CN111592642A - Preparation method of high-toughness bio-based polyester - Google Patents
Preparation method of high-toughness bio-based polyester Download PDFInfo
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- CN111592642A CN111592642A CN202010419899.6A CN202010419899A CN111592642A CN 111592642 A CN111592642 A CN 111592642A CN 202010419899 A CN202010419899 A CN 202010419899A CN 111592642 A CN111592642 A CN 111592642A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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Abstract
The invention relates to the technical field of bio-based polyester, and discloses a preparation method of high-toughness bio-based polyester, which comprises the following steps: (1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, polyhydric alcohol, a catalyst and a heat stabilizer for esterification; (2) mixing the esterification reaction product prepared in the step (1), long-chain fatty acid, catalyst and heat stabilizer to perform esterification reaction; (3) vacuumizing the esterification reaction product prepared in the step (2) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, two-stage polycondensation reaction is carried out, and the high-toughness bio-based polyester is prepared. The preparation method can effectively improve the toughness of the bio-based polyester on the premise of keeping the better heat resistance and tensile strength of the bio-based polyester.
Description
Technical Field
The invention relates to the technical field of bio-based polyester, in particular to a preparation method of high-toughness bio-based polyester.
Background
The bio-based polyester is an environment-friendly material prepared by taking renewable biomass as a raw material, can partially replace the existing petroleum-based polyester which is produced and applied in large scale, and is beneficial to the sustainable development of the polyester industry. Although the production cost of bio-based polyesters is higher than petroleum-based polyesters at present, they have enormous performance and environmental advantages, and in the long run, their production cost is reduced to comparable to or even lower than petroleum-based polyesters. The existing bio-based polymers are mainly focused on polylactic acid (PLA), Polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), and the like.
2, 5-furandicarboxylic acid (FDCA) is obtained by hydrolyzing and oxidizing starch or cellulose rich in source, and the structure contains rigid benzene rings, so that the FDCA can be used for replacing some petroleum-based raw materials containing benzene ring structures, such as terephthalic acid, to prepare some high polymer materials; in addition, due to the aromaticity and the electron conjugation effect of the furan ring structure, the polyfuran dicarboxylic acid diol ester synthesized by using the 2,5-FDCA has more advantages than the traditional polyethylene terephthalate (PET) material in the aspects of barrier property, heat resistance and the like. Currently, biobased 2,5-FDCA is considered by dupont and DSM as a "sleeping giant," which the U.S. department of energy considers to be one of the 12 most potential biobased platform compounds.
Chinese patent publication No. CN201811472510.3 discloses a furan dicarboxylic acid copolyester and a preparation method thereof, comprising the following steps: (1) mixing dibasic acid or an esterified product thereof, dihydric alcohol and an esterification reaction catalyst, and carrying out esterification reaction under an inert atmosphere to obtain a first intermediate product; wherein the dibasic acid comprises furandicarboxylic acid, and the dihydric alcohol comprises ethylene glycol, 1, 4-cyclohexanedimethanol, and 2,2,4, 4-tetramethyl-1, 3-cyclobutanedimethanol; (2) under the vacuum condition, carrying out pre-polycondensation reaction on the first intermediate product to obtain a second intermediate product; (3) and carrying out polycondensation reaction on the second intermediate product under the vacuum condition to obtain the furan dicarboxylic acid copolyester. The furan dicarboxylic acid copolyester prepared by the method has better heat resistance and transparency, but the toughness is not ideal, which is also a common problem of the furan dicarboxylic acid diol ester because: the movement of a polyester molecular chain is limited by a meta furan ring in a furan dicarboxylic acid diol ester structure, the intermolecular steric hindrance is large, the crystallization rate is slow, and the material is large in brittleness and has the elongation at break only one tenth of that of PET.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of high-toughness bio-based polyester. The preparation method can effectively improve the toughness of the bio-based polyester.
The specific technical scheme of the invention is as follows:
a preparation method of high-toughness bio-based polyester comprises the following steps:
(1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, polyhydric alcohol, a catalyst and a heat stabilizer for esterification;
(2) mixing the esterification reaction product prepared in the step (1), long-chain fatty acid, catalyst and heat stabilizer to perform esterification reaction;
(3) vacuumizing the esterification reaction product prepared in the step (2) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, two-stage polycondensation reaction is carried out, and the high-toughness bio-based polyester is prepared.
According to the invention, polyhydroxy alcohol is introduced into the main chain of the polyfurandicarboxylic acid diol ester, and then long-chain fatty acid reacts with the side chain hydroxyl of the polyol to synthesize the bio-based polyester with long-chain side chains. The long-chain side chain plays a role in internal plasticization of a polyfurandicarboxylic acid diol ester network, can be inserted between polyester molecules, weakens acting force between macromolecules, and increases free volume between the polyester molecules, so that the mobility of the polyester molecular chain is increased, and the long-chain side chain can disperse a part of impact energy, so that the toughness of the bio-based polyester material can be improved.
The steps (1) to (2) of the invention adopt a stepwise esterification method, firstly introduce the polyhydroxy alcohol, and then graft the long-chain fatty acid, and do not adopt one-step esterification, because: the temperature of the two esterification reactions is greatly different, the suitable temperature of the esterification reaction of the 2, 5-furandicarboxylic acid is lower than that of the long-chain fatty acid, the two esterification reactions do not intersect, if one-step esterification is adopted, the reaction temperature is difficult to coordinate, if the suitable temperature of the esterification reaction of the 2, 5-furandicarboxylic acid is adopted, the steric hindrance of the long-chain fatty acid is large, the esterification reaction is difficult to completely carry out, the grafting rate is too low, and the toughness of the finally prepared bio-based polyester is poor; if the esterification reaction of the long-chain fatty acid is carried out at a proper temperature, decarboxylation reaction can occur due to unstable carboxyl in the 2, 5-furandicarboxylic acid, and meanwhile, impurities in the 2, 5-furandicarboxylic acid can also generate side reaction, so that the color of the bio-based polyester is poor.
Preferably, in the step (2), the long-chain fatty acid is one or more of 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, and 1, 12-dodecanoic acid.
The long-chain dibasic fatty acid is adopted, so that the free volume can be further increased, a better internal plasticizing effect can be achieved, flexible chain segments can be formed among molecular chains for connection, when the material is impacted or stretched by the outside, force is transmitted on the flexible chain segments, the deformation of the flexible chain segments can absorb and disperse part of energy, a buffering effect is achieved, and the toughness of the bio-based polyester material is further enhanced.
The length of the long-chain fatty acid needs to be controlled within a suitable range because: if the length is too short, the internal plasticization effect of the long-chain side chain grafted to the molecular chain of the bio-based polyester is limited, so that the toughness of the polyester material is poor; if the length is too long, the free volume becomes too large, and the heat resistance (glass transition temperature) and the tensile strength of the polyester material become too low. The invention sets the number of carbon atoms in the long-chain fatty acid to be 6-12 in consideration of the combination of toughness, heat resistance and tensile strength of the material.
Preferably, in the step (1), the molar ratio of the furan dicarboxylic acid to the diol is 1: 1.2-1.6.
Preferably, in the step (1), the amount of the substance of the polyhydric alcohol is 5 to 15% of the total amount of the reaction raw materials in the step (1).
Preferably, in the step (2), the amount of the substance of the long-chain fatty acid is 10 to 30% of the amount of the substance in the reaction raw material in the step (2).
The grafting ratio of the long-chain fatty acid is too low, so that the improvement effect of the long-chain fatty acid on the toughness of the bio-based polyester material is poor; too high a grafting ratio results in too high a free volume, resulting in too low heat resistance and tensile strength of the polyester material. The invention controls the grafting rate of the long-chain fatty acid in a proper range by controlling the dosage of the polyhydroxy alcohol and the long-chain fatty acid, so that the bio-based polyester material has good heat resistance and tensile strength while obtaining ideal toughness.
Preferably, in the step (2), the temperature of the esterification reaction is 220-230 ℃, and the reaction time is 1-5 h.
The esterification reaction temperature of the step (2) needs to be controlled within a suitable range because: the steric hindrance of the long-chain fatty acid is large, if the temperature is too low, the long-chain fatty acid cannot be completely esterified, so that the grafting rate is too low, and the toughness of the finally prepared bio-based polyester is poor; if the temperature is too high, partial degradation of the esterification product occurs, which affects the hue of the bio-based polyester and further affects the subsequent polycondensation reaction, resulting in too low molecular weight and poor properties such as viscosity and toughness of the bio-based polyester. The esterification reaction temperature in the step (2) is controlled at 230 ℃ below 220 ℃, so that the complete esterification reaction can be ensured, the degradation of the esterification product can be prevented, and the bio-based polyester has better color, viscosity and toughness.
Preferably, in the step (1), the temperature of the esterification reaction is 190-200 ℃, and the reaction time is 1-5 h.
The esterification reaction temperature between 2, 5-furandicarboxylic acid, diol, and polyhydric alcohol is controlled in a suitable range because: 2, 5-furandicarboxylic acid is solid during esterification reaction, and the solubility of the 2, 5-furandicarboxylic acid in dihydric alcohol is very low, so that the esterification reaction is a solid-liquid reaction, and the activation energy is relatively high, so that if the temperature is too low, the relatively high energy barrier of the esterification reaction cannot be overcome, the esterification rate is too low, and the viscosity of the finally prepared bio-based polyester is too low; if the temperature is too high, decarboxylation reaction of the 2, 5-furandicarboxylic acid occurs, impurities in the 2, 5-furandicarboxylic acid also generate side reactions, so that the finally prepared bio-based polyester has poor color, and the excessive temperature also causes excessive consumption of hydroxyl in the polyhydroxy alcohol, affects the grafting rate of long-chain fatty acid, so that the effect of improving the toughness of the bio-based polyester is not ideal. The esterification reaction temperature in the step (1) is controlled at 190-.
Preferably, in the step (3), the temperature of the one-stage polycondensation reaction is 230-240 ℃ and the pressure is less than or equal to 0.1 MPa.
Preferably, in the step (3), the temperature of the two-stage polycondensation reaction is 240-260 ℃, the pressure is less than or equal to 100Pa, and the reaction time is 1-5 h.
Preferably, in the step (1), the diol is one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
Preferably, in the step (1), the polyhydric alcohol is one or more of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, butanetetraol, pentaerythritol, pentanol, hexanehexol and sugar alcohol.
The length of the polyhydric alcohol can affect the properties of the final biobased polyester. Compared with furan rings, the main chain of the polyhydroxy alcohol has higher flexibility, a flexible chain segment can be introduced into a polyfurandicarboxylic acid diol ester molecular chain, and the flexible chain segment plays a role in absorbing energy through the movement of the chain segment when being impacted or stretched, so that the toughness of the bio-based polyester is improved, and meanwhile, the heat resistance and the tensile strength of the bio-based polyester are also reduced. Therefore, if the length of the polyhydric alcohol is too short, the toughness of the bio-based polyester is not satisfactory; if the length is too long, the heat resistance and tensile strength of the bio-based polyester are poor.
The number of hydroxyl groups of the polyhydroxy alcohol can also have an effect on the performance of the bio-based polyester. If the number of the hydroxyl groups is too small, the grafted fatty acid chain is too small, and the improvement effect on the toughness of the bio-based polyester is not good; if the number of hydroxyl groups is too large, the graft ratio is too high, and the free volume between the polyester molecular chains is too large, so that the heat resistance and tensile strength of the polyester material are poor.
Preferably, in the step (1) and the step (2), the catalyst is one or more of n-butyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/phosphorus-containing compound.
Preferably, in the step (1) and the step (2), the heat stabilizer is one or more of an antioxidant 1010, an antioxidant 1076, an antioxidant 425, an antioxidant 330, an antioxidant 1178, an antioxidant 618, an antioxidant 626, an antioxidant 168, tetraphenyl dipropylene glycol diphosphite, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl phosphite, pentaerythritol diphosphotridecyl phosphite, pentaerythritol tetrapentaerythritol tetrapentaphenyl tridecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate.
Preferably, after the step (3), the modified tri (2-aminoethyl) amine-methyl acrylate polymer is grafted on the high-toughness bio-based polyester prepared in the step (3) through ester exchange reaction, and the specific steps are as follows: mixing the high-toughness bio-based polyester prepared in the step (3) and the modified tri (2-aminoethyl) amine-methyl acrylate polymer according to the mass ratio of 1:0.005-0.008, and carrying out ester exchange reaction at 180-190 ℃ for 1-2 h.
The activity space of a bio-based polyester molecular chain can be increased by grafting the long-chain fatty acid side chain, but the activity capacity is limited due to the existence of a rigid furan ring in the molecular chain, and the grafting rate of the long-chain side chain is limited due to the requirements on the heat resistance and tensile strength of the polyester material, so the improvement degree of the grafted long-chain side chain on the toughness of the bio-based polyester material is limited. To further improve the toughness of the bio-based polyester, a method of grafting a modified tris (2-aminoethyl) amine-methyl acrylate polymer may be used.
A tris (2-aminoethyl) amine-methyl acrylate polymer can be grafted as a side chain onto multiple biobased polyester chains. The tri (2-aminoethyl) amine-methyl acrylate polymer has higher branching degree, can fill a part of free volume formed by grafting long-chain fatty acid side chains, and reduces the influence of long-chain side chain grafting on the heat resistance and tensile strength of the bio-based polyester material. And the existence of a large number of C-C and C-N flexible chain segments in the molecular chain of the tri (2-aminoethyl) amine-methyl acrylate polymer enables the polymer to keep larger flexibility, so when the bio-based polyester material is impacted or stretched, the long-chain fatty acid side chain can still play a role in dispersing impact energy, meanwhile, force is transmitted on the molecular chain of the tri (2-aminoethyl) amine-methyl acrylate polymer, and the existence of a large number of branched chains and the flexibility of the molecular chain can absorb and disperse a large number of impact energy, thereby effectively increasing the toughness of the bio-based polyester material.
However, the flexible long-chain fatty acid of the tri (2-aminoethyl) amine-methyl acrylate polymer is weak, and the dosage needs to be controlled within a certain range, and the excessive dosage can cause the viscosity of the bio-based polyester to be too high, thereby limiting the application field of the bio-based polyester. Therefore, the long-chain fatty acid and the tri (2-aminoethyl) amine-methyl acrylate polymer are used together, and the functions of the long-chain fatty acid and the tri (2-aminoethyl) amine-methyl acrylate polymer are mutually complemented, so that a better toughening effect can be achieved.
Preferably, the modified tris (2-aminoethyl) amine-methyl acrylate polymer is prepared as follows:
(a) synthesizing: under the protection of inert gas, dropwise adding a mixed solution of methyl acrylate and ethanol into tris (2-aminoethyl) amine, wherein the molar ratio of the methyl acrylate to the tris (2-aminoethyl) amine is 1.5-2:1, reacting at 15-20 ℃ for 2-3h, removing the ethanol, and reacting at 150-160 ℃ under 0.5-0.8kPa for 2.5-3 h;
(b) end capping: adding tris (2-aminoethyl) amine and acetic acid into the reaction system in the step (a) according to the molar ratio of 1:6-7, continuously reacting at the temperature of 150 ℃ and 160 ℃ and under the pressure of 0.5-0.8kPa for 1-2h, pressurizing to 80-85kPa, and continuously reacting until the acid value is reduced to below 30, thus obtaining the tris (2-aminoethyl) amine-methyl acrylate polymer;
(c) modification: dispersing the tri (2-aminoethyl) amine-methyl acrylate polymer prepared in the step (b) and glycidol butyrate into alcohol according to the mass ratio of 1:0.01-0.03, and reacting for 2-3h at the temperature of 100-; then adding ether for precipitation, filtering, dissolving the precipitate into water, adding sodium hydroxide solution, and reacting for 1-2h at 60-70 ℃; then adding ether for precipitation, filtering and drying the precipitate to obtain the modified tri (2-aminoethyl) amine-methyl acrylate polymer.
In step (a), the synthesis process comprises two stages: a first stage of attaching methyl acrylate to the end of tris (2-aminoethyl) amine by addition reaction of a carbon-carbon double bond in methyl acrylate with an amino group in tris (2-aminoethyl) amine; and in the second stage, the ester group and the amino group react to generate polycondensation reaction among the methyl acrylate, the tri (2-aminoethyl) amine and the addition reaction product in the first stage.
In the step (b), the purpose of the end capping is to limit the length of the tri (2-aminoethyl) amine-methyl acrylate polymer so as to prevent the polymer molecular chain from being overlong and intertwined, thereby influencing the toughening effect and the evenness of the bio-based polyester.
In the step (c), the purpose of modification is to enable the tri (2-aminoethyl) amine-methyl acrylate polymer to be grafted to the molecular chain of the bio-based polyester through ester exchange reaction, and the modification mechanism is as follows: the grafting of the tris (2-aminoethyl) amine-methyl acrylate polymer onto the biobased polyester is achieved by grafting the glycidyl butyrate ester onto the polymer via a ring-opening reaction between the imino group in the tris (2-aminoethyl) amine-methyl acrylate polymer and the epoxy group in the glycidyl butyrate ester, which results in the formation of one hydroxyl group followed by hydrolysis of the ester group to form another hydroxyl group.
By controlling the dosage of the glycidol butyrate and ring-opening reaction conditions, the grafting rate of the glycidol butyrate can be controlled within a proper range, so that the situation that the crosslinking degree of a tri (2-aminoethyl) amine-methyl acrylate polymer and bio-based polyester is too small due to too small grafting rate, impact energy cannot be sufficiently and quickly transmitted to a polymer molecular chain to cause insufficient toughness is prevented, and the situation that the crosslinking degree is too large due to too large grafting rate, so that the network chain between two adjacent branch points in a network structure is too short to influence the strain of the network structure under the action of external force, and the toughness is insufficient is prevented.
Compared with the prior art, the invention has the following advantages: the preparation method can effectively improve the toughness of the bio-based polyester on the premise of keeping the better heat resistance and tensile strength of the bio-based polyester.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
Preparing a bio-based polyester by:
(1) mixing 2, 5-furandicarboxylic acid and dihydric alcohol with the molar ratio of 1:1.2-1.6, polyhydric alcohol accounting for 5-15% of the total substance of the raw materials in the step (1), a catalyst and a heat stabilizer, and carrying out esterification reaction at 190-200 ℃ for 1-5 h; the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol; the polyhydric alcohol is one or more of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, butanetetraol, pentaerythritol, pentanol, hexitol and sugar alcohol; the catalyst is one or more of tetrabutyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/phosphorus-containing compound; the heat stabilizer is one or more of an antioxidant 1010, an antioxidant 1076, an antioxidant 425, an antioxidant 330, an antioxidant 1178, an antioxidant 618, an antioxidant 626, an antioxidant 168, tetraphenylpropylene glycol diphosphite, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl phosphite, pentaerythritol diphosphotridecyl phosphite, pentaerythritol tetrapentaerythritol tetrapentaphenyl tridecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate;
(2) mixing the esterification reaction product prepared in the step (1), long-chain fatty acid accounting for 10-30% of the amount of substances in the reaction raw materials in the step (2), a catalyst and a heat stabilizer, and carrying out esterification reaction at the temperature of 220-230 ℃ for 1-5 h; the long-chain fatty acid is one or more of 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid and 1, 12-dodecyl acid; the catalyst is one or more of tetrabutyl titanate, isopropyl titanate, stannous octoate, stannous oxalate, dibutyltin oxide, lithium acetate, potassium acetate, calcium acetate, magnesium acetate, barium acetate, zinc acetate, cobalt acetate, antimony acetate, lead acetate, manganese acetate, a silicon dioxide/titanium dioxide compound, a silicon dioxide/titanium dioxide/nitrogen-containing compound and a silicon dioxide/phosphorus-containing compound; the heat stabilizer is one or more of an antioxidant 1010, an antioxidant 1076, an antioxidant 425, an antioxidant 330, an antioxidant 1178, an antioxidant 618, an antioxidant 626, an antioxidant 168, tetraphenylpropylene glycol diphosphite, trimethyl phosphite, triethyl phosphite, triisooctyl phosphite, triisodecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, triphenyl phosphite, tri-p-tolyl phosphite, ditridecyl phosphite, tris (2, 4-di-tert-butyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl phosphite, pentaerythritol diphosphotridecyl phosphite, pentaerythritol tetrapentaerythritol tetrapentaphenyl tridecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate;
(3) vacuumizing the esterification reaction product prepared in the step (2) until the pressure is less than or equal to 0.1MPa, and performing a one-stage polycondensation reaction at the temperature of 230 ℃ and 240 ℃; when no white liquid is extracted, the vacuum is pumped till the pressure is less than or equal to 100Pa, and two-stage polycondensation reaction is carried out at the temperature of 240-260 ℃ for 1-5h, thus obtaining the bio-based polyester.
Optionally, after the step (3), grafting a modified tri (2-aminoethyl) amine-methyl acrylate polymer on the high-toughness bio-based polyester prepared in the step (3) through ester exchange reaction, and specifically, the following steps are carried out:
(a) synthesis of tris (2-aminoethyl) amine-methyl acrylate polymer: under the protection of inert gas, dropwise adding a mixed solution of methyl acrylate and ethanol into tris (2-aminoethyl) amine, wherein the molar ratio of the methyl acrylate to the tris (2-aminoethyl) amine is 1.5-2:1, reacting at 15-20 ℃ for 2-3h, removing the ethanol, and reacting at 150-160 ℃ under 0.5-0.8kPa for 2.5-3 h; (b) end capping: adding tris (2-aminoethyl) amine and acetic acid into the reaction system in the step (a) according to the molar ratio of 1:6-7, continuously reacting at the temperature of 150 ℃ and 160 ℃ and under the pressure of 0.5-0.8kPa for 1-2h, pressurizing to 80-85kPa, and continuously reacting until the acid value is reduced to below 30, thus obtaining the tris (2-aminoethyl) amine-methyl acrylate polymer;
(c) modification: dispersing the tri (2-aminoethyl) amine-methyl acrylate polymer prepared in the step (b) and glycidol butyrate into alcohol according to the mass ratio of 1:0.01-0.03, and reacting for 2-3h at the temperature of 100-; then adding ether for precipitation, filtering, dissolving the precipitate into water, adding sodium hydroxide solution, and reacting for 1-2h at 60-70 ℃; then adding ether for precipitation, filtering and drying the precipitate to obtain a modified tri (2-aminoethyl) amine-methyl acrylate polymer;
(d) grafting: mixing the bio-based polyester prepared in the step (3) with the modified tri (2-aminoethyl) amine-methyl acrylate polymer prepared in the step (c) according to the mass ratio of 1:0.005-0.008, and carrying out transesterification reaction at 180-190 ℃ for 1-2 h.
Example 1
Preparing a bio-based polyester by:
(1) putting 100g of furan dicarboxylic acid, 60g of ethylene glycol, 11g of butanetriol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a first esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) putting 100g of the esterification reaction product prepared in the step (1), 6g of 1, 6-adipic acid, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a second esterification reaction kettle, and carrying out esterification reaction at 225 ℃ for 2.5 hours;
(3) and (3) transferring the esterification reaction product prepared in the step (2) into a polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 240 ℃ and 0.08MPa, carrying out two-stage polycondensation reaction at 260 ℃ and 80Pa after the reaction time is 1-2h and when no white liquid is extracted, and carrying out the reaction time for 3h to obtain the bio-based polyester.
Example 2
Preparing a bio-based polyester by:
(1) putting 100g of furan dicarboxylic acid, 76g of 1, 3-propylene glycol, 15g of glycerol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a first esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) placing 100g of the esterification reaction product prepared in the step (1), 14g of 1, 8-octanedioic acid, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 in a second esterification reaction kettle, and carrying out esterification reaction at 225 ℃ for 2.5 hours;
(3) and (3) transferring the esterification reaction product prepared in the step (2) into a polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 240 ℃ and 0.08MPa, carrying out two-stage polycondensation reaction at 260 ℃ and 80Pa after the reaction time is 1-2h and when no white liquid is extracted, and carrying out the reaction time for 3h to obtain the bio-based polyester.
Example 3
Preparing a bio-based polyester by:
(1) putting 100g of furan dicarboxylic acid, 92g of 1, 4-butanediol, 19g of tetrol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a first esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) putting 100g of the esterification reaction product prepared in the step (1), 25g of 1, 10-sebacic acid, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a second esterification reaction kettle, and carrying out esterification reaction at 225 ℃ for 2.5 h;
(3) and (3) transferring the esterification reaction product prepared in the step (2) into a polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 240 ℃ and 0.08MPa, carrying out two-stage polycondensation reaction at 260 ℃ and 80Pa after the reaction time is 1-2h and when no white liquid is extracted, and carrying out the reaction time for 3h to obtain the bio-based polyester.
Example 4
Preparing a bio-based polyester by:
(1) putting 100g of furan dicarboxylic acid, 60g of ethylene glycol, 11g of butanetriol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a first esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) putting 100g of the esterification reaction product prepared in the step (1), 6g of 1, 6-adipic acid, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a second esterification reaction kettle, and carrying out esterification reaction at 225 ℃ for 2.5 hours;
(3) transferring the esterification reaction product prepared in the step (2) into a polycondensation reaction kettle, carrying out a one-stage polycondensation reaction at 240 ℃ and 0.08MPa, carrying out a two-stage polycondensation reaction at 260 ℃ and 80Pa for 3 hours after the reaction time is 1-2 hours and no white liquid is extracted out, and thus obtaining polyester;
(4) preparation of a modified tris (2-aminoethyl) amine-methyl acrylate polymer:
(4.1) Synthesis: preparing a mixed solution of 50g of methyl acrylate and 100mL of ethanol; dropwise adding the mixed solution into 56.6g of tri (2-aminoethyl) amine under the protection of nitrogen, reacting for 3h at 20 ℃, removing ethanol, and reacting for 2.5h at 155 ℃ under 0.7 kPa;
(4.2) end capping: adding 10g of tris (2-aminoethyl) amine and 28.7g of acetic acid into the reaction system in the step (a) according to the molar ratio, continuously reacting at 155 ℃ and 0.7kPa for 2h, pressurizing to 80kPa, and continuously reacting until the acid value is reduced to be below 30 to obtain a tris (2-aminoethyl) amine-methyl acrylate polymer;
(4.3) modification: dispersing the tri (2-aminoethyl) amine-methyl acrylate polymer prepared in step (b) with 1.2g of glycidyl butyrate into alcohol, and reacting at 105 ℃ for 2.5 h; then adding ether for precipitation, filtering, dissolving the precipitate into water, adding a sodium hydroxide solution, and reacting for 1.5h at 65 ℃; then adding ether for precipitation, filtering and drying the precipitate to obtain a modified tri (2-aminoethyl) amine-methyl acrylate polymer;
(5) and (3) mixing the polyester prepared in the step (3) with the modified tri (2-aminoethyl) amine-methyl acrylate polymer prepared in the step (4), and performing ester exchange reaction at 185 ℃ for 2 hours to obtain the bio-based polyester.
Comparative example 1
Preparing a bio-based polyester by:
(1) putting 100g of furan dicarboxylic acid, 60g of ethylene glycol, 11g of butanetriol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into a first esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) and (2) transferring the esterification reaction product prepared in the step (1) into a polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 240 ℃ and 0.08MPa, carrying out two-stage polycondensation reaction at 260 ℃ and 80Pa after the reaction time is 1-2h and when no white liquid is extracted, and carrying out the reaction time for 3h to obtain the bio-based polyester.
The bio-based polyesters obtained in examples 1 to 4 and comparative example 1 were subjected to color, intrinsic viscosity, heat resistance, tensile strength and toughness tests as follows:
(1) and (3) color testing: measuring the L value, the a value and the b value of the bio-based polyester by adopting a TES-135 physical color analyzer produced by Taiwan Shishi electronics, wherein according to a Lab color model, the L value represents the black and white value of a sample, the a value represents the red and green value of the color of the sample, and the b value represents the blue and yellow value of the color of the sample;
(2) intrinsic viscosity test: measuring the intrinsic viscosity of the bio-based polyester by adopting a Hangzhou Zhongwang automatic viscometer, wherein the measuring temperature is 25 ℃, and the used solvent is a phenol/tetrachloroethane mixed solution (the mass ratio w/w is 3/2);
(3) and (3) testing heat resistance: the glass transition temperature is used for representing the heat resistance of the bio-based polyester, and the higher the glass transition temperature is, the better the heat resistance is; glass transition temperatures were determined according to ASTM D3418-2015 using a TADSC 2920 instrument from Thermal analysis Instruments at a scan rate of 20 ℃/min;
(4) and (3) testing tensile strength: preparing the bio-based polyester into a dumbbell-shaped small sample strip with the size of 1mm multiplied by 2mm multiplied by 20mm by a Haakeminket II micro injection molding machine, and then testing the tensile strength of the sample strip at the tensile rate of 10mm/min by adopting an Instron 5567 universal testing machine of the American Instron company according to the GB/T1040.1-2006 testing standard;
(5) and (3) toughness testing: the toughness of the bio-based polyester is characterized by the elongation at break, and the higher the elongation at break is, the stronger the toughness is; the biobased polyester was prepared into a dumbbell-shaped specimen having a thickness of 2mm and a width of 4mm by a HaakeMinJet II micro-injection molding machine, and the specimen was tested for elongation at break at 25 ℃ and a tensile rate of 10mm/min according to ASTM D638-2014 using a Roell Z020 model universal material testing machine of Zwick, Germany.
TABLE 1
Example 1 is different from comparative example 1 in that long chain fatty acid is grafted on the bio-based polyester molecular chain through step (2) in example 1, while step (2) is not included in comparative example 1, and the rest of the preparation process is the same. As seen from the data in table 1, the bio-based polyester obtained in example 1 has a decreased glass transition temperature and a decreased tensile strength, but a significantly increased elongation at break, as compared to comparative example 1. This indicates that the preparation method of the present invention is effective in improving the toughness of biobased polyester, though the heat resistance and tensile strength of biobased polyester are reduced compared to the prior art, presumably because: the grafted long-chain side chain plays a role in internal plasticization of a polyfurandicarboxylic acid diol ester network, can be inserted between polyester molecules, weakens acting force between macromolecules, increases free volume between the polyester molecules, and further increases the mobility of the polyester molecular chain, which can cause certain influence on the heat resistance and tensile strength of a bio-based polyester material, but can effectively improve the toughness of the bio-based polyester material.
Example 4 differs from example 1 in that in example 4, a tris (2-aminoethyl) amine-methyl acrylate polymer was grafted onto the polyester via step (4), and in example 1 there was no step (4), and the remainder of the preparation was the same. From the data in Table 1, the glass transition temperature, tensile strength and elongation at break of the bio-based polyester obtained in example 4 were all increased as compared to example 1. This shows that the preparation method of the present invention can reduce the influence of the grafted long-chain fatty acid side chain on the heat resistance and tensile strength of the bio-based polyester by grafting the tri (2-aminoethyl) amine-methyl acrylate polymer, and further improve the toughness of the polyester material, presumably because: the tri (2-aminoethyl) amine-methyl acrylate polymer has higher branching degree, and can fill a part of free volume formed by grafting long-chain fatty acid side chains, thereby reducing the influence of the grafted long-chain fatty acid side chains on the heat resistance and tensile strength of the bio-based polyester material; and the existence of a large number of C-C and C-N flexible chain segments in the molecular chain of the tri (2-aminoethyl) amine-methyl acrylate polymer enables the polymer to keep larger flexibility, so when the bio-based polyester material is impacted or stretched, the long-chain fatty acid side chain can still play a role in dispersing impact energy, meanwhile, force is transmitted on the molecular chain of the tri (2-aminoethyl) amine-methyl acrylate polymer, and the existence of a large number of branched chains and the flexibility of the molecular chain can absorb and disperse a large number of impact energy, thereby effectively increasing the toughness of the bio-based polyester material.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of high-toughness bio-based polyester is characterized by comprising the following steps:
(1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, polyhydric alcohol, a catalyst and a heat stabilizer for esterification;
(2) mixing the esterification reaction product prepared in the step (1), long-chain fatty acid, catalyst and heat stabilizer to perform esterification reaction;
(3) vacuumizing the esterification reaction product prepared in the step (2) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, two-stage polycondensation reaction is carried out, and the high-toughness bio-based polyester is prepared.
2. The method for preparing high-toughness bio-based polyester according to claim 1, wherein in the step (2), the long-chain fatty acid is one or more of 1, 6-adipic acid, 1, 8-suberic acid, 1, 10-sebacic acid, and 1, 12-dodecanoic acid.
3. The method for preparing a high toughness biobased polyester according to claim 1, wherein in step (1), the molar ratio of furan dicarboxylic acid to diol is 1: 1.2-1.6.
4. The process for the preparation of high tenacity bio-based polyester according to claim 1, wherein:
in the step (1), the amount of the polyhydroxy alcohol accounts for 5-15% of the total amount of the reaction raw materials in the step (1); and/or
In the step (2), the amount of the substances of the long-chain fatty acid accounts for 10-30% of the amount of the substances in the reaction raw materials in the step (2).
5. The method for preparing high-toughness bio-based polyester according to claim 1, wherein in the step (2), the temperature of the esterification reaction is 220-230 ℃ and the reaction time is 1-5 h.
6. The method for preparing high-toughness bio-based polyester according to claim 1, wherein in the step (1), the temperature of the esterification reaction is 190-200 ℃ and the reaction time is 1-5 h.
7. The process for the preparation of high tenacity bio-based polyester according to claim 1, wherein:
in the step (3), the temperature of the one-stage polycondensation reaction is 230-; and/or
In the step (3), the temperature of the two-stage polycondensation reaction is 240-260 ℃, the pressure is less than or equal to 100Pa, and the reaction time is 1-5 h.
8. The process for the preparation of high tenacity bio-based polyester according to claim 1, wherein:
in the step (1), the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol; and/or
In the step (1), the polyhydric alcohol is one or more of glycerol, butanetriol, 2-hydroxymethyl-2-methyl-1, 3-propanediol, tetrol, pentaerythritol, pentadecanol, hexitol and sugar alcohol.
9. The process for producing a high toughness biobased polyester according to claim 1 or 2, wherein after the step (3), the modified tris (2-aminoethyl) amine-methyl acrylate polymer is grafted to the high toughness biobased polyester obtained in the step (3) by transesterification, by the following steps: mixing the high-toughness bio-based polyester prepared in the step (3) and the modified tri (2-aminoethyl) amine-methyl acrylate polymer according to the mass ratio of 1:0.005-0.008, and carrying out ester exchange reaction at 180-190 ℃ for 1-2 h.
10. The method of claim 9 wherein said modified tris (2-aminoethyl) amine-methyl acrylate polymer is prepared by the following steps:
(a) synthesizing: under the protection of inert gas, dropwise adding a mixed solution of methyl acrylate and ethanol into tris (2-aminoethyl) amine, wherein the molar ratio of the methyl acrylate to the tris (2-aminoethyl) amine is 1.5-2:1, reacting at 15-20 ℃ for 2-3h, removing the ethanol, and reacting at 150-160 ℃ under 0.5-0.8kPa for 2.5-3 h;
(b) end capping: adding tris (2-aminoethyl) amine and acetic acid into the reaction system in the step (a) according to the molar ratio of 1:6-7, continuously reacting at the temperature of 150 ℃ and 160 ℃ and under the pressure of 0.5-0.8kPa for 1-2h, pressurizing to 80-85kPa, and continuously reacting until the acid value is reduced to below 30, thus obtaining the tris (2-aminoethyl) amine-methyl acrylate polymer;
(c) modification: dispersing the tri (2-aminoethyl) amine-methyl acrylate polymer prepared in the step (b) and glycidol butyrate into alcohol according to the mass ratio of 1:0.01-0.03, and reacting for 2-3h at the temperature of 100-; then adding ether for precipitation, filtering, dissolving the precipitate into water, adding sodium hydroxide solution, and reacting for 1-2h at 60-70 ℃; then adding ether for precipitation, filtering and drying the precipitate to obtain the modified tri (2-aminoethyl) amine-methyl acrylate polymer.
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