CN112920386A - Production and preparation method of PBS (poly butylenes succinate) for degradable product - Google Patents

Production and preparation method of PBS (poly butylenes succinate) for degradable product Download PDF

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CN112920386A
CN112920386A CN202110122021.0A CN202110122021A CN112920386A CN 112920386 A CN112920386 A CN 112920386A CN 202110122021 A CN202110122021 A CN 202110122021A CN 112920386 A CN112920386 A CN 112920386A
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pbs
reactants
total weight
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陈世军
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Linqu Qili Catalyst Co ltd
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Linqu Qili Catalyst Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • C08G63/18Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181Acids containing aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16Dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00Compositions for preparing biodegradable polymers

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a production and preparation method of PBS for degradable products, which relates to the field of degradable plastics and comprises the following steps: step one, placing dihydric alcohol and dibasic acid with the molar ratio of 1.1-2.5: 1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.02-0.3% of the total weight of reactants and a stabilizer accounting for 0.03-4% of the total weight of the reactants; step two, heating to 140-220 ℃ and carrying out esterification reaction for 2-4 hours under normal pressure; step three, after the esterification is finished, adding a chain extender accounting for 0.05 to 5 percent of the total weight of reactants, heating to 200 to 260 ℃, and reducing the pressure to 500Pa to 20Kpa to carry out melt pre-polycondensation reaction for 0.5 to 3 hours; and step four, decompressing the product obtained in the step to 10-200 Pa, and carrying out melt polycondensation reaction for 0.5-3 hours to obtain a PBS product. The method for producing the PBS shortens the time of esterification reaction and polycondensation reaction, reduces the production cost, and simultaneously produces the PBS product with high molecular weight, uniform distribution, good color and luster and excellent mechanical property.

Description

Production and preparation method of PBS (poly butylenes succinate) for degradable product
Technical Field
The invention relates to the field of degradable plastics, in particular to a production and preparation method of PBS for a degradable product.
Background
The degradation of polymer refers to the process of breaking polymeric macromolecular chains caused by chemical and physical factors, the degradation process of breaking macromolecular chains of polymer under the environmental conditions of exposing the polymer to oxygen, water, radiation, chemicals, pollutants, mechanical force, insects and other animals and microorganisms is called environmental degradation, the degradation reduces the molecular weight of the polymer, the physical property of the polymer material is reduced until the polymer material loses workability, the phenomenon is called aging degradation of the polymer material, the aging degradation of the polymer and the stability of the polymer have direct relation, the aging degradation of the polymer shortens the service life of the plastic, therefore, scientists have studied the aging prevention, namely stabilization, of the materials to prepare high-stability polymer materials since the plastic comes out, and scientists of various countries are also competing to develop the environmental degradation plastic by utilizing the degradation behavior of the polymer, the main application fields of the degradable plastics are as follows: agricultural mulching films, various plastic packaging bags, garbage bags, shopping bags in markets, disposable tableware and the like.
The traditional PBS polyester process has long reaction time, low molecular weight, wide distribution and unstable product performance, so that the market urgently needs to be capable of efficiently producing PBS products with high molecular weight, uniform distribution, good color and luster and excellent mechanical property.
Disclosure of Invention
The invention aims to: in order to solve the problems of long reaction time, low molecular weight, wide distribution and unstable product performance of the PBS polyester process, the production preparation method of the PBS for the degradable product is provided.
In order to achieve the purpose, the invention provides the following technical scheme: a method for producing and preparing PBS for degradable products comprises the following steps:
step one, placing dihydric alcohol and dibasic acid with the molar ratio of 1.1-2.5: 1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.02-0.3% of the total weight of reactants and a stabilizer accounting for 0.03-4% of the total weight of the reactants;
step two, heating to 140-220 ℃ and carrying out esterification reaction for 2-4 hours under normal pressure;
step three, after the esterification is finished, adding a chain extender accounting for 0.05 to 5 percent of the total weight of reactants, heating to 200 to 260 ℃, and reducing the pressure to 500Pa to 20Kpa to carry out melt pre-polycondensation reaction for 0.5 to 3 hours;
and step four, decompressing the product obtained in the step to 10-200 Pa, and carrying out melt polycondensation reaction for 0.5-3 hours to obtain a PBS product.
Preferably, the diols are: C2-C10 aliphatic diol.
Preferably, the dibasic acid is: aliphatic dibasic acids of C2-C10.
Preferably, the high efficiency catalyst is: the catalyst comprises a metal oxide and a titanium/silicon organic ester compound catalyst, wherein the metal oxide comprises sodium, aluminum and iron, the titanium/silicon molar ratio in the titanium/silicon organic ester compound is 1-15: 1, the titanium organic ester is dimethyl titanate, and the silicon organic ester is isopropyl n-silicate.
Preferably, the stabilizer is: n, N' -diisopropylcarbodiimide, poly-dicyclohexylcarbodiimide.
Preferably, the chain extender is: an acid anhydride chain extender.
Compared with the prior art, the invention has the beneficial effects that:
the method for producing the PBS shortens the time of esterification reaction and polycondensation reaction, reduces the production cost, and simultaneously produces the PBS product with high molecular weight, uniform distribution, good color and luster and excellent mechanical property.
Detailed Description
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "disposed" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art. The following describes an embodiment of the present invention based on its overall structure.
A method for producing and preparing PBS for degradable products comprises the following steps:
step one, placing dihydric alcohol and dibasic acid with the molar ratio of 1.1-2.5: 1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.02-0.3% of the total weight of reactants and a stabilizer accounting for 0.03-4% of the total weight of the reactants;
step two, heating to 140-220 ℃ and carrying out esterification reaction for 2-4 hours under normal pressure;
step three, after the esterification is finished, adding a chain extender accounting for 0.05 to 5 percent of the total weight of reactants, heating to 200 to 260 ℃, and reducing the pressure to 500Pa to 20Kpa to carry out melt pre-polycondensation reaction for 0.5 to 3 hours;
and step four, decompressing the product obtained in the step to 10-200 Pa, and carrying out melt polycondensation reaction for 0.5-3 hours to obtain a PBS product.
The dihydric alcohol is: C2-C10 aliphatic diol.
The dibasic acid is: aliphatic dibasic acids of C2-C10.
The high-efficiency catalyst is as follows: the catalyst comprises a metal oxide and a titanium/silicon organic ester compound catalyst, wherein the metal oxide comprises sodium, aluminum and iron, the titanium/silicon molar ratio in the titanium/silicon organic ester compound is 1-15: 1, the titanium organic ester is dimethyl titanate, and the silicon organic ester is isopropyl n-silicate.
The stabilizer is as follows: n, N' -diisopropylcarbodiimide, poly-dicyclohexylcarbodiimide.
The chain extender is: an acid anhydride chain extender.
Example one
A method for producing and preparing PBS for degradable products comprises the following steps:
step one, placing dihydric alcohol and dibasic acid with the molar ratio of 1.1:1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.02 percent of the total weight of reactants and a stabilizer accounting for 0.03 percent of the total weight of the reactants;
step two, heating to 140 ℃ and carrying out esterification reaction for 2 hours under normal pressure;
step three, after the esterification is finished, adding a chain extender accounting for 0.05 percent of the total weight of reactants, heating to 200 ℃, and reducing the pressure to 500Pa to carry out melt pre-polycondensation reaction for 0.5 hour;
and step four, decompressing the product obtained in the step to 10Pa, and carrying out melt polycondensation reaction for 0.5 hour to obtain a PBS product.
Example two
A method for producing and preparing PBS for degradable products comprises the following steps:
step one, placing dihydric alcohol and dibasic acid with the molar ratio of 2.5:1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.3 percent of the total weight of reactants and a stabilizer accounting for 4 percent of the total weight of the reactants;
step two, heating to 220 ℃ and carrying out esterification reaction for 4 hours under normal pressure;
step three, after the esterification is finished, adding a chain extender accounting for 0.05 to 5 percent of the total weight of reactants, heating to 260 ℃, and reducing the pressure to 20Kpa to carry out melt pre-polycondensation reaction for 3 hours;
and step four, decompressing the product obtained in the step to 200Pa, and carrying out melt polycondensation for 3 hours to obtain a PBS product.
EXAMPLE III
A method for producing and preparing PBS for degradable products comprises the following steps:
step one, placing dihydric alcohol and dibasic acid with a molar ratio of 1.5:1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.2 percent of the total weight of reactants and a stabilizer accounting for 2 percent of the total weight of the reactants;
step two, heating to 180 ℃ and carrying out esterification reaction for 3 hours under normal pressure;
step three, adding a chain extender accounting for 3 percent of the total weight of reactants after esterification, heating to 230 ℃, and reducing the pressure to 300Kpa to carry out melt pre-polycondensation reaction for 1.8 hours;
and step four, decompressing the product obtained in the step to 100Pa, and carrying out melt polycondensation for 2 hours to obtain a PBS product.
Table one:
the aliphatic diol of C2-C10, the aliphatic dibasic acid of C2-C10, the high-efficiency catalyst and the stabilizer required in the first embodiment, the second embodiment and the third embodiment are as follows:
Figure BDA0002922500900000051
table two: after the test of the finished product in the first embodiment, the second embodiment and the third embodiment, the following data are obtained:
Figure BDA0002922500900000052
table three: the degradation effect of the first embodiment, the second embodiment and the third embodiment in natural environment is as follows:
degradation rate/month Degradation rate/year
Example one 7.3%~8.5% 90%~95%
Example two 7.6%~9.3% 93%~97%
EXAMPLE III 8.2%~9.6% 94%~100%
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (6)

1. A method for producing and preparing PBS for degradable products is characterized by comprising the following steps:
step one, placing dihydric alcohol and dibasic acid with the molar ratio of 1.1-2.5: 1 into a reaction kettle, adding a high-efficiency catalyst accounting for 0.02-0.3% of the total weight of reactants and a stabilizer accounting for 0.03-4% of the total weight of the reactants;
step two, heating to 140-220 ℃ and carrying out esterification reaction for 2-4 hours under normal pressure;
step three, after the esterification is finished, adding a chain extender accounting for 0.05 to 5 percent of the total weight of reactants, heating to 200 to 260 ℃, and reducing the pressure to 500Pa to 20Kpa to carry out melt pre-polycondensation reaction for 0.5 to 3 hours;
and step four, decompressing the product obtained in the step to 10-200 Pa, and carrying out melt polycondensation reaction for 0.5-3 hours to obtain a PBS product.
2. The method for preparing PBS for degradable products according to claim 1, wherein the PBS comprises: the dihydric alcohol is: C2-C10 aliphatic diol.
3. The method for preparing PBS for degradable products according to claim 1, wherein the PBS comprises: the dibasic acid is: aliphatic dibasic acids of C2-C10.
4. The method for preparing PBS for degradable products according to claim 1, wherein the PBS comprises: the high-efficiency catalyst is as follows: the catalyst comprises a metal oxide and a titanium/silicon organic ester compound catalyst, wherein the metal oxide comprises sodium, aluminum and iron, the titanium/silicon molar ratio in the titanium/silicon organic ester compound is 1-15: 1, the titanium organic ester is dimethyl titanate, and the silicon organic ester is isopropyl n-silicate.
5. The method for preparing PBS for degradable products according to claim 1, wherein the PBS comprises: the stabilizer is as follows: n, N' -diisopropylcarbodiimide, poly-dicyclohexylcarbodiimide.
6. The method for preparing PBS for degradable products according to claim 1, wherein the PBS comprises: the chain extender is: an acid anhydride chain extender.
CN202110122021.0A 2021-01-29 2021-01-29 Production and preparation method of PBS (poly butylenes succinate) for degradable product Pending CN112920386A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1223653A (en) * 1984-10-26 1987-06-30 John R. Barrett Pbs-pbse ir detector arrays and fabrication method
CN102558515A (en) * 2011-12-06 2012-07-11 上海聚友化工有限公司 Method for continuously preparing biodegradable plastic
CN103012757A (en) * 2012-11-27 2013-04-03 中国包装科研测试中心 Preparation method of poly(butylene succinate)
CN103214659A (en) * 2013-03-25 2013-07-24 山东汇盈新材料科技有限公司 High molecular weight bio-based poly(butylene succinate) synthesis method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1223653A (en) * 1984-10-26 1987-06-30 John R. Barrett Pbs-pbse ir detector arrays and fabrication method
CN102558515A (en) * 2011-12-06 2012-07-11 上海聚友化工有限公司 Method for continuously preparing biodegradable plastic
CN103012757A (en) * 2012-11-27 2013-04-03 中国包装科研测试中心 Preparation method of poly(butylene succinate)
CN103214659A (en) * 2013-03-25 2013-07-24 山东汇盈新材料科技有限公司 High molecular weight bio-based poly(butylene succinate) synthesis method

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Application publication date: 20210608