CN112080000B - Method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol - Google Patents
Method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol Download PDFInfo
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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 belongs to the technical field of high polymer materials, and relates to a method for synthesizing poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butylene terephthalate, wherein the PBATE material is prepared by synthesizing poly (adipic acid)/butylene terephthalate (PBAT) and m-epoxy pentadecylphenol, wherein the mass ratio of the PBAT to the m-epoxy pentadecylphenol is (1.8-19): 1; the m-epoxy pentadecylphenol is prepared by carrying out epoxidation reaction on m-pentadecylphenol and hydrogen peroxide under the action of weak acid and a catalyst, so that not only is phenolic hydroxyl reserved, but also an epoxy bond is generated; the two functional groups react with the terminal carboxyl in the PBAT together, so that the content of the terminal carboxyl in the PBATE can be obviously reduced, and the aging resistance of the PBATE is improved; and the mechanical property of the material is superior to that of PBAT, so a large amount of cheap filler can be added in practical application, thereby obviously reducing the production cost and having wide market application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a method for synthesizing poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butylene.
Background
In recent years, with the rapid development of social economy, the wide use of polymer materials, especially plastic films, brings great convenience to the life of people. The conventional plastic film material is mainly derived from petroleum, such as polyethylene, polypropylene, etc., and the plastic films also bring a series of environmental and energy problems during the use process. The existing plastic wastes in large quantity seriously affect the health and living environment of people, for example, the yield of agricultural land begins to be reduced due to the influence of waste mulching films, and the 'white pollution' caused by the waste plastics causes serious harm to the environment. Therefore, with the gradual decrease of non-renewable petroleum resources and the high concern of people on environmental protection, the development of a fully biodegradable plastic film material becomes a research hotspot of the whole society.
The poly adipic acid/butylene terephthalate (PBAT) is ternary copolyester polymerized from terephthalic acid, adipic acid and 1, 4-butanediol, and the structure of the copolyester contains flexible aliphatic chain and rigid aromatic bond, so that the copolyester has high toughness and high temperature resistance, and can be directly prepared into film materialsFeeding; due to the existence of aliphatic ester bond, the aliphatic ester bond is promoted to have biodegradability, and can be completely degraded by microorganisms in nature after being used, and finally CO is formed2And H2O, does not pollute the environment, and is a recognized environment-friendly material. PBAT is the most promising material for replacing the traditional plastics at present, but the large-scale development and application of the PBAT are restricted, and the PBAT is mainly expensive compared with the traditional plastics. In addition, the PBAT main chain structure has terminal carboxyl, so that the PBAT can be catalyzed to degrade, the aging resistance of the PBAT film is poor, the mechanical property in the use process can not meet the use requirement, and the like. Therefore, the optimization of the structure of the PBAT, the reduction of the content of the terminal carboxyl group in the structure, the improvement of the mechanical property and the reduction of the application cost have very important practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing poly (p-phthalic acid) -adipic acid-m-epoxy pentadecyl phenol butanediol, and the material synthesized by the method has low application cost, high mechanical property and low carboxyl end group content and can be completely biodegraded.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for synthesizing poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butylene, which comprises the following steps:
1) synthesis of m-epoxy pentadecylphenol: carrying out epoxidation reaction on m-pentadecenylphenol and hydrogen peroxide under the action of weak acid and a catalyst to prepare m-epoxy pentadecenylphenol, wherein the epoxy value of the m-epoxy pentadecenylphenol is more than or equal to 3.8 percent, and the viscosity at 25 ℃ is 8000-12000 cps;
2) synthesis of poly (butylene adipate/terephthalate): adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification reaction and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1 (1.8-2.2), and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: (0.001-0.003); the obtained poly adipic acidThe density of the butylene terephthalate is 1.20-1.30g/cm3The weight average molecular weight Mw is 10-15 ten thousand, and the melting point is 116-122 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl diester:
after the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into the reaction kettle in the step 2) to simultaneously perform esterification reaction and etherification reaction, wherein the reaction time is 1-3h, the reaction temperature is 160-180 ℃, and after the reaction is finished, the poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butanediol material is prepared by pulling strips and cutting particles;
or adding the m-epoxy pentadecylphenol obtained in the step 1) and the poly (butylene adipate)/terephthalate obtained in the step 2) into a reactive double-screw extruder for extrusion reaction for 10-20min, and after the reaction, drawing into strips and cutting into granules to obtain the poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butylene material.
Preferably, in the epoxidation reaction in step 1), the mass ratio of m-pentadecenylphenol, hydrogen peroxide, weak acid and catalyst is 1: (0.5-0.8): (0.1-0.3): (0.01-0.03).
Preferably, in the epoxidation reaction in the step 1), the reaction temperature is 40-60 ℃ and the reaction time is 3-5 h.
Preferably, in the epoxidation reaction in step 1), the catalyst is sulfuric acid or phosphoric acid, and the weak acid is at least one of formic acid and acetic acid.
Preferably, the epoxidation reaction in the step 1) further comprises the following processes of washing with water and removing water by reduced pressure distillation, wherein the washing with warm water at 30-50 ℃ is carried out for more than three times, and the temperature of the reduced pressure distillation is 50-70 ℃.
The purpose of washing with warm water at 30-50 ℃ for more than three times is to wash away residual hydrogen peroxide and formic acid in the epoxidation reaction product.
Preferably, the esterification reaction temperature in the step 2) is 170-210 ℃, the esterification reaction time is 3-4h, and the reaction is a normal pressure reaction.
Preferably, the polycondensation reaction temperature in the step 2) is 240-.
Preferably, the weight ratio of the polybutylene adipate/terephthalate to the m-epoxy pentadecylphenol in step 3) is (1.8-19): 1.
more preferably, the weight ratio of the polybutylene adipate/terephthalate to the m-epoxy pentadecylphenol in step 3) is (4-9): 1.
preferably, the reactive twin-screw extruder in the step 3) is a co-rotating twin-screw extruder, the operating temperature is 160-180 ℃, and the screw rotating speed is 50-150 rpm.
Compared with the prior art, the invention has the following advantages:
1) the method comprises the steps of carrying out epoxidation reaction on m-pentadecenylphenol on the premise of keeping phenolic hydroxyl to generate m-epoxy pentadecenylphenol, reacting the phenolic hydroxyl and epoxy bonds in the m-epoxy pentadecenylphenol with terminal carboxyl in poly adipic acid/butylene terephthalate (PBAT for short), wherein the phenolic hydroxyl reacts with the terminal carboxyl in the PBAT to generate ester bonds, and the epoxy bonds are opened to react with the terminal carboxyl in the PBAT to generate ether bonds, so that the content of the terminal carboxyl in the PBAT can be effectively reduced, and the aging resistance of the PBAT material is improved;
2) the m-epoxy pentadecylphenol not only has the rigidity of a benzene ring compound, but also has the flexibility of an aliphatic compound, the structure of the PBAT is optimized and synthesized by using the m-epoxy pentadecylphenol to obtain the PBATE material, the mechanical property of the material is obviously superior to that of the PBAT, and a large amount of cheap filler can be added in practical application, so that the application cost is effectively reduced.
Drawings
FIG. 1 is an FTIR chart of m-epoxy pentadecylphenol obtained in step 1) of example 4;
FIG. 2 is an FTIR plot of the PBAT obtained in step 2) of example 4;
FIG. 3 is a FTIR plot of the PBATE obtained in step 3) of example 4;
FIG. 4 shows the preparation of m-pentadecylphenol obtained in step 1) of example 41H-NMR spectrum;
FIG. 5 shows the PBAT obtained in step 2) of example 41H-NMR spectrum;
FIG. 6 shows the PBATE obtained in step 3) of example 41H-NMR spectrum.
Detailed Description
The following further describes embodiments of the present invention with reference to specific examples.
Example 1
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) synthesis of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 50g of formic acid were charged into a three-necked round-bottomed flask with mechanical stirring, a separatory funnel and a thermometer at 390g of 50% H2O2Adding 5g of phosphoric acid, adding into a separating funnel, dropwise adding, wherein the dropwise adding temperature is not more than 40 ℃, heating to 60 ℃ after the dropwise adding is finished, continuing to react for 3 hours, standing for layering after the reaction is finished, separating out lower-layer acid water, washing upper-layer oil ester to be neutral, and distilling under reduced pressure at 50 ℃ to remove water to obtain light yellow oily substance m-epoxy pentadecyl phenol, wherein the epoxy value of the m-epoxy pentadecyl phenol is 4.52%, and the viscosity at 25 ℃ is 8250 cps;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:1.8, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.003, the esterification reaction temperature is 170 ℃, the esterification reaction time is 4h, and the normal pressure is realized; the polycondensation reaction temperature is 240 ℃, the polycondensation reaction time is 3h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.22g/cm3Weight average molecular weight Mw of 10 ten thousand and melting point of 116.5 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
After the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into a reaction kettle to perform esterification and etherification reactions for 1h at 180 ℃, wherein the mass ratio of PBAT to the m-epoxy pentadecylphenol is 95:5, and after the reaction is finished, drawing strips and cutting particles to obtain the PBATE material.
Example 2
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 70g of formic acid are introduced into a three-necked round-bottomed flask with mechanical stirring, a separating funnel and a thermometer at 350g of 50% H2O2Adding 8g of phosphoric acid, adding into a separating funnel, dropwise adding, wherein the dropwise adding temperature is not more than 40 ℃, heating to 55 ℃ after the dropwise adding is finished, continuing to react for 3.5 hours, standing for layering after the reaction is finished, separating out lower acid water, washing upper oil ester to be neutral, and distilling under reduced pressure at 55 ℃ to remove water to obtain light yellow oily substance m-epoxy pentadecylphenol, wherein the epoxy value of the m-epoxy pentadecylphenol is 4.47%, and the viscosity at 25 ℃ is 8968 cps;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:1.9, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.0025, the esterification reaction temperature is 180 ℃, the esterification reaction time is 3.5h, and the pressure is normal; the polycondensation reaction temperature is 250 ℃, the polycondensation reaction time is 2h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.27g/cm3The weight average molecular weight Mw is 12 ten thousand, and the melting point is 117.2 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
After the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into a reaction kettle to perform esterification and etherification reactions for 2 hours at the same time, wherein the mass ratio of PBAT to the m-epoxy pentadecylphenol is 90:10, and after the reaction is finished, drawing strips and cutting particles to obtain the PBATE material.
Example 3
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 100g of formic acid were charged in a three-necked round-bottomed flask with mechanical stirring, a separating funnel and a thermometer at 300g of 50% H2O2Adding 10g of phosphoric acid, adding into a separating funnel, dropwise adding, wherein the dropwise adding temperature is not more than 40 ℃, heating to 50 ℃ after the dropwise adding is finished, continuously reacting for 4 hours, standing for layering after the reaction is finished, separating out lower-layer acid water, washing upper-layer oil ester to be neutral, and distilling under reduced pressure at 60 ℃ to remove water to obtain light yellow oily substance m-epoxy pentadecylphenol, wherein the epoxy value of the m-epoxy pentadecylphenol is 4.31%, and the viscosity at 25 ℃ is 9525 cps;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the usage amount of the adipic acid and the terephthalic acid to the usage amount of the butanediol is 1:2, and the molar ratio of the sum of the usage amount of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.002, the esterification reaction temperature is 190 ℃, the esterification reaction time is 3.5h, and the pressure is normal; the polycondensation reaction temperature is 260 ℃, the polycondensation reaction time is 2 hours, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.25g/cm3The weight average molecular weight Mw is 13 ten thousand, and the melting point is 118.1 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
After the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into a reaction kettle to perform esterification and etherification reactions for 3 hours at the same time, wherein the mass ratio of PBAT to the m-epoxy pentadecylphenol is 85:15, and after the reaction is finished, drawing strips and cutting particles to obtain the PBATE material.
Example 4
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 115g of formic acid are introduced into a three-necked round-bottomed flask with mechanical stirring, a separating funnel and a thermometer at 280g of 50% H2O2Adding 12g of concentrated sulfuric acid into the mixture, adding the mixture into a separating funnel, beginning to dropwise add the mixture, keeping the dropwise adding temperature below 40 ℃, heating to 45 ℃ after the dropwise adding is finished, continuing to react for 4.5 hours, standing and layering the mixture after the reaction is finished, separating acid water on the lower layer, washing oil ester on the upper layer to be neutral, and distilling under reduced pressure at 65 ℃ to remove water to obtain light yellow oily substance-m-epoxy pentadecyl phenol, wherein the epoxy value of the m-epoxy pentadecyl phenol is 4.23%, and the viscosity at 25 ℃ is 10246;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:2.1, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.0015, the esterification reaction temperature is 200 ℃, the esterification reaction time is 3 hours, and the pressure is normal; the polycondensation reaction temperature is 270 ℃, the polycondensation reaction time is 1.5h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.30g/cm3The weight average molecular weight Mw is 14 ten thousand, and the melting point is 119.6 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
After the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into a reaction kettle for esterification and etherification reactions for 2 hours at the same time, wherein the reaction temperature is 175 ℃, the mass ratio of PBAT to m-epoxy pentadecylphenol is 80:20, and after the reaction is finished, drawing strips and cutting particles to obtain the PBATE material.
Example 5
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 127g of formic acid were added with mechanical stirringIn a three necked round bottom flask with liquid funnel and thermometer at 270g 50% H2O2Adding 13g of concentrated sulfuric acid into the mixture, adding the mixture into a separating funnel, beginning to dropwise add the mixture, keeping the dropwise adding temperature below 40 ℃, continuing to react for 5 hours at 40 ℃ after the dropwise adding is finished, standing and layering the mixture after the reaction is finished, separating acid water at the lower layer, washing oil ester at the upper layer to be neutral, and distilling the mixture under reduced pressure at 70 ℃ to remove water to obtain light yellow oily substance m-epoxy pentadecylphenol, wherein the epoxy value of the m-epoxy pentadecylphenol is 4.08%, and the viscosity of the m-epoxy pentad;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:2.2, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.001, the esterification reaction temperature is 210 ℃, the esterification reaction time is 3h, and the pressure is normal; the polycondensation reaction temperature is 250 ℃, the polycondensation reaction time is 2h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.24g/cm3The weight average molecular weight Mw is 15 ten thousand, and the melting point is 121.3 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
Carrying out bracing and dicing on the PBAT obtained in the step 2) to obtain PBAT granules, and carrying out vacuum drying on the PBAT granules at 70 ℃ for 4 h; setting the rotating speed of the reaction type double-screw extruder at 50rpm and 180 ℃, adding the dried PBAT and the m-epoxy pentadecylphenol prepared in the step 1) into the reaction type double-screw extruder at a mass ratio of 75:25, and performing extrusion reaction for 20min to obtain the PBATE material.
Example 6
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 140g of formic acid are introduced into a three-necked round-bottomed flask with mechanical stirring, a separating funnel and a thermometer at 250g of 50% H2O2Adding 15g of concentrated sulfuric acid into the mixture, adding the mixture into a separating funnel, beginning to dropwise add the mixture, keeping the dropwise adding temperature below 40 ℃, heating to 55 ℃ after the dropwise adding is completed, continuing to react for 4 hours, standing and layering the mixture after the reaction is finished, separating acid water at the lower layer, washing oil ester at the upper layer to be neutral, and distilling under reduced pressure at 60 ℃ to remove water to obtain light yellow oily substance m-epoxy pentadecylphenol, wherein the epoxy value of the m-epoxy pentadecylphenol is 3.92%, and the viscosity of the m-epoxy pentadec;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:2, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.0015, the esterification reaction temperature is 180 ℃, the esterification reaction time is 4 hours, and the pressure is normal; the polycondensation reaction temperature is 260 ℃, the polycondensation reaction time is 1.5h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.23g/cm3The weight average molecular weight Mw is 11 ten thousand, and the melting point is 119.8 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
Carrying out bracing and dicing on the PBAT obtained in the step 2) to obtain PBAT granules, and carrying out vacuum drying on the PBAT granules at 80 ℃ for 3 h; setting the rotating speed of the reaction type double-screw extruder as 100rpm, setting the temperature as 170 ℃, adding the dried PBAT and the m-epoxy pentadecylphenol prepared in the step 1) into the reaction type double-screw extruder at a mass ratio of 70:30, and performing extrusion reaction for 15min to obtain the PBATE material.
Example 7
A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl diester comprises the following steps:
1) preparation of m-epoxy pentadecyl phenol
500g of m-pentadecenylphenol and 150g of formic acid are introduced into a three-necked round-bottomed flask with mechanical stirring, a separating funnel and a thermometer at 320g of 50% H2O2Adding 7g of phosphoric acid, adding into a separating funnel, and starting dropwise addingThe dripping temperature is not more than 40 ℃, the temperature is raised to 50 ℃ after the dripping is finished, the reaction is continued for 5 hours, the mixture is kept stand and layered after the reaction is finished, the lower acid water layer is separated, the upper oil ester is washed to be neutral, and the light yellow oily substance m-epoxy pentadecyl phenol is obtained by reduced pressure distillation and water removal at 55 ℃, the epoxy value of the m-epoxy pentadecyl phenol is 3.65 percent, and the viscosity at 25 ℃ is 11967 cps;
2) synthesis of Poly (butylene adipate terephthalate) (PBAT)
Adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1:1.9, and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: 0.002, the esterification reaction temperature is 190 ℃, the esterification reaction time is 3h, and the pressure is normal; the polycondensation reaction temperature is 240 ℃, the polycondensation reaction time is 3h, and the pressure is less than 50 Pa; the density of the PBAT obtained was 1.29g/cm3The weight average molecular weight Mw is 13 ten thousand, and the melting point is 118.7 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl ester (PBATE)
Carrying out bracing and dicing on the PBAT obtained in the step 2) to obtain PBAT granules, and carrying out vacuum drying on the PBAT granules at 90 ℃ for 2 h; setting the rotating speed of the reaction type double-screw extruder at 150r/min and the temperature at 160 ℃, adding the dried PBAT and the m-epoxy pentadecylphenol prepared in the step 1) into the reaction type double-screw extruder at a mass ratio of 65:35, and performing extrusion reaction for 10min to obtain the PBATE material.
Structural analysis:
a. infrared spectrogram
Samples of example 4 were taken for infrared testing in three steps, and the results are shown in fig. 1-3.
As shown in FIG. 1, 3373cm in the infrared spectrum of the m-epoxypentadecylphenol produced in step 1)-1The stretching vibration absorption of hydroxyl groups; 2927cm-1Is a saturated hydrocarbon CH2C-H asymmetric telescopic vibration absorption; 2854cm-1Is a saturated hydrocarbon CH2C-H symmetric telescopic vibration absorption; 1599cm-1A backbone vibration absorption for aromatic ring C ═ C; 1276cm-1C-OH stretching vibration absorption of phenol; 828cm-1Is asymmetrical telescopic vibration absorption of ternary cyclic ether (epoxy bond) C-O-C; 724cm-1Plane rocking vibration of methylene; 696cm-1Is aromatic ring ═ C-H shock absorbing.
As shown in FIG. 2, 2952cm in the infrared spectrum of the PBAT obtained in step 2)-1Is a saturated hydrocarbon CH2C-H asymmetric telescopic vibration absorption; 1708cm-1C ═ O stretching shock absorption for the ester, indicating that there are more carbonyl groups in PBAT; 1504cm-1Is the stretching vibration absorption of aromatic ring C ═ C; 1458cm-1Is a saturated hydrocarbon-CH2-in-plane bending vibration absorption; 1268cm-1-C-O-telescopic vibration absorption; 726cm-1Out-of-plane bending vibration absorption of-CH-which is an aromatic ring.
As can be seen from a comparison of FIGS. 1 and 2, 3412cm in the infrared spectrum of the PBATE obtained in step 3) of FIG. 3 is found-1The peak ratio of the absorption of stretching vibration of hydroxyl group at (A) is 3373cm in FIG. 1-1The peak is obviously weakened and originally 828cm-1The position shows that the asymmetric stretching vibration absorption peak of ternary cyclic ether (epoxy bond) C-O-C disappears, which indicates that phenolic hydroxyl in meta-epoxy pentadecylphenol reacts with terminal carboxyl in PBAT to generate ester bond, the epoxy bond is opened to react with the terminal carboxyl in PBAT to generate ether bond, and thus the content of the terminal carboxyl in PBAT is obviously reduced (see table 1 below).
b. Nuclear magnetic resonance hydrogen spectrum
The hydrogen nuclear magnetic test was performed on the samples obtained in the three steps of example 4, and the results are shown in FIGS. 4 to 6, in which the solvent peak is at 7.26 ppm.
As shown in FIG. 4, in the preparation of m-epoxypentadecylphenol obtained in the step 1)1In the H-NMR spectrum, the peak at δ ═ 0.89ppm was assigned to the methyl group, the peak at δ ═ 1.30ppm was assigned to the methylene group on the backbone chain, the peak at δ ═ 1.51ppm was assigned to the methylene group attached to the methyl group, the peak at δ ═ 2.52ppm was assigned to the methylene group attached to the ethylenic bond, the peak at δ ═ 2.95ppm was assigned to the H on the carbon attached to O in the epoxy structure, and the peak at δ ═ 3.4 to 3.8ppm was assigned to the phenolic hydroxyl groupThe peak at 6.65-7.12ppm of H, delta, is assigned to the aromatic ring.
As shown in FIG. 5, in the PBAT obtained in step 2)1In the H-NMR spectrum, the peak at δ ═ 1.56ppm was assigned to the methylene group in the middle of the adipic acid fragment, the peak at δ ═ 1.69ppm was assigned to the methylene group in the middle of the butanediol fragment connected to adipic acid, the peak at δ ═ 1.97ppm was assigned to the methylene group in the middle of the butanediol fragment connected to terephthalic acid, the peak at δ ═ 2.33ppm was assigned to the methylene group in the adipic acid fragment connected to the ester bond formed by adipic acid and butanediol, the peak at δ ═ 4.09 to 4.15ppm was assigned to the methylene group in the butanediol fragment connected to the ester bond formed by adipic acid and butanediol, the peak at δ ═ 4.38 to 4.43ppm was assigned to the methylene group in the butanediol fragment connected to the ester bond formed by terephthalic acid and butanediol, and the peak at δ ═ 8.10ppm was assigned to H on the aromatic ring of terephthalic acid fragment.
As can be seen from a comparison of FIGS. 4 and 5, in FIG. 6 the PBATE obtained in step 3)1In the H-NMR spectrum, the peak area attributed to H on the O-linked carbon in the epoxy structure at δ of 2.95ppm was reduced from 1.40 in fig. 4 to 0.34 in fig. 6, and was significantly reduced; the peak area of the methylene group at δ ═ 2.33ppm, assigned to the adipic acid fragment connected to the ester bond, increased from 1.06 in fig. 5 to 1.34 in fig. 6, indicating that the phenolic hydroxyl group in m-epoxypentadecylphenol reacted with the terminal carboxyl group in PBAT to form an ester bond, and the epoxy bond was opened to react with the terminal carboxyl group in PBAT to form an ether bond.
The detailed analysis of FIGS. 1-6 fully illustrates the synthesis of a new poly (p-phenylene terephthalate) -adipic acid-m-epoxy pentadecylphenol butylene ester material by the method of the present invention.
Comparative example: the pure PBAT pellets were dried under vacuum at 90 ℃ for 2h until use.
The carboxyl end group contents of the PBATE materials prepared in examples 1 to 7 and the pure PBAT material of the comparative example were tested according to the method for testing the carboxyl end group content of polyester in GB/T14190-20175.4; the PBATE materials prepared in examples 1-7 and the pure PBAT material of the comparative example were pressed into sheets of 1mm thickness for mechanical property testing according to GB/T1040-.
TABLE 1 PBAT and PBATE mechanical Properties and end carboxyl content test results
| Film samples | Elongation at break/% | Tensile strength/MPa | Content of terminal carboxyl groups/(mol/t) |
| Comparative example | 684.51 | 28.92 | 56.46 |
| Example 1 | 760.58 | 28.90 | 45.85 |
| Example 2 | 829.34 | 28.97 | 38.67 |
| Example 3 | 1014.82 | 32.20 | 27.98 |
| Example 4 | 1301.86 | 32.56 | 16.68 |
| Example 5 | 986.34 | 25.41 | 11.24 |
| Example 6 | 956.63 | 19.43 | 7.10 |
| Example 7 | 900.56 | 18.38 | 2.35 |
As shown in Table 1, the carboxyl end group content of the pure PBAT material in the comparative example is 56.46mol/t, from example 1 to example 7, the carboxyl end group content of the PBAT material obtained by synthesis is obviously reduced along with the increasing weight ratio of the m-epoxy pentadecylphenol to the PBAT, when the weight ratio of the m-epoxy pentadecylphenol to the PBAT in example 7 is 35: at 65, the carboxyl end group content of the PBATE material was reduced to 2.35 mol/t. In the synthesis reaction, phenolic hydroxyl and epoxy bond in m-epoxy pentadecylphenol react with terminal carboxyl in PBAT to generate ester bond, and the epoxy bond is opened to react with the terminal carboxyl in PBAT to generate ether bond, so that the content of the terminal carboxyl in PBAT can be effectively reduced, and the aging resistance of the PBATE material is improved.
As shown in table 1, the elongation at break of the pure PBAT material in the comparative example is 684.51%, and from example 1 to example 7, the elongation at break of the synthesized PBAT material shows a tendency of increasing and then decreasing with increasing weight ratio of m-epoxy pentadecylphenol to PBAT, but all are significantly greater than the elongation at break of the pure PBAT material in the comparative example, where when the weight ratio of m-epoxy pentadecylphenol to PBAT in example 4 is 20: at 80, the elongation at break of the PBATE material is 1301.86%, which is about 90% higher than that of the pure PBAT material in the comparative example; when the weight ratio of m-epoxy pentadecylphenol to PBAT in example 7 is 35: 65, the elongation at break of this PBATE material is 900.56%, which is about 31% higher than the elongation at break of the pure PBAT material in the comparative example. Similarly, from example 1 to example 7, the tensile strength of the synthesized PBATE material also shows a tendency of increasing first and then decreasing with the increasing weight ratio of m-epoxy pentadecylphenol to PBAT, wherein the tensile strength of the PBATE material in example 4 is 32.56MPa, which is greater than that of the pure PBAT material in the comparative example; the tensile strength of the PBATE material in example 7 was 18.38MPa, which, although less than the tensile strength of the pure PBAT material in the comparative example, still met the daily use requirements of people. The reason is that the structure of the m-epoxy pentadecylphenol contains a long C15 chain and a benzene ring structure, so that the m-epoxy pentadecylphenol not only has the rigidity of a benzene ring compound, but also has the flexibility of an aliphatic compound, thereby obviously improving the elongation at break of the PBATE material, and also improving the tensile strength of the PBATE material within a certain addition range.
Meanwhile, it is found that when the weight proportion of the m-pentadecylphenol exceeds 35%, after a thin film product prepared from the synthesized PBATE material is placed in the air for 7 days, oil stains on the surface of the thin film product seep out and become sticky, so that the weight proportion of the m-pentadecylphenol used in synthesizing the PBATE material is not more than 35%.
Application example:
according to GB/T1040-.
TABLE 2 PBAT and PBATE test formulas with filler addition and mechanical property test results
| Experiment number | ① | ② | ③ | ④ | ⑤ | ⑥ |
| PBAT/ |
100 | 100 | 100 | |||
| PBATE/ |
100 | 100 | 100 | |||
| Calcium carbonate/ |
50 | 100 | 150 | 50 | 100 | 150 |
| Lubricant/g | 1 | 1 | 1 | 1 | 1 | 1 |
| Elongation at break/% | 389.23 | 250.46 | 123.84 | 820.14 | 455.12 | 262.25 |
| Tensile strength/MPa | 23.15 | 15.22 | 13.75 | 25.26 | 18.57 | 16.31 |
As shown in Table 2, when the same amount of calcium carbonate is added, the elongation at break and tensile strength of the film product made of PBATE material are both greater than those of pure PBAT material; with the increase of the proportion of calcium carbonate in the formula, the elongation at break and the tensile strength of the film product made of the PBATE material are reduced, but the elongation at break is more than 200%, and the tensile strength is more than 16MPa, so that the daily use requirement of people can be met. Therefore, in the practical application of PBATEs, a large amount of inorganic filler can be added, reducing the cost of their application.
The present invention has been described in detail with reference to the preferred embodiments. However, variations and additions to the embodiments will become apparent to those of ordinary skill in the art upon a reading of the foregoing description. It is the intention of the applicants that all such variations and additions fall within the scope of the claims. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any modification and improvement of this product, and the substitution and use of the same or similar substances within the scope or range of patents, shall fall within the scope of protection of this invention.
Claims (9)
1. A method for synthesizing poly terephthalic acid-adipic acid-m-epoxy pentadecylphenol butyl ester is characterized by comprising the following steps:
1) synthesis of m-epoxy pentadecylphenol: carrying out epoxidation reaction on m-pentadecenylphenol and hydrogen peroxide under the action of weak acid and a catalyst to prepare m-epoxy pentadecenylphenol, wherein the epoxy value of the m-epoxy pentadecenylphenol is more than or equal to 3.8 percent, and the viscosity at 25 ℃ is 8000-12000 cps; wherein the catalyst is sulfuric acid or phosphoric acid, and the weak acid is at least one of formic acid and acetic acid;
2) synthesis of poly (butylene adipate/terephthalate): adopting a co-esterification mode, taking tetrabutyl titanate as a catalyst, and putting adipic acid, terephthalic acid and butanediol into a reaction kettle to carry out esterification reaction and polycondensation reaction in sequence, wherein the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the use amount of the butanediol is 1 (1.8-2.2), and the molar ratio of the sum of the use amounts of the adipic acid and the terephthalic acid to the tetrabutyl titanate is 1: (0.001-0.003); the density of the prepared poly (butylene adipate/terephthalate) is 1.20-1.30g/cm, the weight average molecular weight Mw is 10-15 ten thousand, and the melting point is 116-122 ℃;
3) synthesis of poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butyl diester:
after the polycondensation reaction in the step 2) is finished, adding the m-epoxy pentadecylphenol obtained in the step 1) into the reaction kettle in the step 2) to simultaneously perform esterification reaction and etherification reaction, wherein the reaction time is 1-3h, the reaction temperature is 160-180 ℃, and after the reaction is finished, the poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butanediol material is prepared by pulling strips and cutting particles;
or adding the m-epoxy pentadecylphenol obtained in the step 1) and the poly (butylene adipate)/terephthalate obtained in the step 2) into a reactive double-screw extruder for extrusion reaction for 10-20min, and after the reaction, drawing into strips and cutting into granules to obtain the poly (terephthalic acid) -adipic acid-m-epoxy pentadecylphenol butylene material.
2. The method of claim 1, wherein the method comprises the steps of: in the epoxidation reaction in the step 1), the mass ratio of m-pentadecenylphenol, hydrogen peroxide, weak acid and a catalyst is 1: (0.5-0.8): (0.1-0.3): (0.01-0.03).
3. The method of claim 1, wherein the method comprises the steps of: in the epoxidation reaction in the step 1), the reaction temperature is 40-60 ℃, and the reaction time is 3-5 h.
4. The method of claim 1, wherein the method comprises the steps of: the epoxidation reaction in the step 1) also comprises the following processes of washing with water and removing water by reduced pressure distillation, wherein the washing with water is carried out for more than three times at the temperature of 30-50 ℃, and the temperature of the reduced pressure distillation is 50-70 ℃.
5. The method of claim 1, wherein the method comprises the steps of: the esterification reaction temperature in the step 2) is 170-210 ℃, the esterification reaction time is 3-4h, and the reaction is a normal pressure reaction.
6. The method of claim 1, wherein the method comprises the steps of: the polycondensation reaction temperature in the step 2) is 240-270 ℃, the polycondensation reaction time is 1.5-3h, and the pressure is less than 50 Pa.
7. The method of claim 1, wherein the method comprises the steps of: the weight ratio of the polybutylene adipate/terephthalate to the m-epoxy pentadecylphenol in the step 3) is (1.8-19): 1.
8. the method of claim 1, wherein the method comprises the steps of: the weight ratio of the polybutylene adipate/terephthalate to the m-epoxy pentadecylphenol in the step 3) is (4-9): 1.
9. the method of claim 1, wherein the method comprises the steps of: the reactive double-screw extruder in the step 3) is a co-rotating double-screw extruder, the operating temperature is 160-180 ℃, and the screw rotating speed is 50-150 rpm.
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