CN114790282B - Preparation method and application of nano-microparticle in-situ polymerization catalyst - Google Patents
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention relates to a preparation method and application of a poly (terephthalic acid) -butanediol adipate nano microparticle in-situ polymerization catalyst, wherein the catalyst is prepared by the following steps: (1) Adding metal carboxylate with certain mass into a mixed solution of an alcohol compound with a molecular structure only provided with one hydroxyl and distilled water for reaction; (2) After alpha-hydroxy acid or alpha-amino acid is added, the system is refluxed and reacted for a period of time to prepare the in-situ polymerization catalyst. The poly (butylene terephthalate) -adipate nano microparticle in-situ polymerization catalyst disclosed by the invention is small in particle size, good in dispersity, high in activity, deliquescent-resistant, heat-resistant and light-resistant, can be stored for a long time in a natural environment, can be used for catalytically synthesizing poly (butylene terephthalate) -adipate with high molecular weight and low chroma, and can also be used for greatly improving the crystallization rate and the crystallization temperature. The physical and mechanical properties of the PBAT are improved and the application market range thereof is expanded.
Description
Technical Field
The invention belongs to the technical field of synthesis of biodegradable aliphatic polyester high polymer materials, and relates to a preparation method and application of a nanoparticle in-situ polymerization catalyst for preparing poly (butylene adipate-terephthalate).
Background
Increasingly exhausted fossil resources, CO 2 Under the background of global warming and serious environmental pollution caused by excessive emission and the like, the global consensus is achieved by turning to low-carbon circular economy, policies such as carbon peak reaching and carbon neutralization are brought into the overall layout of ecological civilization construction, and new energy and new materials are searched to replace petrochemical products, so that the global common mission is realized.
The main chain of poly (butylene adipate terephthalate) (PBAT) is formed by connecting aliphatic structural units and aromatic structural units through ester bonds which are easy to hydrolyze, and the poly (butylene terephthalate) (PBAT) is easy to be decomposed and metabolized by a plurality of microorganisms or animal and plant enzymes in the nature and finally converted into CO2 and H2O. Compared with the traditional biodegradable polyester, the PBAT has higher melting point, good mechanical ductility, processability and physical and mechanical properties, can be processed by injection molding, blow molding, film blowing and other forming methods, has wide application, can be applied to the field of packaging, medicine and health, agriculture and the like, and meets the requirements of environmental protection and sustainable development strategy.
Patent CN 100528929C discloses a process for preparing aliphatic polyester, which comprises compounding metal alkoxide and titanium silicon oxide with phosphoric acid compound to synthesize aliphatic dibasic acid ester with high molecular weight and good chromaticity. However, the preparation steps of the catalyst are complicated, and the production energy consumption is greatly increased.
Patent CN 103130992A relates to a preparation method of high molecular weight poly (butylene adipate-terephthalate), wherein the catalyst is a mixture of metal oxide and titanium organic ester, and the method of adding the catalyst in the esterification stage and adding the heat stabilizer in the polycondensation stage is adopted to improve the molecular weight of the polymer and reduce the terminal carboxyl value of the polymer. However, the preparation process of the catalyst is complicated, the problem that the titanium organic ester catalyst is easy to hydrolyze is not solved, and unstable factors are added to the production process.
Patent CN 104558574B synthesizes a titanium polyester catalyst, metal salt compounds, titanates and dihydric alcohol are mixed and reacted, then phosphoric acid compounds are added for continuous reaction to prepare the catalyst, the problem that in the prior art, the prepared dihydric alcohol compounds of titanium have side reactions such as thermal degradation and the like caused by overhigh catalyst activity is solved, but titanium dioxide/ethylene glycol slurry is required to be supplemented in the operation process, the process steps are complicated, and the reaction temperature is too high.
The patent CN 112280259A uses the commercial polybutylene adipate-terephthalate (PBAT), uses polybutylene terephthalate (PBT) accounting for 0-50% of the total weight of raw materials as a nucleating agent, and also selects inorganic substances such as boron nitride, calcium carbonate and the like as auxiliary nucleating agents, so that the crystallization temperature and the crystallization rate of the commercial PBAT are improved. Although the PBAT copolyester composite material with higher crystallinity and excellent mechanical property is prepared by the method using a large amount of non-degradable PBT as the nucleating agent, the application of PBAT as biodegradable plastic is greatly limited, and the environmental burden is increased.
Patent CN 108384201A relates to a PBAT material with a high crystallization speed and a preparation method thereof, wherein a xylylene dialkyl urea is used as a nucleating agent to promote crystallization of PBAT, so that the crystallization speed and mechanical properties of PBAT can be improved. But the PBAT matrix and the nucleating agent are from commercial products, and the nucleating agent contains a benzene ring structure with toxicity, so that the application of biodegradable PBAT is greatly limited.
Patent CN 108384200A mentions that melamine/cyanuric acid complex is used as a nucleating agent to promote crystallization of PBAT, so that crystallization speed and mechanical properties of PBAT are improved, and the highest crystallization temperature is 74.2 ℃. But the PBAT matrix comes from commercial products and the nucleating agent contains a toxic melamine/acid structure, which greatly limits the application of biodegradable PBAT.
Patent CN 108047503A relates to a PBAT copolyester composition, a preparation method thereof and a nucleating agent used therein, the nucleating agent is composed of one or more thermoplastic starches, which are dispersed throughout the PBAT to increase crystallization rate and crystallinity. The thermoplastic starch consists of starch, a modifier and a plasticizer, and also comprises at least one of an aging resistant agent, a flow assistant, an opening agent, a blocking agent, a filler, a compatilizer and a pigment, so that the preparation process is complicated. The highest crystallization temperature of PBAT was 70.6 ℃ and the crystallinity was only 29.8%.
It can be seen that the existing research can only increase the molecular weight of PBAT unilaterally or increase the crystallization rate of commercialized PBAT, the preparation process of the related catalyst or nucleating agent is complicated, the production energy consumption is increased, and the PBAT cannot have high molecular weight and high crystallization rate at the same time. Therefore, it is of great significance to develop and prepare the nano-microparticle in-situ polymerization catalyst which can accelerate the crystallization rate and improve the crystallization temperature of PBAT while catalytically synthesizing PBAT with high molecular weight and low chroma.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method and application of a poly (butylene terephthalate-adipate) nano-microparticle in-situ polymerization catalyst. The preparation method of the poly (butylene terephthalate) -adipate nano-microparticle in-situ polymerization catalyst provided by the invention adopts alpha-hydroxy acid or alpha-amino acid of biological origin as a raw material, and can accelerate the crystallization rate and improve the crystallization temperature of PBAT while catalytically synthesizing high molecular weight and low chroma PBAT.
The invention provides a nano-microparticle in-situ catalyst for preparing polybutylene terephthalate-adipate, which is prepared by the following steps:
(1) Adding metal carboxylate with certain mass into a mixed solution of alcohol compounds with a certain proportion of molecular structures and only one hydroxyl and distilled water at low temperature, and stirring;
(2) Adding alpha-hydroxy acid or alpha-amino acid, stirring, slowly heating to 10 ℃ above the boiling point of the low-boiling-point monohydric alcohol, and carrying out reflux reaction on the system;
(3) And after the reaction is finished, closing the mechanical stirring, cooling to room temperature, carrying out suction filtration under a reduced pressure condition, washing a filter cake for three times by using absolute ethyl alcohol, and carrying out vacuum drying at room temperature to obtain the in-situ polymerization catalyst.
Wherein the mass ratio of the alcohol compound with only one hydroxyl group in the molecular structure to the distilled water is 20-40:1; the mass ratio of the alpha-hydroxy acid or the alpha-amino acid to the metal acetate is 1.6-2.8:1.
Wherein the low temperature condition in the step (1) is-5-5 ℃, the stirring speed is 300r/min, and the stirring time is 10min;
the stirring time in the step (2) is 10-30min, and the reflux reaction time is 2-5 hours.
Wherein the alcohol compound with only one hydroxyl in the molecular structure is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol.
Wherein the alpha-hydroxy acid is more than one of glycolic acid, lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid; the alpha-amino acid is at least one of glycine, alanine, phenylalanine, threonine, valine, leucine or isoleucine.
Wherein the mass of the metal carboxylate in the step (1) is 0.01-0.03 times of that of the mixed solution; the metal carboxylate is at least one of metal calcium, magnesium, zinc, aluminum, iron, cobalt, nickel and copper acetate, oxalate, malonate, succinate, glutarate and adipate.
Wherein the nano-microparticle in-situ polymerization catalyst is white powdery solid; the particle size of the nanometer microparticle in-situ polymerization catalyst is 50-100nm.
The invention also provides a preparation method of the polybutylene terephthalate-adipate, which takes adipic acid, terephthalic acid and 1, 4-butanediol as raw materials and sequentially carries out esterification reaction, pre-polycondensation reaction and final polycondensation reaction under the action of the in-situ catalyst to prepare the polybutylene adipate-terephthalate.
Wherein the prepared in-situ polymerization catalyst is added into a reaction system before the ester exchange reaction, and the using amount is 0.5-1.5 per mill of the total mass of the system.
Wherein the molar ratio of the alkyd in the reaction system is 1.4:1, wherein the mass ratio of adipic acid to terephthalic acid is 1:1; the esterification temperature is 200-220 ℃, and the esterification time is 150-200min; the pre-polycondensation temperature is 230-250 ℃, the pre-polycondensation pressure is 1k-2kPa absolute, and the pre-polycondensation time is 30-50min; the polycondensation temperature is 230-250 deg.C, the polycondensation pressure is 5-30Pa, and the polycondensation time is 120-180min.
The preparation method of the poly (butylene terephthalate) -adipate nano-microparticle in-situ polymerization catalyst provided by the invention is prepared by adopting alpha-hydroxy acid or alpha-amino acid from biological sources as a raw material, and the preparation process is simple and convenient, is easy to operate and has no pollution to the environment. Compared with other catalysts, the in-situ polymerization catalyst used in the invention has the following advantages:
(1) The in-situ polymerization catalyst has simple synthesis steps and low energy consumption;
(2) The used alpha-hydroxy acid or alpha-amino acid is environment-friendly, and the application range of biodegradable PBAT is not influenced;
(3) The synthesized in-situ polymerization catalyst is nano-micro particles, the particle size is small, the nano-scale is realized, the addition amount is small, and the dispersibility is good;
(4) Meanwhile, the method can catalyze and synthesize high molecular weight and low chroma PBAT, accelerate the crystallization rate and improve the crystallization temperature.
Drawings
FIG. 1 shows DSC thermograms of polybutylene terephthalate-adipate (PBAT) catalyzed by tetrabutyl titanate, polybutylene terephthalate-adipate (PBAT) catalyzed by zinc mandelate, and polybutylene terephthalate-adipate (PBT-PBAT) catalyzed by tetrabutyl titanate, after PBT is added.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The invention provides a nano-microparticle in-situ catalyst for preparing polybutylene terephthalate-adipate, which is prepared by the following steps:
(1) Adding a certain mass of metal carboxylate into a mixed solution of an alcohol compound with a certain proportion of molecular structure and only one hydroxyl and distilled water at a low temperature of-5-5 ℃, and stirring at a stirring speed of 300r/min for 10min;
(2) Adding alpha-hydroxy acid or alpha-amino acid, stirring for 10-30min, slowly heating to 10 deg.C above the boiling point of low-boiling monohydric alcohol, and refluxing for 2-5 hr;
(3) And after the reaction is finished, closing the mechanical stirring, cooling to room temperature, carrying out suction filtration under a reduced pressure condition, washing a filter cake for three times by using absolute ethyl alcohol, and carrying out vacuum drying at room temperature to obtain the in-situ polymerization catalyst.
Wherein the mass of the metal carboxylate is 0.01 to 0.03 time of that of the mixed solution; the mass ratio of the alcohol compound with only one hydroxyl group in the molecular structure to the distilled water is 20-40:1; the mass ratio of the alpha-hydroxy acid or the alpha-amino acid to the metal acetate is 1.6-2.8:1.
wherein, the alcohol compound with only one hydroxyl in the molecular structure is at least one of methanol, ethanol, normal propyl alcohol, isopropyl alcohol, normal butanol, isobutyl alcohol or tertiary butanol.
Wherein the alpha-hydroxy acid is more than one of glycolic acid, lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid; the alpha-amino acid is at least one of glycine, alanine, phenylalanine, threonine, valine, leucine or isoleucine.
Wherein the metal carboxylate is at least one of metal acetate, oxalate, malonate, succinate, glutarate and adipate of calcium, magnesium, zinc, aluminum, iron, cobalt, nickel and copper.
Wherein the nano-microparticle in-situ polymerization catalyst is white powdery solid; the particle size of the nanometer microparticle in-situ polymerization catalyst is 50-100nm.
The structural formula and the preparation equation of the in-situ catalyst are as follows:
or is
Wherein, with R 1 The alpha-hydroxycarboxylic acid of the radical has the formula
M is metal atoms such as Ca, zn, mg, mn, co, fe and the like;
with R 2 The carboxylic acid of the group has the formula
With R 2 The structural formula of the radical alpha-amino carboxylic acid is shown in the specification,
The invention also provides a preparation method of the polybutylene terephthalate-adipate, which takes adipic acid, terephthalic acid and 1, 4-butanediol as raw materials and sequentially carries out esterification reaction, pre-polycondensation reaction and final polycondensation reaction under the action of the in-situ catalyst to prepare the polybutylene adipate-terephthalate.
The prepared in-situ polymerization catalyst is added into a reaction system before ester exchange reaction, and the using amount of the catalyst is 0.5-1.5 per mill of the total mass of the system.
The molar ratio of the alkyd in the reaction system is 1.4:1, wherein the mass ratio of adipic acid to terephthalic acid is 1:1; the esterification temperature is 200-220 ℃, and the esterification time is 150-200min; the pre-polycondensation temperature is 230-250 ℃, the pre-polycondensation pressure is 1k-2kPa absolute, and the pre-polycondensation time is 30-50min; the polycondensation temperature is 230-250 deg.C, the polycondensation pressure is 5-30Pa, and the polycondensation time is 120-180min.
Embodiment 1
Preparation of in-situ polymerization catalyst:
1) Adding 20g of calcium acetate into a mixed solution of 2kg of methanol and distilled water at the temperature of-5 ℃, wherein the mass ratio of the methanol to the distilled water is 20, and stirring at the stirring speed of 300r/min for 10min;
2) Adding 32g of glycollic acid into the system, stirring for 10min, heating to 80 ℃, and carrying out reflux reaction on the system for 2h;
3) After the reflux is finished, the mechanical stirring is stopped, the system is cooled to the room temperature, the pumping filtration is carried out under the reduced pressure condition, the filter cake is washed three times by absolute ethyl alcohol, and the in-situ polymerization catalyst calcium glycolate is obtained after the vacuum drying at the room temperature, the particle size of the catalyst calcium glycolate is 69nm, and the structural formula of the catalyst calcium glycolate is shown in the specification
Example II
Preparation of in-situ polymerization catalyst:
1) Adding 15g of zinc acetate into a mixed solution of 3kg of ethanol and distilled water at the temperature of-0 ℃, wherein the mass ratio of the ethanol to the distilled water is 30, and stirring at the stirring speed of 300r/min for 10min;
2) Adding 33g of mandelic acid into the system, stirring for 10min, and heating to 75 ℃ to enable the system to perform reflux reaction for 3h;
3) After the reflux is finished, the mechanical stirring is closed, the system is cooled to room temperature, the pumping filtration is carried out under the reduced pressure condition, the filter cake is washed three times by absolute ethyl alcohol, and the in-situ polymerization catalyst zinc mandelate is obtained after the vacuum drying at room temperature, the particle size of the zinc mandelate is 57nm, and the structural formula of the zinc mandelate is shown in the specification
Example three
Preparation of in-situ polymerization catalyst:
1) Adding 30g of magnesium adipate into a mixed solution of 4kg of n-propanol and distilled water at the temperature of 5 ℃, wherein the mass ratio of the n-propanol to the distilled water is 40, and stirring at the stirring speed of 300r/min for 10min;
2) Adding 84g of 6-hydroxycaproic acid into the system, stirring for 10min, heating to 75 ℃, and carrying out reflux reaction on the system for 4h;
3) After the reflux is finished, the mechanical stirring is stopped, the system is cooled to the room temperature, the suction filtration is carried out under the reduced pressure condition, the filter cake is washed three times by absolute ethyl alcohol, and the in-situ polymerization catalyst, namely the magnesium hydroxycaproate, is obtained after the vacuum drying at the room temperature, has the particle diameter of 81nm and the structural formula of 81nm
Example four
Preparation of polybutylene terephthalate-adipate:
1) Respectively adding 900g of terephthalic acid (5.4 mol), 900g of adipic acid (6.2 mol) and 1464g of butanediol (16.2 mol) into a 5L reaction kettle, then adding 1.63g of self-made zinc mandelate in-situ polymerization catalyst (0.5 per mill of the total mass of the system), heating the system to 200 ℃ for esterification reaction, wherein the reaction time is 150 minutes;
2) After the esterification reaction is finished, heating the system to 230 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1kPa for 30min;
3) After the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 230 ℃ and under the absolute pressure of 5Pa, and the polycondensation time is 120min. Thus obtaining the polybutylene terephthalate-adipate melt. The weight-average molecular weight was found to be 12.7w, the color number L was 92 and the crystallization temperature was 85 ℃.
Example five
Preparation of polybutylene terephthalate-adipate:
1) Respectively adding 900g of terephthalic acid (5.4 mol), 900g of adipic acid (6.2 mol) and 1464g of butanediol (16.2 mol) into a 5L reaction kettle, then adding 3.26g of a home-made calcium glycolate in-situ polymerization catalyst (1 per mill of the total mass of the system), heating the system to 210 ℃ for esterification reaction, wherein the reaction time is 180 minutes;
2) After the esterification reaction is finished, heating the system to 230 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1.4kPa for 40min;
3) After the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 240 ℃ under the absolute pressure of 25Pa, and the polycondensation time is 130min. Thus obtaining the polybutylene terephthalate-adipate melt. The weight-average molecular weight was 11.3w, the color number L was 90 and the crystallization temperature was 79 ℃.
Comparative example 1
Preparation of polybutylene terephthalate-adipate:
1) Respectively adding 900g of terephthalic acid (5.4 mol), 900g of adipic acid (6.2 mol) and 1464g of butanediol (16.2 mol) into a 5L reaction kettle, then adding 3g of tetrabutyl titanate, heating the system to 200 ℃ for esterification reaction, wherein the reaction time is 200 minutes;
2) After the esterification reaction is finished, heating the system to 220 ℃, and carrying out pre-polycondensation reaction under the absolute pressure of 1.9kPa for 20min;
3) After the pre-polycondensation reaction is finished, the system is subjected to polycondensation reaction at 250 ℃ and under the absolute pressure of 49Pa, and the polycondensation time is 180min. Thus obtaining the polybutylene terephthalate-adipate melt under the catalysis of tetrabutyl titanate. The weight-average molecular weight was found to be 7.3w, the color number L was 75 and the crystallization temperature was 69 ℃.
The nanoparticle in-situ polymerization catalyst and polybutylene terephthalate-adipate prepared in the above examples were tested according to the following methods:
the particle size tester is a QUANTA450 tungsten filament scanning electron microscope manufactured by FEI corporation of America.
The method for testing the chroma L value comprises the following steps: the test was carried out as specified in GB/T14190-2008 at 5.5.2. The CIE1976L a b color series was used.
The molecular weight measuring instrument is 1515GPC gel chromatograph manufactured by Waters corporation in USA, and the mobile phase is chloroform.
The crystallization temperature was measured by DSC25, an instrument model of TA, USA, and the crystallization temperature and melting point of the polymer were calculated from the results of the measurement. During testing, the adopted procedure is as follows: under the nitrogen atmosphere (the flow rate is 50 ml/min), the temperature rising and falling speed is 10 ℃/min.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (4)
1. A preparation method of polybutylene terephthalate-adipate is characterized in that adipic acid, terephthalic acid and 1, 4-butanediol are used as raw materials, and esterification reaction, pre-polycondensation reaction and final polycondensation reaction are sequentially carried out under the action of a nanoparticle in-situ catalyst to prepare the polybutylene terephthalate-adipate; the nanometer microparticle in-situ catalyst is added into a reaction system before esterification reaction, and the using amount of the nanometer microparticle in-situ catalyst is 0.5-1.5 per mill of the total mass of the system;
the nano-microparticle in-situ catalyst is prepared by the following method:
(1) Adding metal carboxylate into a mixed solution of an alcohol compound with a molecular structure only having one hydroxyl and distilled water at a temperature of between 5 ℃ below zero and 5 ℃, and stirring;
(2) Adding alpha-hydroxy acid, stirring, slowly heating to 10 ℃ above the boiling point of the alcohol compound, and carrying out reflux reaction on the system;
(3) After the reaction is finished, the mechanical stirring is closed, the reaction product is cooled to room temperature, suction filtration is carried out under the reduced pressure condition, the filter cake is washed by absolute ethyl alcohol for three times, and the nano-microparticle in-situ catalyst is obtained after vacuum drying at room temperature;
the alpha-hydroxy acid is more than one of lactic acid, mandelic acid, phenyl lactic acid, 4-hydroxybutyric acid, 6-hydroxybutyric acid and 10-hydroxydecanoic acid;
the metal carboxylate is at least one of acetate, oxalate, malonate, succinate, glutarate and adipate of metal magnesium, aluminum, iron, cobalt, nickel and copper;
the particle size of the nano-microparticle in-situ catalyst is 50-100nm;
the mass ratio of the alcohol compound with only one hydroxyl group in the molecular structure to the distilled water is 20-40:1; the mass ratio of the alpha-hydroxy acid to the metal carboxylate is 1.6-2.8:1; the mass of the metal carboxylate is 0.01-0.03 times of that of the mixed solution.
2. The preparation method according to claim 1, wherein the molar ratio of the alkyds in the reaction system is 1.4:1, wherein the mass ratio of adipic acid to terephthalic acid is 1:1; the esterification temperature is 200-220 ℃, and the esterification time is 150-200min; the pre-polycondensation temperature is 230-250 ℃, the pre-polycondensation pressure is 1k-2kPa absolute, and the pre-polycondensation time is 30-50min; the final polycondensation temperature is 230-250 deg.C, the final polycondensation pressure is 5-30Pa, and the final polycondensation time is 120-180min.
3. The method according to claim 1, wherein the alcohol compound having only one hydroxyl group in the molecular structure is one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol.
4. The method according to claim 2, wherein the stirring rate in the step (1) is 300r/min, and the stirring time is 10min;
the stirring time in the step (2) is 10-30min, and the reflux reaction time is 2-5 hours.
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