zinc chloride and 1, 3-propylene glycol to obtain the liquid bismuth composition catalyst. The mixing and dissolving specifically comprises the following steps: adding bismuth chloride, cerium chloride and zinc chloride into 1, 3-propylene glycol, stirring and heating to 130-150 ℃, mixing for 2h, and cooling to room temperature to obtain a liquid mixture. Wherein the molar ratio of the bismuth chloride to the 1, 3-propylene glycol is preferably (0.2-0.4): (10-20).
The common polyester catalysts are antimony, titanium, germanium and the like, and the antimony catalysts have low activity, large addition amount, poor product color and antimony heavy metal pollution; although the germanium catalyst has high activity and good product color, the cost is high, the addition amount is small, and the dispersion is difficult; the titanium system has low cost and high activity, but is easy to hydrolyze and has poor stability. The invention does not select a conventional catalyst, but self-prepares the bismuth composition catalyst; the acid-alcohol reaction is accelerated by utilizing the strong coordination and displacement capability of the coordination of various metal ions of bismuth, cerium and zinc. During polycondensation, hydrogen atoms in a complex formed by the intramolecular hydrogen bond action of hydroxyl hydrogen and carbonyl oxygen are replaced by a plurality of metal ions, and the metal ions with strong coordination capacity are coordinated and combined with the carbonyl oxygen, so that the electropositivity of carbonyl carbon atoms is greatly increased, the reaction speed is accelerated, the polymerization time is greatly shortened, and the color and the acid value of a product are improved.
In the invention, the reaction raw materials and the catalyst are mixed, stirred and heated to the reaction temperature, and after esterification reaction for 1-3 h, vacuum pumping is carried out, and then the reaction is continued for 2-4 h, so that the PPST oligomer is obtained. Wherein the reaction temperature is preferably 240 ℃, and the PPST oligomer is obtained through esterification and polycondensation. In the present invention, the number average molecular weight of the obtained PPST oligomer is preferably 1.5 to 3 ten thousand.
With respect to step b): and mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST.
In the invention, the chain extender comprises a main chain extender and an auxiliary chain extender. Wherein the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride. In the present invention, the mass ratio of the main chain extender to the PPST oligomer is preferably 0.5% to 1.5%.
In the present invention, the chain extender is preferably 4-dimethylaminopyridine and a metal salt. Wherein the metal salt is a metal carbonate and/or a metal bicarbonate. In the invention, the metal carbonate is preferably one or more of sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and barium carbonate; the metal bicarbonate is preferably one or more of sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and magnesium bicarbonate. In the present invention, the mass ratio of the chain extender to the PPST oligomer is preferably 1% to 3%.
In the present invention, the reaction is preferably carried out in a co-rotating parallel three-screw extruder. The length-diameter ratio of the co-rotating parallel three-screw extruder is preferably (36-44): 1, and more preferably 40: 1. In the invention, the reaction temperature is preferably 160-230 ℃.
Specifically, the PPST oligomer obtained in the step a) is added into a co-rotating parallel three-screw extruder, a main chain extender and an auxiliary chain extender are added at the temperature of 160-230 ℃, and the PPST material with high molecular weight is obtained through melt chain extension and extrusion. In the invention, the number average molecular weight of the obtained chain-extended high molecular weight PPST material is 5-8 ten thousand.
The fatty acyl chloride compound has strong and stable activityThe method has the advantages that the 2,2, 2-trichloroethoxyphosphoryl dichloride with moderate activity and strong stability is selected to react with the polyester oligomer terminal hydroxyl for chain extension, a byproduct HCl is generated in the reaction process of acyl chloride and the terminal hydroxyl, the chain extension reaction cannot be carried out in the forward and reverse reaction direction due to the existence of the byproduct HCl, and the chain extension reaction can be carried out in the forward and reverse reaction direction only if the byproduct HCl is removed, so that the high-molecular-weight polyester is obtained, and if the HCl is not removed, the thermal stability of the polyester is reduced, and the color of the polyester is also deteriorated. The chain extender is a phosphorus and chlorine compound, and the color is greatly improved after the chain extender is embedded into a main chain. On the basis, the invention selects the composition of 4-dimethylamino pyridine and metal carbonate or metal bicarbonate as a chain extender, which can react with HCl to generate stable pyridine salt and chlorinated metal salt and CO2And water, CO2And water are pumped out under vacuum at high temperature, and the pyridine salt and the metal chloride salt are remained in the product to play a role in improving the color. Thus, HCl is reacted to form stable pyridinium and metal chloride salts, which facilitate the chain extension reaction. At present, no case of chain extension of polyester by adopting 2,2, 2-trichloroethoxy phosphoryl dichloride is found, and no case of introducing a chain extender in the chain extension process of acyl chloride is found. The 4-dimethylaminopyridine and carbonate or bicarbonate composition is introduced in the chain extension process, so that a small molecular byproduct HCl generated in the chain extension reaction can be removed, the chain extension reaction is promoted to be carried out in the forward reaction direction, the acid value of the product is reduced, and the color (b value is reduced).
In addition, for chain extension reaction equipment, a conventional tackifying kettle or a double-screw extruder is not selected, but a three-screw extruder which is parallel in the same direction and is provided with three screws arranged in a straight line and rotates in the same direction, the effect of the two pairs of double screws is equivalent, the screws with the same length-diameter ratio and the three-screw structure enlarge the grinding area, the kneading effect is enhanced, the residence time is long, the plastication effect is better, and due to the existence of two meshing areas, the grinding area is multiplied, so that the dispersion is more uniform, the yield is high, the energy is saved, and the occupied area is small. Therefore, in order to realize sufficient chain extension reaction of acyl chloride and polyester, a three-screw extruder with a small length-diameter ratio (36/1-44/1) is preferably adopted, so that the chain extension effect is better.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples and comparative examples, a three-screw extruder was used for the chain extension, having a length-to-diameter ratio of 40/1 and a screw diameter of 65 mm. In the following examples, the bismuth composition catalyst was obtained by the following method: adding 0.3mol of bismuth chloride, 0.2mol of cerium chloride and 0.1mol of zinc chloride into 15mol of 1, 3-propylene glycol, stirring, heating to 150 ℃, cooling to room temperature after 2h, and obtaining the liquid catalyst. The 180-day relative biodegradation rate test standard of the chain extended PPST is GB/T19277.1.
Example 1
S1, preparation of PPST oligomer:
6.7kg of terephthalic acid, 7.0kg of succinic acid, 11.4kg of 1, 3-propanediol and 25.1g of bismuth composition catalyst are added into a reaction kettle, stirred and heated to 240 ℃, and subjected to esterification reaction for 2 hours, then vacuum pumping is carried out until the pressure reaches 100Pa, and the reaction is carried out for 1 hour, so that the PPST oligomer is obtained.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 0.8% of 2,2, 2-trichloroethoxyphosphoryl dichloride and 1.6% of a chain extender (a composition of 4-dimethylaminopyridine and magnesium carbonate, the mass ratio of the two is 9: 1) at the screw temperature of 200 ℃, and carrying out reaction, extrusion and grain cutting to obtain the chain extended PPST.
Comparative example 1
The procedure of example 1 was followed except that the catalyst was replaced with an equal amount of tetrabutyltitanate to obtain chain-extended PPST.
Example 2
S1, preparation of PPST oligomer:
adding 7.5kg of terephthalic acid, 6.5kg of succinic acid, 13.3kg of 1, 3-propanediol and 50g of bismuth composition catalyst into a reaction kettle, stirring and heating to 240 ℃, performing esterification reaction for 2 hours, then vacuumizing to 100Pa, and reacting for 1 hour to obtain the PPST oligomer.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 0.8% of 2,2, 2-trichloroethoxyphosphoryl dichloride and 1.6% of a chain extender (a composition of 4-dimethylaminopyridine and magnesium carbonate, the mass ratio of the two is 9: 1) at the same time when the temperature of a screw is 200 ℃, and carrying out reaction extrusion and granulation to obtain the chain extended PPST.
Comparative example 2
The procedure of example 2 was followed except that the catalyst was replaced with an equal amount of tetrabutyltitanate to obtain chain-extended PPST.
Example 3
S1, preparation of PPST oligomer:
adding 8.3kg of terephthalic acid, 5.9kg of succinic acid, 13.3kg of 1, 3-propanediol and 55.0g of bismuth composition catalyst into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2h, then vacuumizing to 100Pa, and carrying out reaction for 2h to obtain the PPST oligomer.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 1.5% of 2,2, 2-trichloroethoxyphosphoryl dichloride and 3% of a chain extender (a composition of 4-dimethylaminopyridine and sodium bicarbonate with the mass ratio of 9: 1) at the same time at the screw temperature of 200 ℃, and carrying out reaction, extrusion and grain cutting to obtain the chain extended PPST.
Comparative example 3
The procedure of example 3 was followed except that the catalyst was replaced with an equal amount of antimony trioxide to obtain chain-extended PPST.
Example 4
S1, preparation of PPST oligomer:
adding 8.3kg of terephthalic acid, 5.9kg of succinic acid, 19.0kg of 1, 3-propanediol and 99.6g of bismuth composition catalyst into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2h, then vacuumizing to 100Pa, and carrying out reaction for 2h to obtain the PPST oligomer.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 0.9% of 2,2, 2-trichloroethoxy phosphoryl dichloride and 1.8% of a chain extender (a composition of 4-dimethylaminopyridine and calcium carbonate, the mass ratio of the two is 9: 1) at the same time when the screw temperature is 200 ℃, and carrying out reaction, extrusion and grain cutting to obtain the chain extended PPST.
Comparative example 4
The procedure of example 4 was followed except that the catalyst was replaced with an equal amount of antimony trioxide to obtain chain-extended PPST.
Example 5
S1, preparation of PPST oligomer:
adding 10.0kg of terephthalic acid, 4.7kg of succinic acid, 15.2kg of 1, 3-propanediol and 30.0g of bismuth composition catalyst into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, then vacuumizing to 100Pa, and carrying out reaction for 3 hours to obtain the PPST oligomer.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 1% of 2,2, 2-trichloroethoxyphosphoryl dichloride and 2% of a chain extender (a composition of 4-dimethylaminopyridine and magnesium carbonate, the mass ratio of the two is 9: 1) at the same time when the screw temperature is 200 ℃, and carrying out reaction, extrusion and grain cutting to obtain the chain-extended PPST.
Comparative example 5
The preparation process of example 5 was followed, except that only 2,2, 2-trichloroethoxyphosphoryl dichloride was added in the chain extension process, and no chain extender was added, to obtain chain extended PPST.
Example 6
S1, preparation of PPST oligomer:
adding 10.0kg of terephthalic acid, 4.7kg of succinic acid, 19.0kg of 1, 3-propanediol and 168.0g of bismuth composition catalyst into a reaction kettle, stirring and heating to 240 ℃, carrying out esterification reaction for 2 hours, then vacuumizing to 100Pa, and carrying out reaction for 3 hours to obtain the PPST oligomer.
S2, preparing chain extension PPST:
adding the PPST oligomer into a three-screw extruder, adding 1.3% of 2,2, 2-trichloroethoxyphosphoryl dichloride and 2.6% of a chain extender (a composition of 4-dimethylaminopyridine and barium carbonate, the mass ratio of the two is 9: 1) at the same time at the screw temperature of 200 ℃, and carrying out reaction, extrusion and grain cutting to obtain the chain extended PPST.
Comparative example 6
The preparation process of the embodiment 6 is carried out, except that only 2,2, 2-trichloroethoxy phosphoryl dichloride is added in the chain extension process, and no chain extender is added, so as to obtain the chain extension PPST.
Comparative example 7
The procedure was as in example 6 except that the chain extension procedure replaced 2,2, 2-trichloroethoxyphosphoryl dichloride with succinyl chloride to give a chain extended PPST.
Comparative example 8
The preparation process of example 6 was followed, except that 2,2, 2-trichloroethoxyphosphoryl dichloride was replaced with succinyl chloride in the chain extension process, and no chain extender was added, to obtain chain extended PPST.
Comparative example 9
The procedure was followed as in example 6 except that the chain extension procedure replaced 2,2, 2-trichloroethoxyphosphoryl dichloride with adipoyl chloride to give a chain extended PPST.
The relevant indexes of the PPST before and after chain extension of the examples 1-6 and the comparative examples 1-9 are shown in the table 1:
TABLE 1 relevant indices of PPST before and after chain extension in examples 1-6 and comparative examples 1-9
As can be seen from the data of examples 1-2 and comparative examples 1-2 in Table 1, the b value of the PPST prepolymer is higher (color is poorer) when the catalyst is replaced by tetrabutyl titanate from a bismuth composition, the molecular weight of the PPST prepolymer is lower with the same polymerization time, but the chain extension effect is close, and the b value of the chain extension PPST prepolymer is lower than that of the PPST prepolymer, which shows that the existence of the chain extender 4-dimethylaminopyridine and carbonate or bicarbonate can improve the color of the polymer.
As can be seen from the data of examples 3-4 and comparative examples 3-4 of Table 1, the results are similar to those of the tetrabutyl titanate catalyst after the catalyst was replaced with antimony trioxide from the bismuth composition.
As can be seen from the data of example 5 and comparative example 5 in Table 1, the combination of 4-dimethylaminopyridine and magnesium carbonate as chain extension aid is not added, and the chain extension reaction is difficult to proceed in the positive reaction direction because the chain extension by-product HCl is not reacted, so that not only is the chain extension effect poor, but also the b value of the polymer is increased (color is deteriorated) and the acid value is increased due to the existence of the by-product HCl.
As can be seen from the data of example 6 and comparative example 6 of Table 1, the 4-dimethylaminopyridine and barium carbonate composition without the co-chain extender gave results similar to those of comparative example 5. As can be seen from the data of example 6 and comparative examples 7-9 in Table 1, when the chain extender 2,2, 2-trichloroethoxyphosphoryl dichloride is replaced by succinyl chloride or adipoyl chloride, the b value is increased, the molecular weight after chain extension is lower, and the acid value is higher, which indicates that the chain extension effect is not better than that of the 2,2, 2-trichloroethoxyphosphoryl dichloride, and similarly, the chain extender 4-dimethylaminopyridine and barium carbonate composition is not added, and the chain extension effect is poor even if the chain extender uses succinyl chloride.
As can be seen from all the examples and comparative example data in Table 1, all the chain-extended PPST had good biodegradability and all the chain-extended PPST met the biodegradability standard GB/T19277.1.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for preparing biodegradable poly (terephthalic acid) -1, 3-propylene glycol succinate by a chain extension method is characterized by comprising the following steps:
a) mixing the reaction raw materials with a catalyst for reaction to obtain a PPST oligomer;
the reaction raw materials are terephthalic acid, succinic acid and 1, 3-propanediol;
in the reaction raw materials, the molar ratio of terephthalic acid to succinic acid to 1, 3-propanediol is (40-60) to (60-40) to (150-250);
the catalyst is a bismuth-based composition catalyst;
the bismuth-based composition catalyst comprises bismuth chloride, cerium chloride and zinc chloride;
the molar ratio of the bismuth chloride to the cerium chloride to the zinc chloride is (0.2-0.4) to (0.1-0.2);
the bismuth-based composition catalyst is prepared by the following method: mixing and dissolving bismuth chloride, cerium chloride, zinc chloride and 1, 3-propylene glycol to obtain a liquid bismuth composition catalyst;
the dissolving temperature is 130-150 ℃;
b) mixing the PPST oligomer with a chain extender for reaction to obtain chain-extended PPST;
the chain extender comprises a main chain extender and an auxiliary chain extender;
the main chain extender is 2,2, 2-trichloroethoxy phosphoryl dichloride;
the chain extender is 4-dimethylaminopyridine and metal salt;
the metal salt is a metal carbonate and/or a metal bicarbonate;
the metal carbonate is selected from one or more of sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate and barium carbonate;
the metal bicarbonate is one or more selected from sodium bicarbonate, potassium bicarbonate, calcium bicarbonate and magnesium bicarbonate.
2. The method of claim 1, wherein the mass ratio of the 4-dimethylaminopyridine to the metal salt is 9: 1.
3. The method according to claim 1, wherein the mass ratio of the main chain extender to the PPST oligomer is 0.5% to 1.5%;
the mass ratio of the chain extender to the PPST oligomer is 1-3%.
4. The method of claim 1,
the mass ratio of the catalyst to the reaction raw material is 0.1-0.5%.
5. The method according to claim 1, wherein the temperature of the reaction in step a) is 240 ℃;
the number average molecular weight of the PPST oligomer obtained in the step a) is 1.5-3 ten thousand;
in the step b), the reaction temperature is 160-230 ℃.
6. The process according to claim 1, wherein in step b), the reaction is carried out in a co-rotating parallel three-screw extruder;
the length-diameter ratio of the equidirectional parallel three-screw extruder is (36-44) to 1.
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