CN113896868A - Method for preparing polybutylene succinate by taking dimethyl succinate as raw material - Google Patents

Method for preparing polybutylene succinate by taking dimethyl succinate as raw material Download PDF

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CN113896868A
CN113896868A CN202111142932.6A CN202111142932A CN113896868A CN 113896868 A CN113896868 A CN 113896868A CN 202111142932 A CN202111142932 A CN 202111142932A CN 113896868 A CN113896868 A CN 113896868A
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phosphite
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containing compound
phosphate
inorganic metal
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CN113896868B (en
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郑柳春
刘义
周天博
任万成
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Tianjin Polytechnic University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract

The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a method for preparing polybutylene succinate by taking dimethyl succinate as a raw material, which provides a method for preparing polybutylene succinate by taking dimethyl succinate as a raw material, and comprises the following steps: catalyzing dimethyl succinate and butanediol by using an ester exchange catalyst to perform ester exchange reaction to obtain an ester exchange product; and mixing the transesterification product with a polycondensation catalyst, and carrying out polycondensation reaction to obtain the polybutylene succinate. The preparation method can effectively reduce the generation of side reaction and the yield of the byproduct tetrahydrofuran, and obtain the poly (butylene succinate) with higher molecular weight. Meanwhile, the raw materials of the invention are cheap and easy to obtain, which is beneficial to reducing the reaction cost.

Description

Method for preparing polybutylene succinate by taking dimethyl succinate as raw material
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a method for preparing polybutylene succinate by taking dimethyl succinate as a raw material.
Background
Polybutylene succinate (PBS) is an important high polymer material, has good mechanical and mechanical properties and good heat resistance; meanwhile, the poly (butylene succinate) has excellent biodegradability, and can be widely applied to the fields of medical supplies, agricultural films, slow-release materials, packaging, tableware and cosmetic bottles.
At present, the preparation of poly (butylene succinate) mostly takes succinic acid and butanediol as raw materials, and adopts a direct esterification polycondensation method to prepare the poly (butylene succinate) under the action of a catalyst. The direct esterification polycondensation method has the problems that the selectivity of a catalyst is poor, the generation amount of tetrahydrofuran generated by side reaction is large, generally more than 10%, the molecular weight of a polymer is low, and the number average molecular weight of industrial PBS is difficult to exceed one hundred thousand, so that the application of the PBS is severely limited.
Disclosure of Invention
In view of the above, the invention provides a method for preparing polybutylene succinate by using dimethyl succinate as a raw material. The poly (butylene succinate) prepared by the method provided by the invention has few by-products and high molecular weight.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a method for preparing polybutylene succinate by taking dimethyl succinate as a raw material, which comprises the following steps:
catalyzing dimethyl succinate and butanediol by using an ester exchange catalyst to perform ester exchange reaction to obtain an ester exchange product;
mixing the ester exchange product with a polycondensation catalyst to carry out polycondensation reaction to obtain the polybutylene succinate;
the transesterification catalyst comprises one or more of inorganic metal acetate, inorganic metal carbonate, inorganic metal bicarbonate, inorganic metal oxide, inorganic metal chloride, organic metal compound, phosphorus-containing compound and nitrogen-containing compound;
the polycondensation catalyst comprises a mixture of a phosphorus-containing compound, a nitrogen-containing compound, and an organometallic compound, a mixture of a phosphorus-containing compound and an organometallic compound, or a mixture of a nitrogen-containing compound and an organometallic compound.
The inorganic metal acetate comprises one or more of antimony acetate, magnesium acetate, manganese acetate and zinc acetate;
the inorganic metal carbonate comprises one or more of potassium carbonate, lithium carbonate, cesium carbonate, sodium carbonate and calcium carbonate;
the inorganic metal bicarbonate comprises sodium bicarbonate and/or potassium bicarbonate;
the inorganic metal oxide comprises germanium dioxide and/or antimony trioxide;
the inorganic metal chloride comprises one or more of zinc chloride, stannic chloride, stannous chloride and germanium chloride;
the organic metal compound comprises one or more of organic titanium compound, organic tin compound and organic germanium compound; the organic titanium compound comprises alkyl titanium with the total number of carbon atoms of 4-40 and/or alkoxy titanium with the total number of carbon atoms of 4-40; the organic tin compound comprises alkyl tin with the total number of carbon atoms of 4-40; the organic germanium compound includes alkyl germanium having a total carbon number of 4 to 40.
Preferably, the polycondensation catalyst further comprises one or more of inorganic metal carbonate, inorganic metal bicarbonate, inorganic metal oxide, and inorganic metal chloride.
Preferably, the phosphorus-containing compound includes phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripropyl phosphate, tripentyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tripropyl phosphite, triisodecyl phosphite, triisopropyl phosphite, trilauryl phosphite, bis (octadecyl) pentaerythritol diphosphite, triphenyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, phenyl-bis (4-octylphenyl) phosphite, tris [ (4-octylethylphenyl) ] phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenyldiphosphite, di (2, 4-tert-butylphenyl) pentaerythritol diphosphite and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol tetraphosphite.
Preferably, the nitrogen-containing compound comprises one or more of imidazole salt, C2-C18 alkyl substituted imidazole halogen salt, pyridine salt, C2-C18 alkyl substituted pyridine halogen salt, amino acid derivative, lactam derivative, coupling agent, polyvinylpyrrolidone or polyacrylamide.
Preferably, when the polycondensation catalyst is a mixture of an organic metal compound and a phosphorus-containing compound, the mass ratio of the phosphorus-containing compound to the organic metal compound is 0.05-1.5: 1;
when the polycondensation catalyst is a mixture of an organic metal compound and a nitrogen-containing compound, the mass ratio of the nitrogen-containing compound to the organic metal compound is 0.05-1.5: 1;
when the polycondensation catalyst is a mixture of an organometallic compound, a phosphorus-containing compound and a nitrogen-containing compound, the mass ratio of the sum of the substances of the phosphorus-containing compound and the nitrogen-containing compound to the substance of the organometallic compound is 0.05 to 1.5: 1.
preferably, the mass of the polycondensation catalyst is 0.005-3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol.
Preferably, the mass of the ester exchange catalyst is 0.002-3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol.
Preferably, the molar ratio of the dimethyl succinate to the butanediol is 1: 1-1: 2.5.
Preferably, the pressure of the ester exchange reaction is 10-120 kPa, the temperature is 110-190 ℃, and the time is 1-6 h.
Preferably, the pressure of the polycondensation reaction is 0-500 Pa, the temperature is 170-250 ℃, and the time is 1-6 h.
The invention also provides the polybutylene succinate prepared by the technical scheme, wherein the weight average molecular weight of the polybutylene succinate is more than 200000.
According to the invention, cheap and easily-obtained dimethyl succinate and butanediol are used as raw materials, and then a high-efficiency ester exchange catalyst is matched to catalyze the dimethyl succinate and the butanediol to carry out an ester exchange reaction, so as to obtain an ester exchange product; and then carrying out polycondensation reaction by using the ester exchange product in the presence of a polycondensation catalyst, wherein the polycondensation catalyst comprises a phosphorus-containing compound or a nitrogen-containing compound and also comprises an organic metal compound, and N or P elements in the phosphorus-containing or nitrogen-containing compound can be coordinated with titanium, tin or germanium elements in a metal compound to regulate and control the electronic environment of metal atoms, so that the catalytic activity of the polycondensation catalyst is improved, the activity of the polycondensation catalyst for the positive reaction of polycondensation is improved, and the catalytic activity of the polycondensation catalyst for the side reaction is reduced. Therefore, the preparation method can effectively reduce the generation of side reaction and the yield of the byproduct tetrahydrofuran, and obtain the poly butylene succinate with high molecular weight and good color. Meanwhile, the raw materials of the invention are cheap and easy to obtain, which is beneficial to reducing the reaction cost.
Furthermore, the polycondensation catalyst can also be one or more of inorganic metal carbonate, inorganic metal bicarbonate, inorganic metal oxide and inorganic metal chloride, and the inorganic metal carbonate, the inorganic metal bicarbonate, the inorganic metal oxide or the inorganic metal chloride is compounded with a phosphorus-containing compound, a nitrogen-containing compound and an organic metal compound to regulate and control the catalytic activity of the polycondensation catalyst, improve the activity of the polycondensation catalyst on the positive reaction and the negative reaction of the polycondensation catalyst and reduce the catalytic activity of the polycondensation catalyst on the side reaction.
In addition, the catalyst used in the invention is a commercial catalyst, has high activity and strong selectivity, can perform high-efficiency catalytic reaction, is beneficial to improving the production efficiency and is easy to industrialize.
The data of the embodiment shows that the amount of tetrahydrofuran generated in the reaction process is 1-4% of the mass of the butanediol, which is far less than 10% of the tetrahydrofuran generated in the prior art, and the weight average molecular weight of the polybutylene succinate prepared by the invention can reach more than 20 ten thousand.
Drawings
FIG. 1 is a schematic representation of a polybutylene succinate pellet PBS3 prepared in example 2, run 2.2;
FIG. 2 is a GPC chart of PBS3, a polybutylene succinate prepared in example 2, run 2.2.
Detailed Description
The invention provides a method for preparing polybutylene succinate by taking dimethyl succinate as a raw material, which comprises the following steps:
catalyzing dimethyl succinate and butanediol by using an ester exchange catalyst to perform ester exchange reaction to obtain an ester exchange product;
mixing the ester exchange product with a polycondensation catalyst to carry out polycondensation reaction to obtain the polybutylene succinate;
in the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The invention utilizes ester exchange catalyst to catalyze succinic acid dimethyl ester and butanediol to carry out ester exchange reaction, thereby obtaining ester exchange product.
In the present invention, the transesterification catalyst includes one or more of inorganic metal acetate, inorganic metal carbonate, inorganic metal bicarbonate, inorganic metal oxide, inorganic metal chloride, organic metal compound, phosphorus-containing compound and nitrogen-containing compound, and more preferably inorganic metal acetate, a mixture of inorganic metal acetate and organic metal compound and a mixture of phosphorus-containing compound or a mixture of phosphorus-containing compound and organic metal acetate.
In the invention, the inorganic metal acetate comprises one or more of antimony acetate, magnesium acetate, manganese acetate and zinc acetate, and further preferably comprises magnesium acetate and/or zinc acetate.
In the present invention, the inorganic metal carbonate includes one or more of potassium carbonate, lithium carbonate, cesium carbonate, sodium carbonate, and calcium carbonate.
In the present invention, the inorganic metal bicarbonate includes sodium bicarbonate and/or potassium bicarbonate.
In the present invention, the inorganic metal oxide includes germanium dioxide and/or antimony trioxide.
In the present invention, the inorganic metal chloride includes one or more of zinc chloride, tin tetrachloride, stannous chloride and germanium chloride.
In the present invention, the organometallic compound includes one or more of an organotitanium compound, an organotin compound, and an organogermanium compound.
In the present invention, the organic titanium compound includes alkyl titanium having a total number of carbon atoms of 4 to 40 and/or alkoxy titanium having a total number of carbon atoms of 4 to 40, and is preferably tetrabutyl titanate.
In the invention, the organic tin compound comprises alkyl tin with the total number of carbon atoms of 4-40.
In the invention, the organic germanium compound comprises alkyl germanium with the total number of carbon atoms of 4-40.
In the present invention, the phosphorus-containing compound preferably includes phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripropyl phosphate, tripentyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, tripropyl phosphite, triisodecyl phosphite, triisopropyl phosphite, trilauryl phosphite, bis (octadecyl) pentaerythritol diphosphite, triphenyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, phenyl-bis (4-octylphenyl) phosphite, tris [ (4-octylethylphenyl) ] phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenyldiphosphonite, pentaerythritol diphosphite bis (2, 4-tert-butylphenyl) ester and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, and further preferably one or more of phosphoric acid, triphenyl phosphate, triphenyl phosphite and trimethyl phosphate.
In the present invention, the nitrogen-containing compound preferably includes one or more of imidazole salt, C2-C18 alkyl-substituted imidazole halogen salt, pyridine salt, C2-C18 alkyl-substituted pyridine halogen salt, amino acid derivative, lactam derivative, coupling agent, polyvinylpyrrolidone and polyacrylamide, and more preferably lactam derivative and/or polyvinylpyrrolidone. In the present invention, the lactam derivative preferably includes caprolactam and/or capryllactam, and more preferably caprolactam. In the present invention, the amino acid derivative preferably includes one or more of an omega-amino acid, an alpha-amino acid and 12-aminododecanoic acid.
In the invention, the mass of the ester exchange catalyst is preferably 0.002-3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol, and more preferably 0.005-3%.
In the invention, the mass ratio of the dimethyl succinate to the butanediol is preferably 1: 1-1: 2.5, and further preferably 1: 1-1: 2.2. In the invention, the pressure intensity of the ester exchange reaction is preferably 10-120 kPa; the temperature of the ester exchange reaction is preferably 110-190 ℃; the time is preferably 1-6 h.
After the ester exchange product is obtained, the ester exchange product is mixed with a polycondensation catalyst to carry out polycondensation reaction, and the poly (butylene succinate) is obtained.
In the present invention, the polycondensation catalyst includes a mixture of a phosphorus-containing compound, a nitrogen-containing compound and an organometallic compound, a mixture of a phosphorus-containing compound and an organometallic compound, and a mixture of a nitrogen-containing compound and an organometallic compound.
In the present invention, the polycondensation catalyst preferably further comprises an inorganic metal carbonate, an inorganic metal bicarbonate, an inorganic metal oxide and an inorganic metal chloride.
In the present invention, when the polycondensation catalyst is a mixture of an organometallic compound and a phosphorus-containing compound, the mass ratio of the phosphorus-containing compound to the organometallic compound is preferably 0.05 to 1.5: 1. in the present invention, when the polycondensation catalyst is a mixture of an organic metal compound and a nitrogen-containing compound, the mass ratio of the nitrogen-containing compound to the organic metal compound is preferably 0.05 to 1.5: 1. in the present invention, when the polycondensation catalyst is a mixture of an organometallic compound, a phosphorus-containing compound and a nitrogen-containing compound, the ratio of the sum of the amounts of the substances of the phosphorus-containing compound and the nitrogen-containing compound to the amount of the substance of the organometallic compound is 0.05 to 1.5: 1.
in the present invention, the mass of the polycondensation catalyst is preferably 0.005 to 3%, more preferably 0.01 to 3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol.
In the invention, the pressure of the polycondensation reaction is preferably 0-500 Pa, more preferably 10-300 Pa, the temperature of the polycondensation reaction is preferably 170-250 ℃, and the time is preferably 1-6 h.
The method for preparing polybutylene succinate using dimethyl succinate as a raw material according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding dimethyl succinate and butanediol (wherein the molar ratio of dimethyl succinate to butanediol is 1:1.3, and the mass sum of dimethyl succinate and butanediol is 35kg) into a reaction device, then adding 0.7g of magnesium acetate (the mass of the transesterification catalyst is 0.005% of the total mass of dimethyl succinate and butanediol), carrying out transesterification reaction for 3h under the condition of negative pressure of 10kPa and at the temperature of 155 ℃, then heating to 225 ℃, adding 1.75g of tetrabutyl titanate and 0.36g of trimethyl phosphate (the amount of the trimethyl phosphate is 0.5 times of that of the tetrabutyl titanate), and reducing the pressure to 20Pa to carry out polycondensation reaction for 6h to obtain polybutylene succinate, which is recorded as PBS 1.
Example 2
Example 2 a total of 4 and 4 tests were performed, test 2.1, test 2.2, test 2.3 and test 2.4.
Run 2.1 differed from example 1 only in a 1:1.0 molar ratio of succinic to butanediol, resulting in PBS 2.
Run 2.2 differed from example 1 only in a 1:1.65 molar ratio of succinic to butanediol, resulting in PBS 3.
Run 2.3 differed from example 1 only in a 1:1.8 molar ratio of succinic to butanediol, resulting in PBS 4.
Run 2.4 differed from example 1 only in a 1:2.2 molar ratio of succinic to butanediol, resulting in PBS 5.
The invention also tests the mechanical properties of PBS1, PBS2, PBS3, PBS4 and PBS5, and the tensile strength is as per GB/T1040.2-2006 part 2: test conditions for molded and extruded plastics were tested; the bending strength is tested according to the bending performance test of GB/T9341-2008; the intrinsic viscosity is tested according to the method specified in GB/T14190-; the test results are shown in Table 1.
TABLE 1 mechanical Properties test results of PBS
Figure BDA0003284650650000071
Figure BDA0003284650650000081
FIG. 1 is a schematic representation of PBS3, a poly (butylene succinate) pellet prepared in example 2, run 2.2, and as can be seen from FIG. 1, PBS3 prepared in accordance with the present invention is white in color.
The invention also utilizes a color difference meter to test the colorimetric value of the PBS3, and the test result is that the L value is 83, the a value is-0.3, and the b value is 3.
Fig. 2 shows a GPC chart of the polybutylene succinate PBS3 obtained, and as can be seen from fig. 2, the viscosity average molecular weight of the polybutylene succinate PBS3 is 350820.
The present invention also examined the molecular weight, weight average molecular weight, and molecular weight distribution of PBS3, with the results shown in table 2:
TABLE 2 data molecular weight, weight average molecular weight and molecular weight distribution measurements of PBS3
PBS3 Data molecular weight Weight average molecular weight Molecular weight distribution
The result of the detection 132483 214908 1.322650
As can be seen from Table 2, the weight average molecular weight of PBS3 can reach more than 20 ten thousand.
Example 3
Example 3 a total of 5 tests were carried out, test 3.1, test 3.2, test 3.3, test 3.4 and test 3.5.
Experiment 3.1 differs from experiment 2.2 in example 2 only in that the amount of transesterification catalyst was 0.005% by mass of the total mass of dimethyl succinate and butanediol, and PBS6 was finally obtained, with a content of by-product tetrahydrofuran of 4% by mass of butanediol.
Experiment 3.2 differs from experiment 2.2 in example 2 only in that the amount of transesterification catalyst was 0.02% of the total mass of dimethyl succinate and butanediol, and PBS7 was finally obtained with a tetrahydrofuran content as a by-product of 1% of the mass of butanediol.
Experiment 3.3 differs from experiment 2.2 in example 2 only in that the amount of transesterification catalyst was 0.03% of the total mass of dimethyl succinate and butanediol, and PBS8 was finally obtained with a tetrahydrofuran content as a by-product of 2% of the mass of butanediol.
Experiment 3.4 differs from experiment 2.2 in example 2 only in that the amount of transesterification catalyst was 0.06% of the total mass of dimethyl succinate and butanediol, and PBS9 was finally obtained, with the amount of by-product tetrahydrofuran being 1% of the mass of butanediol.
Experiment 3.5 differs from experiment 2.2 in example 2 only in that the amount of transesterification catalyst was 3% by mass of the total mass of dimethyl succinate and butanediol, and PBS10 was finally obtained with a content of by-product tetrahydrofuran of 0.5% by mass of butanediol.
Example 4
Example 4 a total of 5 tests were carried out, test 4.1, test 4.2, test 4.3, test 4.4 and test 4.5.
Run 4.1 differs from run 3.3 of example 3 only in that the pressure of the transesterification reaction is 10kPa and the temperature of the transesterification reaction is 190 ℃; the polycondensation reaction temperature is 230 ℃, the polycondensation reaction pressure is 200Pa, PBS11 is finally obtained, and the content of the by-product tetrahydrofuran is 3 percent of the mass of the butanediol.
Run 4.2 differs from run 3.3 of example 3 only in that the pressure of the transesterification reaction is 30 kPa and the temperature of the transesterification reaction is 110 ℃; the temperature of the polycondensation reaction is 170 ℃, the pressure of the polycondensation reaction is 10Pa, PBS12 is finally obtained, and the content of the by-product tetrahydrofuran is 0.5 percent of the mass of the butanediol.
Run 4.3 differs from run 3.3 of example 3 only in that the pressure of the transesterification reaction is 40 kPa and the temperature of the transesterification reaction is 180 ℃; the polycondensation reaction temperature is 240 ℃, the polycondensation reaction pressure is 100Pa, PBS13 is finally obtained, and the content of the by-product tetrahydrofuran is 3 percent of the mass of the butanediol.
Run 4.4 differs from run 3.3 of example 3 only in that the pressure of the transesterification reaction is 60 kPa and the temperature of the transesterification reaction is 165 ℃; the temperature of the polycondensation reaction is 235 ℃, the pressure of the polycondensation reaction is 50Pa, PBS14 is finally obtained, and the content of the by-product tetrahydrofuran is 4 percent of the mass of the butanediol.
Run 4.5 differs from run 3.3 of example 3 only in that the pressure of the transesterification reaction is 120kPa and the temperature of the transesterification reaction is 200 ℃; the polycondensation reaction temperature is 250 ℃, the pressure of the polycondensation reaction is 300 Pa, PBS15 is finally obtained, and the content of the by-product tetrahydrofuran is 2 percent of the mass of the butanediol.
Example 5
Example 5 a total of 5 tests 5.1, 5.2, 5.3, 5.4 and 5.5 were carried out.
Run 5.1 differed from run 3.3 in example 3 only in that the transesterification catalyst of the transesterification reaction was replaced with zinc acetate to give PBS16 with a by-product tetrahydrofuran content of 4% by mass of butanediol.
Run 5.2 differed from run 3.3 in example 3 only in that the transesterification catalyst was replaced with a mixture of magnesium acetate and tetrabutyl titanate (where the mass ratio of magnesium acetate to tetrabutyl titanate was 1:2) to finally give PBS17 with a by-product tetrahydrofuran content of 4% by mass of butanediol.
Run 5.3 differed from run 3.3 in example 3 only in that the transesterification catalyst of the transesterification reaction was replaced with a mixture of magnesium acetate and tetrabutyl titanate and phosphoric acid (where the mass ratio of magnesium acetate, tetrabutyl titanate and phosphoric acid was 1: 2: 0.7), resulting in PBS18 with a by-product tetrahydrofuran content of 2% by mass of the butanediol.
Run 5.4 differed from run 3.3 in example 3 only in that the transesterification catalyst of the transesterification reaction was replaced with a mixture of tetrabutyl titanate and trimethyl phosphate (in which the mass ratio of tetrabutyl titanate to trimethyl phosphate was 3:1), resulting in PBS19 with a by-product tetrahydrofuran content of 1% by mass of butanediol.
Run 4.5 differs from run 3.3 of example 3 only in that the transesterification catalyst of the transesterification reaction was replaced with a mixture of titanium glycol and triphenyl phosphate (where the mass ratio of titanium glycol to triphenyl phosphate is 3:2), resulting in PBS20 with a by-product tetrahydrofuran content of 3% by mass of butanediol.
Example 6
Example 6 a total of 5 tests 6.1, 6.2, 6.3, 6.4 and 6.5 were carried out.
Run 6.1 differed from example 1 only in that the transesterification reaction time was 6h, which resulted in PBS21 with a by-product tetrahydrofuran content of 4% by mass of butanediol.
Run 6.2 differed from example 1 only in that the transesterification reaction time was 2h, which resulted in PBS22 with a by-product tetrahydrofuran content of 2% by mass of the butanediol.
Run 6.3 differed from example 1 only in that the transesterification reaction time was 4h, which resulted in PBS23 with a by-product tetrahydrofuran content of 3% by mass of the butanediol.
Run 6.4 differed from example 1 only in that the transesterification reaction time was 1h, which resulted in PBS24 with a by-product tetrahydrofuran content of 1% by mass of butanediol.
Run 6.5 differed from example 1 only in that the transesterification reaction time was 5h, which resulted in PBS25 with a by-product tetrahydrofuran content of 4% by mass of butanediol.
Example 7
Example 7 a total of 5 tests were performed, test 7.1, test 7.2, test 7.3, test 7.4 and test 7.5.
The difference between test 7.1 and example 1 is that only trimethyl phosphate in example 1 is replaced by phosphoric acid, and PBS26 (the amount of phosphoric acid is 1.5 times of that of tetrabutyl titanate) is finally obtained, and the content of byproduct tetrahydrofuran is 0.5% of the mass of butanediol.
Experiment 7.2 differed from example 1 only in that trimethyl phosphate in example 1 was replaced with triphenyl phosphate (the amount of triphenyl phosphate was 1.0 times the amount of tetrabutyl titanate), and PBS27 was finally obtained with a by-product tetrahydrofuran content of 0.6% by mass of butanediol.
Experiment 7.3 differed from example 1 only in that trimethyl phosphate in example 1 was replaced with triphenyl phosphite (the amount of triphenyl phosphite material was 0.75 times the amount of tetrabutyl titanate material), and finally PBS28 was obtained with a by-product tetrahydrofuran content of 1% by mass of butanediol.
Run 7.4 differed from example 1 only in that trimethyl phosphate was replaced by caprolactam in example 1 (the amount of caprolactam material was 0.25 times the amount of tetrabutyl titanate material), resulting in PBS29 with a by-product tetrahydrofuran content of 2% by mass of butanediol.
Experiment 7.5 differs from example 1 only in that trimethyl phosphate in example 1 was replaced with polyvinylpyrrolidone (the amount of the substance of polyvinylpyrrolidone is 0.05 times the amount of the substance of tetrabutyl titanate), and PBS30 was finally obtained with a content of by-product tetrahydrofuran of 4% by mass of butanediol.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for preparing poly (butylene succinate) by taking dimethyl succinate as a raw material is characterized by comprising the following steps:
catalyzing dimethyl succinate and butanediol by using an ester exchange catalyst to perform ester exchange reaction to obtain an ester exchange product;
mixing the transesterification product with a polycondensation catalyst, and carrying out a polycondensation reaction to obtain the polybutylene succinate;
the transesterification catalyst comprises one or more of inorganic metal acetate, inorganic metal carbonate, inorganic metal bicarbonate, inorganic metal oxide, inorganic metal chloride, organic metal compound, phosphorus-containing compound and nitrogen-containing compound;
the polycondensation catalyst comprises a mixture of a phosphorus-containing compound, a nitrogen-containing compound, and an organometallic compound, a mixture of a phosphorus-containing compound and an organometallic compound, or a mixture of a nitrogen-containing compound and an organometallic compound.
The inorganic metal acetate comprises one or more of antimony acetate, magnesium acetate, manganese acetate and zinc acetate;
the inorganic metal carbonate comprises one or more of potassium carbonate, lithium carbonate, cesium carbonate, sodium carbonate and calcium carbonate;
the inorganic metal bicarbonate comprises sodium bicarbonate and/or potassium bicarbonate;
the inorganic metal oxide comprises germanium dioxide and/or antimony trioxide;
the inorganic metal chloride comprises one or more of zinc chloride, stannic chloride, stannous chloride and germanium chloride;
the organic metal compound comprises one or more of organic titanium compound, organic tin compound and organic germanium compound; the organic titanium compound comprises alkyl titanium with the total number of carbon atoms of 4-40 and/or alkoxy titanium with the total number of carbon atoms of 4-40; the organic tin compound comprises alkyl tin with the total number of carbon atoms of 4-40; the organic germanium compound includes alkyl germanium having a total carbon number of 4 to 40.
2. The method of claim 1, wherein the polycondensation catalyst further comprises one or more of an inorganic metal carbonate, an inorganic metal bicarbonate, an inorganic metal oxide, and an inorganic metal chloride.
3. The method of claim 1, wherein the phosphorus-containing compound comprises phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripropyl phosphate, tripentyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triisodecyl phosphite, triisopropyl phosphite, trilauryl phosphite, bis (octadecyl) pentaerythritol diphosphite, triphenyl phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, phenyl-bis (4-octylphenyl) phosphite, tris [ (4-octylethylphenyl) ] phosphite, tris (4-octylethylphenyl) ] phosphite, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphite, triethyl phosphite, tributyl phosphate, tributyl phosphite, triisodecyl phosphite, tributyl phosphite, triisodecyl phosphite, tributyl phosphite, triisodecyl phosphite, pentaerythritol, tributyl phosphite, and triisodecyl phosphite, tributyl phosphite, or tributyl phosphite, triisodecyl phosphite, tributyl phosphite, triisodecyl phosphite, or a mixture, pentaerythritol, and tributyl phosphite, and/pentaerythritol, and/s, or a mixture, wherein the mixture of pentaerythritol, and/s, and, One or more of tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, tetrakis (2, 4-di-tert-butylphenyl) -4, 4' -biphenyldiphosphite, di (2, 4-tert-butylphenyl) pentaerythritol diphosphite and bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite.
4. The method of claim 1, wherein the nitrogen-containing compound comprises one or more of imidazole salt, C2-C18 alkyl substituted imidazole halogen salt, pyridine salt, C2-C18 alkyl substituted pyridine halogen salt, amino acid derivative, lactam derivative, coupling agent, polyvinylpyrrolidone or polyacrylamide.
5. The process for producing polybutylene succinate according to claim 1, 3 or 4, wherein,
when the polycondensation catalyst is a mixture of an organic metal compound and a phosphorus-containing compound, the mass ratio of the phosphorus-containing compound to the organic metal compound is 0.05-1.5: 1;
when the polycondensation catalyst is a mixture of an organic metal compound and a nitrogen-containing compound, the mass ratio of the nitrogen-containing compound to the organic metal compound is 0.05-1.5: 1;
when the polycondensation catalyst is a mixture of an organometallic compound, a phosphorus-containing compound and a nitrogen-containing compound, the ratio of the sum of the amounts of the substances of the phosphorus-containing compound and the nitrogen-containing compound to the amount of the substance of the organometallic compound is 0.05 to 1.5: 1.
6. the method for preparing polybutylene succinate according to any one of claims 1 to 4, wherein the mass of the polycondensation catalyst is 0.005 to 3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol; the mass of the ester exchange catalyst is 0.002-3% of the sum of the mass of the dimethyl succinate and the mass of the butanediol.
7. The method for preparing polybutylene succinate according to claim 1, wherein the molar ratio of the dimethyl succinate to the butanediol is 1: 1-1: 2.5.
8. The method for preparing polybutylene succinate according to claim 1, wherein the pressure of the transesterification reaction is 10-120 kPa, the temperature is 110-190 ℃, and the time is 1-6 h.
9. The method for preparing polybutylene succinate according to claim 1, wherein the pressure of the polycondensation reaction is 0-500 Pa, the temperature is 170-250 ℃, and the time is 1-6 h.
10. The poly (butylene succinate) prepared by the method for preparing poly (butylene succinate) according to claim 1 to 9, wherein the weight average molecular weight of the poly (butylene succinate) is more than 200000.
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