CN111621006B - Preparation method of high-toughness bio-based antibacterial polyester - Google Patents
Preparation method of high-toughness bio-based antibacterial polyester Download PDFInfo
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- 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
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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 antibacterial polyester, which comprises the following steps: (1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, a catalyst and a heat stabilizer for esterification reaction; (2) mixing guanidine hydrochloride, diamine, a catalyst and a heat stabilizer, and carrying out polycondensation reaction; (3) mixing the esterification reaction product obtained in the step (1) and the polycondensation reaction product obtained in the step (2) to perform ester exchange reaction; (4) vacuumizing the transesterification reaction product obtained in the step (3) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, carrying out two-stage polycondensation reaction to obtain the high-toughness bio-based antibacterial polyester. The preparation method of the invention can endow the bio-based antibacterial polyester material with better antibacterial property and effectively improve the toughness.
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 antibacterial polyester.
Background
The bio-based material is a novel material and chemicals and the like which are manufactured by using renewable biomass such as grains, leguminous plants, straws, bamboo wood powder and the like as raw materials, and comprises basic bio-based chemicals such as bioalcohol, organic acid, alkane, olefin and the like obtained in the processes of biosynthesis, biological processing and biorefinery, and also comprises plastic materials and the like obtained by performing thermoplastic processing on bio-based plastics, bio-based fibers, sugar engineering products, bio-based rubber and biomass. Bio-based materials widely used at present are mainly concentrated 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, has a rigid furan ring in the structure, and is the only compound containing a rigid aromatic ring in 12 most potential bio-based platform compounds selected by the U.S. department of energy. Because of the extremely similar structure, FDCA is an important ideal substitute of petroleum-based aromatic ring-containing monomer terephthalic acid (PTA), and the bio-based aromatic polyester polyfuran dicarboxylic acid diol ester can be obtained by polycondensation of FDCA instead of terephthalic acid and diol. Due to the aromaticity and the electronic conjugation effect of the furan ring structure, the synthesized polyfuran dicarboxylic acid diol ester is more excellent than the traditional polyethylene terephthalate diol ester material in aspects of barrier property, heat resistance and the like. As a bio-based material with excellent performance, the material has great application prospect in fibers, films and biomedical materials.
Chinese patent publication No. CN106243331A discloses a method for preparing polyethylene furandicarboxylate, comprising the following steps: (1) esterification or transesterification reaction: adding furan dicarboxylic acid or furan dicarboxylic acid diester, ethylene glycol and a nitrogen-containing catalyst into a reactor, and reacting for 2-5 hours at 160-210 ℃ to obtain an esterification or ester exchange product; (2) and (3) polycondensation reaction: the esterification or ester exchange product reacts for 1 to 8 hours under the conditions that the pressure is less than or equal to 150Pa and the temperature is 220 to 250 ℃, and the polyethylene glycol furanoate with the intrinsic viscosity of more than or equal to 0.6dL/g and the absorbance of less than 0.1 is prepared. The polyethylene furan dicarboxylate (PEF) prepared by the method has the characteristics of no color or light color, less side reaction products and good structural regularity, but the common defects of polyethylene furan dicarboxylate materials including PEF still exist: (1) the movement of a polymer molecular chain is limited by a meta-furan ring in the structure, the steric hindrance between molecules is large, the crystallization rate is slow, and the brittleness of the material is large; (2) the polyfurandioctyl phthalate dihydric alcohol ester does not have antibacterial property, so that the current report about antibacterial modification of the polyfurandioctyl phthalate dihydric alcohol ester is few, and the toughness of the polyfurandioctyl phthalate dihydric alcohol ester is easily reduced after the antibacterial modification is carried out by a conventional method, so that the application of the polyfurandioctyl phthalate dihydric alcohol ester in the fields of medical materials and the like is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of high-toughness bio-based antibacterial polyester. The preparation method can endow the bio-based antibacterial polyester material with better antibacterial property and effectively improve the toughness.
The specific technical scheme of the invention is as follows:
a preparation method of high-toughness bio-based antibacterial polyester comprises the following steps:
(1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, a catalyst and a heat stabilizer for esterification reaction;
(2) mixing guanidine hydrochloride, diamine, a catalyst and a heat stabilizer, and carrying out polycondensation reaction;
(3) mixing the esterification reaction product obtained in the step (1) and the polycondensation reaction product obtained in the step (2) to perform ester exchange reaction;
(4) vacuumizing the transesterification reaction product obtained in the step (3) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, carrying out two-stage polycondensation reaction to obtain the high-toughness bio-based antibacterial polyester.
The invention introduces guanidino into the polyfurandicarboxylic acid diol ester, the guanidino can be protonated and positively charged, and is combined with cell membranes of bacteria and fungi through electrostatic attraction and hydrogen bonds, and finally the cell membranes are ruptured to kill the bacteria and the fungi, so that the antibacterial property can be given to the polyfurandicarboxylic acid diol ester material.
The invention introduces guanidino into the molecular chain of polyfuran dicarboxylic acid diol ester in the form of guanidine group-containing dihydric fatty amine, and the reason is that: the guanidino is relatively rigid, the introduction of the guanidino can limit the movement of a molecular chain, so that the toughness of the polyfurandicarboxylic acid diol ester material is reduced, the guanidino is introduced in the form of dihydric fatty amine containing the guanidino, the C-C chain segment in the dihydric fatty amine has relatively high flexibility, a flexible chain segment can be introduced into the polyfurandicarboxylic acid diol ester, when the polyfurandicarboxylic acid diol ester material is impacted by the outside, the flexible chain segment absorbs a part of impact energy through the movement of the chain segment, the influence of the guanidino introduction on the toughness is eliminated, and the bio-based antibacterial polyester material is endowed with higher toughness compared with the pure polyfurandicarboxylic acid diol ester.
In the steps (1) to (3) of the invention, guanidine hydrochloride and diamine are reacted to synthesize guanidine-containing dihydric fatty amine, and then the guanidine hydrochloride and the guanidine-containing dihydric fatty amine are connected with 2, 5-furandicarboxylic acid through ester exchange reaction, but the four monomers are not mixed and then polymerized in one step, because: the esterification reaction of 2, 5-furandicarboxylic acid and diol and the polycondensation reaction of guanidine hydrochloride and diamine differ greatly in temperature, the former being suitably at a higher temperature than the latter. When a one-step polymerization method is adopted, if the proper temperature of the esterification reaction is adopted, the molecular weight of guanidino-containing dibasic aliphatic amine obtained by the polycondensation reaction is too large, so that the glass transition temperature and the barrier property of the finally prepared bio-based antibacterial polyester material are obviously reduced; if the proper temperature of the polycondensation reaction is adopted, the energy barrier of the esterification reaction cannot be overcome, the esterification reaction cannot be fully carried out, the subsequent one-stage polycondensation reaction and two-stage polycondensation reaction are influenced, and the finally prepared bio-based antibacterial polyester has too low molecular weight, so that the viscosity, the toughness, the heat resistance and the barrier property are too low. The stepwise reaction can ensure that the esterification reaction is fully carried out, and is convenient to control the content of guanidyl in the bio-based antibacterial polyester and the length of a guanidyl-containing diamine chain segment, so that the polyester material has better antibacterial property, toughness, heat resistance and barrier property.
Preferably, in step (2), the reaction temperature of the polycondensation reaction is 140-160 ℃, and the reaction time is 1-5 h.
The polycondensation reaction temperature between guanidine hydrochloride and diamine needs to be controlled within a suitable range because: if the temperature is too low, the polycondensation reaction cannot be carried out; if the temperature is too high, the polymerization degree of the obtained product is too high, so that the molecular chain migration capability of the product is weak, the ester exchange reaction is not facilitated, the content of guanidino in the finally prepared bio-based antibacterial polyester is too low, the antibacterial capability of the polyester material is poor, and the heat resistance and the barrier property of the bio-based antibacterial polyester can be influenced due to the fact that the length of a diamine chain segment containing guanidino in the molecular chain of the bio-based antibacterial polyester is too large.
Preferably, in the step (2), the molar ratio of the guanidine hydrochloride to the diamine is 1: 1-1.2.
Preferably, in step (3), the molar ratio of the esterification reaction product obtained in step (1) to the polycondensation reaction product obtained in step (2) is from 1:1.2 to 1.4.
In the transesterification reaction, the ratio of the amount of the esterification reaction product obtained in the step (1) to the amount of the polycondensation reaction product obtained in the step (2) is controlled within a suitable range for the following reasons: if the relative amount of the esterification reaction product is too large, the content of a rigid chain segment in a molecular chain of the bio-based antibacterial polyester is too large, so that the toughness of the polyester material is poor, and the antibacterial property of the polyester material is poor due to too small content of guanidino in the molecular chain; if the relative amount of the polycondensation reaction product is too large, the content of the flexible chain segment in the molecular chain of the bio-based polyester is too large, and the heat resistance and the barrier property of the polyester material are poor. The molar ratio of the esterification reaction product to the polycondensation reaction product is set to be 1:1.2-1.4, so that the heat resistance and the barrier property of the polyester material can be ensured while the toughness and the antibacterial property of the polyester material are effectively improved.
Preferably, in the step (1), the molar ratio of the 2, 5-furandicarboxylic acid to the diol is 1: 1.6-2.
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 and diol needs to be controlled within a suitable range because: 2, 5-furandicarboxylic acid is solid during esterification reaction, the solubility of the 2, 5-furandicarboxylic acid in dihydric alcohol is low, the esterification reaction is a solid-liquid reaction, the activation energy is high, so that if the temperature is too low, the high energy barrier of the esterification reaction cannot be overcome, the reaction is incomplete, and the viscosity of the finally prepared bio-based antibacterial polyester is too low; if the temperature is too high, decarboxylation reaction of the 2, 5-furandicarboxylic acid occurs, and impurities in the 2, 5-furandicarboxylic acid also undergo side reactions, so that the finally prepared bio-based antibacterial polyester has poor color. The invention controls the esterification reaction temperature at 190-200 ℃, can ensure the complete esterification reaction and reduce side reactions, so that the finally prepared bio-based antibacterial polyester has ideal viscosity and color.
Preferably, in the step (3), the reaction temperature of the transesterification reaction is 180-190 ℃ and the reaction time is 1-5 h.
Preferably, in the step (4), the reaction temperature of the one-stage polycondensation reaction is 210-230 ℃, the pressure is less than 0.1MPa, and the reaction time is 1-2 h.
Preferably, in the step (4), the reaction temperature of the two-stage polycondensation reaction is 230-260 ℃, the pressure is less than 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 (2), the diamine is one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine and 1, 10-decanediamine.
The length of the diamine should be controlled within a suitable range for the following reasons: the length of diamine is too short, which can cause the length of a flexible chain segment in a molecular chain of the bio-based antibacterial polyester to be too small, so that the toughness of the polyester material is poor; the excessive length of the diamine can cause the excessive length of the flexible chain segment in the molecular chain of the bio-based antibacterial polyester, so that the heat resistance and the barrier property of the polyester material are poor. According to the invention, the linear chain diamine is adopted, so that the influence of a branched chain on the flexibility of a chain section can be prevented, and the carbon number of the diamine is controlled within the range of 4-10, so that the finally prepared bio-based antibacterial polyester material has high toughness, heat resistance and barrier property.
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, 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 diphosphotriester, pentaerythritol tetrapentaphenyl tridecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate.
Preferably, after the step (4), grafting the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer to the high-toughness bio-based antibacterial polyester obtained in the step (4), and specifically, the method comprises the following steps: mixing the high-toughness bio-based antibacterial polyester obtained in the step (4) with the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer according to the mass ratio of 1:0.008-0.01, and performing ester exchange reaction at 180-190 ℃ for 2-3 h.
The requirement on the heat resistance and the barrier property of the bio-based polyester limits the introduction amount of the guanidino-containing dihydric aliphatic amine, so that the improvement of the toughness and the antibacterial property of the polyester material is limited. The toughness and antibacterial property can be further improved by grafting the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer, because: the guanidino in the molecular chain of the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer can play an antibacterial role, meanwhile, C-C and C-N chain segments in the copolymer enable the copolymer to have larger flexibility, when the bio-based polyester material is impacted or stretched, force is transmitted on the molecular chain of the copolymer, the larger branching degree and the higher flexibility can absorb and disperse a large amount of impact energy to play a buffering role, and therefore the toughness of the polyester material can be further improved; in addition, due to the higher branching degree of the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer, the free volume increase degree caused by the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer is smaller, so that the influence on the heat resistance and the barrier property of the polyester material is smaller.
However, the viscosity of the bio-based polyester is too high due to the excessive addition of the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer, and the application of the bio-based polyester is limited, so that the improvement of the toughness and antibacterial property of the copolymer to a polyester material is limited by the viscosity requirement of the polyester. The method combines two methods of introducing guanidine-containing diamine and grafting triethylene tetramine-methyl acrylate-triaminoguanidine copolymer, and can improve the toughness and antibacterial property of the bio-based polyester to a greater extent on the premise of meeting the requirements of heat resistance, barrier property and viscosity of the bio-based polyester.
Preferably, the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer 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 a mixed solution of triethylene tetramine and triaminoguanidine hydrochloride, wherein the molar ratio of the methyl acrylate to the triethylene tetramine to the triaminoguanidine hydrochloride is 1.7-2:1:0.1-0.3, reacting at 20-25 ℃ for 2-3h, removing the ethanol, and reacting at 150-160 ℃ and 0.2-0.5kPa for 3-4h to obtain a triethylene tetramine-methyl acrylate-triaminoguanidine copolymer;
(b) modification: dispersing the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer and glycidyl butyrate obtained in the step (a) 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 triethylene tetramine-methyl acrylate-triaminoguanidine copolymer.
In the step (a), the synthesis of the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer comprises two stages: in the first stage, carbon-carbon double bonds in methyl acrylate and amino groups in triethylene tetramine and triaminoguanidine hydrochloride are subjected to addition reaction, and simultaneously, carbon-carbon double bonds and one imino group in part of triethylene tetramine are subjected to addition reaction; and in the second stage, condensation polymerization is carried out between the addition product and the three reactants in the first stage through the reaction between the amino group and the ester group to form the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer.
Triethylene tetramine, methyl acrylate and triaminoguanidine are used as monomers for synthesizing a copolymer, wherein the triethylene tetramine is used for providing more C-N flexible chain segments, so that the bio-based polyester has higher toughness; the guanidino in the triaminoguanidine can affect the flexibility of the molecular chain of the copolymer, but has the functions of sterilization and bacteriostasis, and can improve the antibacterial property of the bio-based polyester.
In the step (b), the purpose of modification is to graft a molecule with two hydroxyl groups as a side chain onto a molecular chain of the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer, so that the copolymer can be grafted onto a molecular chain of the bio-based polyester through ester exchange reaction, and the modification mechanism is as follows: firstly, performing ring-opening reaction on amino and imino in a triethylene tetramine-methyl acrylate-triaminoguanidine copolymer and epoxy in glycidyl butyrate to graft the glycidyl butyrate onto the copolymer, wherein a hydroxyl group is formed in the process; the grafted ester group is then hydrolyzed to form another hydroxyl group.
Compared with the prior art, the invention has the following advantages:
(1) guanidino is introduced into the bio-based polyester in the form of the guanidino-containing dihydric fatty amine, so that the heat resistance and barrier property of the bio-based polyester can be ensured, the bio-based polyester is endowed with better antibacterial property, and the toughness of the bio-based polyester is effectively improved;
(2) the grafted triethylene tetramine-methyl acrylate-triaminoguanidine copolymer can further improve the antibacterial property and toughness 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 according to a molar ratio of 1:1.6-2, adding a catalyst and a heat stabilizer, and performing an 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 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-butylphenyl) phosphite, pentaerythritol dioctadecyl phosphite, pentaerythritol diisodecyl diphosphite, pentaerythritol diphosphotriester, pentaerythritol tetrapentaphenyl tridecyl phosphite, phosphoric acid, phosphorous acid, polyphosphoric acid and triethyl phosphonoacetate;
(2) mixing guanidine hydrochloride and diamine according to the molar ratio of 1:1-1.2, adding a catalyst and a heat stabilizer, and carrying out polycondensation reaction at the temperature of 140-; the diamine is one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine and 1, 10-decanediamine; 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) mixing the esterification reaction product obtained in the step (1) and the polycondensation reaction product obtained in the step (2) according to the molar ratio of 1:1.2-1.4, and carrying out an ester exchange reaction at the temperature of 180-190 ℃ for 1-5 h;
(4) and (3) vacuumizing the transesterification reaction product obtained in the step (3) to the pressure of less than 0.1Mpa, carrying out the one-stage polycondensation reaction at the temperature of 230 ℃ for 1-2h, then vacuumizing to the pressure of less than 100Pa when no white liquid is extracted, and carrying out the two-stage polycondensation reaction at the temperature of 260 ℃ for 1-5h to obtain the high-toughness bio-based antibacterial polyester.
Optionally, after the step (4), grafting the modified triethylenetetramine-methyl acrylate-triaminoguanidine copolymer to the high-toughness bio-based antibacterial polyester obtained in the step (4), specifically comprising the following steps:
(a) preparing a triethylene tetramine-methyl acrylate-triaminoguanidine copolymer: under the protection of inert gas, dropwise adding a mixed solution of methyl acrylate and ethanol into a mixed solution of triethylene tetramine and triaminoguanidine hydrochloride, wherein the molar ratio of the methyl acrylate to the triethylene tetramine to the triaminoguanidine hydrochloride is 1.7-2:1:0.1-0.3, reacting at 20-25 ℃ for 2-3h, removing the ethanol, and reacting at 150-160 ℃ and 0.2-0.5kPa for 3-4h to obtain a triethylene tetramine-methyl acrylate-triaminoguanidine copolymer;
(b) preparing a modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer: dispersing the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer and the glycidol butyrate obtained in the step (a) 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 triethylene tetramine-methyl acrylate-triaminoguanidine copolymer.
(c) Mixing the high-toughness bio-based antibacterial polyester obtained in the step (4) with the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer obtained in the step (b) according to the mass ratio of 1:0.008-0.01, and performing ester exchange reaction at 180-190 ℃ for 2-3 h.
Example 1
Preparing a bio-based polyester by:
(1) putting 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into an esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) placing 74g of guanidine hydrochloride, 100g of 1, 4-butanediamine, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 in a polycondensation reaction kettle, and carrying out polycondensation reaction at 145 ℃ for 2.5 h;
(3) transferring all esterification reaction products obtained in the step (1) and polycondensation reaction products obtained in the step (2) into an ester exchange reaction kettle, replacing air in the reaction kettle with nitrogen, and carrying out ester exchange reaction at 190 ℃ for 2.5 h;
(4) and (3) transferring the transesterification reaction product obtained in the step (3) to a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product to a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, and thus obtaining the high-toughness bio-based antibacterial polyester.
Example 2
Preparing a bio-based polyester by:
(1) putting 100g of 2, 5-furandicarboxylic acid, 88g of 1, 3-propylene glycol, 0.1g of zinc acetate and 0.1g of antioxidant 1076 into an esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 1 h;
(2) putting 68g of guanidine hydrochloride, 110g of 1, 5-pentanediamine, 0.1g of zinc acetate and 0.1g of antioxidant 1076 into a polycondensation reaction kettle, and carrying out polycondensation reaction at 145 ℃ for 1 h;
(3) transferring all esterification reaction products obtained in the step (1) and polycondensation reaction products obtained in the step (2) into an ester exchange reaction kettle, replacing air in the reaction kettle with nitrogen, and carrying out ester exchange reaction at 190 ℃ for 5 hours;
(4) and (3) transferring the transesterification reaction product obtained in the step (3) to a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product to a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, and thus obtaining the high-toughness bio-based antibacterial polyester.
Example 3
Preparing a bio-based polyester by:
(1) putting 100g of 2, 5-furandicarboxylic acid, 116g of 1, 4-butanediol, 0.1g of stannous octoate and 0.1g of triphenyl phosphite in an esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 5 hours;
(2) placing 74g of guanidine hydrochloride, 142g of 1, 6-hexanediamine, 0.1g of stannous octoate and 0.1g of triphenyl phosphite in a polycondensation reaction kettle, and carrying out polycondensation reaction at 145 ℃ for 5 hours;
(3) transferring all esterification reaction products obtained in the step (1) and polycondensation reaction products obtained in the step (2) into an ester exchange reaction kettle, replacing air in the reaction kettle with nitrogen, and carrying out ester exchange reaction at 190 ℃ for 1 h;
(4) and (3) transferring the transesterification reaction product obtained in the step (3) to a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product to a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, and thus obtaining the high-toughness bio-based antibacterial polyester.
Example 4
Preparing a bio-based polyester by:
(1) 100g of 2, 5-furandicarboxylic acid, 122g of 1, 6-hexanediol, 0.1g of a silicon dioxide/titanium dioxide/nitrogen-containing compound and 0.1g of triethyl phosphonoacetate are placed in an esterification reaction kettle, and an esterification reaction is carried out at 195 ℃, wherein the reaction time is 2.5 h;
(2) placing 74g of guanidine hydrochloride, 134g of 1, 10-decamethylene diamine, 0.1g of silicon dioxide/titanium dioxide/nitrogen-containing compound and 0.1g of triethyl phosphonoacetate in a polycondensation reaction kettle, and carrying out polycondensation reaction at 145 ℃ for 2.5 hours;
(3) transferring all esterification reaction products obtained in the step (1) and polycondensation reaction products obtained in the step (2) into an ester exchange reaction kettle, replacing air in the reaction kettle with nitrogen, and carrying out ester exchange reaction at 190 ℃ for 2.5 h;
(4) and (3) transferring the transesterification reaction product obtained in the step (3) to a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product to a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, and thus obtaining the high-toughness bio-based antibacterial polyester.
Example 5
Preparing a bio-based polyester by:
(1) putting 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into an esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) placing 74g of guanidine hydrochloride, 100g of 1, 4-butanediamine, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 in a polycondensation reaction kettle, and carrying out polycondensation reaction at 145 ℃ for 2.5 h;
(3) transferring all esterification reaction products obtained in the step (1) and polycondensation reaction products obtained in the step (2) into an ester exchange reaction kettle, replacing air in the reaction kettle with nitrogen, and carrying out ester exchange reaction at 190 ℃ for 2.5 h;
(4) transferring the transesterification reaction product obtained in the step (3) into a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product into a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, thus obtaining the high-toughness bio-based antibacterial polyester;
(5) grafting a modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer to the polyester obtained in the step (4):
(5.1) preparation of triethylene tetramine-methyl acrylate-triaminoguanidine copolymer: preparing 60g of methyl acrylate and 150mL of ethanol into a mixed solution; dropwise adding the mixed solution into a mixed solution of 51g of triethylene tetramine and 14.6g of triaminoguanidine hydrochloride under the protection of nitrogen, reacting for 2.5 hours at the temperature of 20 ℃, removing ethanol, and reacting for 3.5 hours at the temperature of 155 ℃ and under the pressure of 0.3kPa to obtain triethylene tetramine-methyl acrylate-triaminoguanidine copolymer;
(5.2) preparing a modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer: dispersing the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer obtained in the step (5.1) and 1.3g of glycidyl butyrate into alcohol, and reacting for 2.5h at 105 ℃; 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 the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer.
And (5.3) mixing the high-toughness bio-based antibacterial polyester obtained in the step (4) with the modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer obtained in the step (5.2), and performing ester exchange reaction at 185 ℃ for 2.5 hours to obtain the high-toughness bio-based antibacterial polyester.
Comparative example 1
Preparing a bio-based polyester by:
(1) putting 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 into an esterification reaction kettle, and carrying out esterification reaction at 195 ℃ for 2.5 h;
(2) and (2) transferring the esterification reaction product obtained in the step (1) into a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product into a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa for 3h, and thus obtaining the high-toughness bio-based antibacterial polyester.
Comparative example 2
Preparing a bio-based polyester by:
(1) placing 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 74g of guanidine hydrochloride, 100g of 1, 4-butanediamine, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 in a reaction kettle, and carrying out polymerization reaction at 195 ℃ for 7.5 h;
(2) and (2) transferring the polymerization reaction product obtained in the step (1) into a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product into a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa, and carrying out the reaction time for 3h to obtain the high-toughness bio-based antibacterial polyester.
Comparative example 3
Preparing a bio-based polyester by:
(1) 100g of 2, 5-furandicarboxylic acid, 64g of ethylene glycol, 74g of guanidine hydrochloride, 100g of 1, 4-butanediamine, 0.1g of n-butyl titanate and 0.1g of antioxidant 1010 are placed in a reaction kettle, and polymerization reaction is carried out at 145 ℃ for 7.5 h;
(2) and (2) transferring the polymerization reaction product obtained in the step (1) into a one-stage polycondensation reaction kettle, carrying out one-stage polycondensation reaction at 220 ℃ and 0.08MPa, transferring the product into a two-stage polycondensation reaction after the reaction time is 1-2h and when no white liquid is extracted, carrying out two-stage polycondensation reaction at 240 ℃ and 80Pa, and carrying out the reaction time for 3h to obtain the high-toughness bio-based antibacterial polyester.
The bio-based polyesters prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to color, intrinsic viscosity, heat resistance, barrier property, toughness and antibacterial property tests, the test methods were as follows:
(1) and (3) color testing: adopting a TES-135 material color analyzer produced by Taiwan Shishi electronics to measure the L, a and b values of the bio-based polyester, 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 TA DSC 2920 instrument from Thermal analysis Instruments at a scan rate of 20 ℃/min;
(4) barrier properties: with O 2 And CO 2 The gas permeation coefficient of (2) represents the barrier property of the bio-based polyester, and the smaller the gas permeation coefficient is, the better the barrier property is; using a Labthink VAC-V2 pressure differential gas permeameter for CO with pressures of 0.4-0.6MPa 2 And O 2 As air source, under the conditions of 23 deg.C and 50% RH of temperature and humidity, respectively, selecting the size phi of 97mm and the transmission area of 38.5cm 2 The gas transmission coefficient of a sample with the thickness of 130- 3 /(m 2 ·24h·0.1MPa)；
(5) And (3) testing toughness: 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; preparing a dumbbell-shaped sample strip with the thickness of 2mm and the width of 4mm from the bio-based polyester by using a HaakeMinJet II micro injection molding machine, and testing the elongation at break of the sample strip at 25 ℃ and at a tensile rate of 10mm/min by adopting a Roell Z020 type universal material testing machine of Germany Zwick according to the standard of ASTM D638-2014;
(6) and (3) antibacterial property test: the antibacterial property of the bio-based polyester is characterized by the antibacterial rate, and the higher the antibacterial rate is, the better the antibacterial property is; an oscillation method is adopted for carrying out experiments, and staphylococcus aureus is used as a sample for testing the bacteriostasis rate.
The test results are shown in table 1.
TABLE 1
Example 1 is different from comparative example 1 in that in example 1, a guanidino group is introduced into a bio-based polyester in the form of a guanidino group-containing di-aliphatic amine by the polycondensation reaction of step (2) and the transesterification reaction of step (3), whereas in comparative example 1, these two steps are not performed and the remaining preparation processes are the same. As can be seen from the data in table 1, the bio-based polyester obtained in example 1 has a lower glass transition temperature and an increased gas permeability coefficient, but the elongation at break and the bacteriostatic rate are greatly improved, compared to comparative example 1. This suggests that the heat resistance and barrier properties of the bio-based polyester are slightly reduced by the production method of the present invention, but the toughness and antibacterial property are effectively enhanced, presumably because: the guanidino can be combined with the bacterial cell membrane and finally leads the cell membrane to be broken to kill the cell, so that the introduction of the guanidino can endow the bio-based polyester with antibacterial effect; meanwhile, the guanidino is introduced in the form of the guanidino-containing dihydric fatty amine, and as the C-C chain segment in the dihydric fatty amine has larger flexibility, a flexible chain segment can be introduced into the polyfuran dicarboxylic acid diol ester, and when the external impact is applied, the flexible chain segment absorbs a part of impact energy through the movement of the chain segment, so that the toughness of the bio-based polyester can be improved.
Example 1 differs from comparative example 2 in that in example 1, the steps (1) to (3) introduce a guanidine group into a bio-based polyester by esterification, polycondensation and transesterification, while in comparative example 2, the steps are combined, a guanidine group is introduced into a bio-based polyester by one-step polymerization, the temperature of the esterification in step (1) of example 1 is selected, and the rest of the preparation process is the same. From the data in table 1, the elongation at break and the bacteriostatic rate of the bio-based polyester prepared in comparative example 1 are increased, but the glass transition temperature is significantly decreased and the gas permeability coefficient is significantly increased, compared to example 1. The reason for this may be: the esterification reaction temperature is too high for the polycondensation reaction, and the molecular weight of the guanidine group-containing diamine obtained by the polycondensation reaction is too high by adopting the esterification reaction temperature for one-step polymerization, so that the heat resistance and the barrier property of the finally prepared bio-based antibacterial polyester material are obviously reduced.
Example 1 differs from comparative example 3 in that in example 1, the steps (1) to (3) introduce a guanidine group into a bio-based polyester by esterification, polycondensation and transesterification, while in comparative example 3, the steps are combined, a guanidine group is introduced into a bio-based polyester by one-step polymerization, the temperature of the polycondensation in step (2) of example 1 is selected, and the rest of the preparation is the same. As seen from the data in Table 1, the bio-based polyester obtained in comparative example 3 has an improved bacteriostasis rate as compared to example 1, but the intrinsic viscosity, glass transition temperature, and elongation at break are all significantly reduced, and the gas permeability is significantly increased. The reason for this speculation may be: the polycondensation reaction temperature is too low for the esterification reaction, the polycondensation reaction temperature is adopted for one-step polymerization, the energy barrier of the esterification reaction is difficult to overcome, the esterification reaction cannot be fully performed, and the polycondensation reaction between guanidine hydrochloride and diamine can be normally performed, so that the content of guanidyl in the molecular chain of the finally prepared bio-based polyester is higher, and the antibacterial property is stronger; however, the esterification reaction cannot be sufficiently carried out, which affects the subsequent one-stage polycondensation reaction and two-stage polycondensation reaction, resulting in that the molecular weight of the prepared bio-based polyester is too low, and the viscosity, heat resistance, barrier property and toughness of the prepared bio-based polyester are too low.
Example 5 is different from example 1 in that in example 5, modified triethylene tetramine-methyl acrylate-triaminoguanidine copolymer is grafted on bio-based polyester by (5), but in example 1, the procedure is not adopted, and the rest of the preparation process is the same. As seen from the data in Table 1, the glass transition temperature of the resulting bio-based polyester of example 5 was decreased, the gas permeability coefficient was increased, but the range was not so large, and the elongation at break and the antibacterial ratio were greatly increased, as compared to example 1. The reason for this speculation may be: after the triethylene tetramine-methyl acrylate-triaminoguanidine copolymer is grafted, the free volume of the polyester is increased, so that the barrier property and the heat resistance are reduced, but the reduction range of the barrier property and the heat resistance is small due to the higher esterification degree of the copolymer; and moreover, the guanidino in the copolymer can play an antibacterial role, so that the copolymer can endow the bio-based polyester with better antibacterial property, meanwhile, the C-C and C-N chain segments in the molecular chain of the copolymer enable the copolymer to have larger flexibility, when the bio-based polyester material is impacted or stretched, force is transmitted on the molecular chain of the copolymer, and the larger branching degree and the higher flexibility can absorb and disperse a large amount of impact energy to play a buffering role, so that the toughness of the polyester material can be further improved.
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 (6)
1. A preparation method of high-toughness bio-based antibacterial polyester is characterized by comprising the following steps:
(1) mixing 2, 5-furandicarboxylic acid, dihydric alcohol, a catalyst and a heat stabilizer, and carrying out an esterification reaction at 190-200 ℃ for 1-5 h;
(2) mixing guanidine hydrochloride, diamine, a catalyst and a heat stabilizer, and carrying out polycondensation reaction at the temperature of 140-; the diamine is one or more of 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 8-octanediamine and 1, 10-decanediamine;
(3) mixing the esterification reaction product obtained in the step (1) and the polycondensation reaction product obtained in the step (2) in a molar ratio of 1:1.2-1.4, and carrying out an ester exchange reaction;
(4) vacuumizing the transesterification reaction product obtained in the step (3) and carrying out a one-stage polycondensation reaction; when no white liquid is extracted, carrying out two-stage polycondensation reaction to obtain the high-toughness bio-based antibacterial polyester.
2. The method for preparing high-toughness bio-based antibacterial polyester according to claim 1, wherein in the step (2), the molar ratio of guanidine hydrochloride to diamine is 1: 1-1.2.
3. The method for preparing a high-toughness bio-based antibacterial polyester as claimed in claim 1, wherein in the step (1), the molar ratio of 2, 5-furandicarboxylic acid to diol is 1: 1.6-2.
4. The method for preparing the high-toughness bio-based antibacterial polyester as claimed in claim 1, wherein in the step (3), the reaction temperature of the transesterification reaction is 180-190 ℃, and the reaction time is 1-5 h.
5. The method for preparing high-toughness bio-based antibacterial polyester as claimed in claim 1, wherein:
in the step (4), the reaction temperature of the one-stage polycondensation reaction is 210-; and/or
In the step (4), the reaction temperature of the two-stage polycondensation reaction is 230-260 ℃, the pressure is less than 100Pa, and the reaction time is 1-5 h.
6. The method for preparing a high toughness bio-based antibacterial polyester as claimed in claim 1, wherein in step (1), said diol is one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol.
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