CN113444234B - Antibacterial polyester copolymerization modification process - Google Patents
Antibacterial polyester copolymerization modification process Download PDFInfo
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- CN113444234B CN113444234B CN202110730981.5A CN202110730981A CN113444234B CN 113444234 B CN113444234 B CN 113444234B CN 202110730981 A CN202110730981 A CN 202110730981A CN 113444234 B CN113444234 B CN 113444234B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Polymers & Plastics (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses an antibacterial polyester copolymerization modification process, which relates to the technical field of antibacterial high polymer materials and is characterized in that a hydroxyl-terminated polyester oligomer and a compound with a structure shown in a formula (I) are subjected to polycondensation reaction in the presence of a catalyst to obtain antibacterial modified polyester. The invention adopts the hydroxyl-terminated polyester oligomer as a prepolymer and prepares the antibacterial modified polyester through polycondensation reaction with the compound of the formula (I), so that the original structure of polyester molecules can be reserved to the greatest extent, and the excellent antibacterial effect of the polyester material can be endowed through the introduction of a small amount of the compound of the formula (I).
Description
Technical field:
the invention relates to the technical field of antibacterial high polymer materials, in particular to an antibacterial polyester copolymerization modification process.
The background technology is as follows:
the polyester is a polymer obtained by polycondensation of polyalcohol and polybasic acid, mainly refers to polyethylene terephthalate (PET), and conventionally comprises linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate, is an engineering plastic with excellent performance and wide application, and can be also made into polyester fibers and polyester films. Polyesters include polyester resins and polyester elastomers. The polyester resin in turn includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate (PAR), and the like. Polyester elastomers (TPEEs) are typically polymerized from dimethyl terephthalate, 1, 4-butanediol, and polybutanol, with segments comprising hard and soft segments being thermoplastic elastomers.
In recent years, common methods for producing antibacterial polyesters include melt blending, surface treatment, graft copolymerization, and the like. The melt blending process is easier to implement, but because of the high processing temperatures of polyesters, high temperature antimicrobial agents must be selected. The surface treatment method has simple process, but is not wash-resistant, has poor antibacterial durability and is mostly applied to disposable products. The graft copolymerization method requires the use of an antimicrobial agent that reacts with the polyester, and thus has a requirement on the molecular structure of the antimicrobial agent.
Currently, antibacterial agents that can be used to make antibacterial polyesters mainly include inorganic antibacterial agents, organic antibacterial agents, and natural antibacterial agents. The inorganic antibacterial agent is prepared by fixing metals (or ions thereof) such as silver, copper, zinc and the like on the surface of porous materials such as fluorite, silica gel and the like by utilizing the antibacterial capability of the metals such as silver, copper, zinc and the like through physical adsorption ion exchange and other methods, and then adding the materials into polyester to obtain the material with antibacterial capability. However, the inorganic antibacterial agent is difficult to disperse in polyester, and the defects of poor flexibility, low breaking strength and the like of the polyester material are easily caused. The natural antibacterial agent mainly comes from natural plant extraction, such as chitin, mustard, castor oil, horseradish, etc., and has simple and convenient use, but has limited antibacterial effect, poor heat resistance, low sterilization rate, no broad-spectrum long-acting use and small quantity. The organic antibacterial agents mainly include acylanilines, imidazoles, thiazoles, isothiazolone derivatives, quaternary ammonium salts, biguanides, phenols and the like, and although the antibacterial agents are strong in pertinence, the heat resistance and the water washing resistance are poor.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing an antibacterial polyester copolymerization modification process, which introduces a benzophenone derivative into a polyester molecular chain through polymerization reaction, so that the prepared polyester has excellent antibacterial property and water washing resistance, and can solve the problem of poor water washing resistance of the conventional antibacterial agent.
The technical problems to be solved by the invention are realized by adopting the following technical scheme:
an antibacterial polyester copolymerization modification process comprises the steps of carrying out polycondensation reaction on a hydroxyl-terminated polyester oligomer and a compound with a structure shown in a formula (I) in the presence of a catalyst to obtain antibacterial modified polyester;
the hydroxyl-terminated polyester oligomer and the compound of the formula (I) are subjected to polycondensation reaction, and the compound of the formula (I) is introduced into a polyester molecular chain, so that the generated modified polyester has antibacterial property, physical or chemical addition of an antibacterial agent can not be carried out, and the antibacterial durability can be ensured.
The polyester oligomer is one or more of polyethylene terephthalate prepolymer, polypropylene terephthalate prepolymer and polybutylene terephthalate prepolymer.
The number average molecular weight of the polyester oligomer is 10000-50000.
The catalyst is antimony trioxide, antimony acetate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate or tetraisopropyl titanate.
Preferably, the catalyst is antimony trioxide or tetraisopropyl titanate.
The mass ratio of the polyester oligomer to the compound of the formula (I) is 1000 (5-50).
The absolute pressure of the polycondensation reaction is less than or equal to 1kPa, and the temperature is 200-280 ℃.
The compound of the formula (I) is prepared by substitution reaction of 4,4' -dichlorobenzophenone and glycine in the presence of an acid binding agent.
The molar ratio of the 4,4' -dichlorobenzophenone to glycine is 1 (1-1.05).
The acid binding agent is triethylamine or pyridine.
Synthetic route for compounds of formula (I):
the mechanism of synthesis of the compounds of formula (I):
1 molecule 4,4' -dichloro diphenyl ketone and 1 molecule glycine undergo substitution reaction to generate a compound shown in a formula (I), triethylamine or pyridine is adopted as an acid binding agent, hydrogen chloride generated by the reaction is neutralized immediately, and forward progress of the reaction is promoted.
The beneficial effects of the invention are as follows:
(1) The invention adopts the hydroxyl-terminated polyester oligomer as a prepolymer and prepares the antibacterial modified polyester through polycondensation reaction with the compound of the formula (I), so that the original structure of polyester molecules can be reserved to the greatest extent, and the excellent antibacterial effect of the polyester material can be endowed through the introduction of a small amount of the compound of the formula (I).
(2) According to the invention, the compound shown in the formula (I) is introduced into a polyester molecular chain in a covalent bond form, so that the antibacterial durability of the polyester material can be greatly improved, and the problem that the antibacterial performance of the conventional antibacterial polyester material is obviously reduced due to stripping of an antibacterial agent or an antibacterial group after water washing is solved.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
The compounds of formula (I) in the following examples were prepared using the following procedure:
synthesis of compounds of formula (I): adding 10.2g of triethylamine into 25g of acetone solution containing 4,4' -dichlorobenzophenone, heating to 65 ℃ after complete dissolution, maintaining the temperature and stirring, beginning to dropwise add aqueous solution containing 7.6g of glycine, continuously reacting at 65 ℃ for 2 hours after the dropwise addition, distilling to remove acetone and water, separating out solid, and carrying out column chromatography on the solid (the volume ratio of ethyl acetate to petroleum ether is 2-5:1), thereby obtaining the compound of the formula (I) with the yield of 95.8%. 1 H NMR(DMSO-d6,400MHz),δ:12.98(s,2H),7.65(d,4H),6.77(d,4H),6.23(s,2H),3.96(s,4H).
Example 1
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxyl-terminated polyethylene terephthalate prepolymer (with the number average molecular weight of 22000), 30g of compound of formula (I) and 0.5g of tetraisopropyl titanate are added into the reaction kettle, the reaction is carried out for 2 hours at the pressure of 1kPa and the temperature of 220 ℃, the reaction is carried out for 1 hour at the pressure of 100Pa and the temperature of 280 ℃, and the antibacterial modified polyester is obtained after cooling and discharging.
Example 2
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxy-terminated polytrimethylene terephthalate prepolymer (with the number average molecular weight of 25000), 35g of compound of formula (I) and 0.25g of antimonous oxide are added into the reaction kettle, the mixture is reacted for 2 hours at the pressure of 1kPa and the temperature of 200 ℃, then reacted for 1 hour at the pressure of 100Pa and the temperature of 280 ℃, and the mixture is cooled and discharged to obtain the antibacterial modified polyester.
Example 3
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxyl-terminated polybutylene terephthalate prepolymer (with the number average molecular weight of 18000), 40g of compound of formula (I) and 0.4g of tetraisopropyl titanate are added into the reaction kettle, the mixture is reacted for 2 hours at the temperature of 210 ℃ under the pressure of 1kPa, the mixture is reacted for 2 hours at the temperature of 250 ℃ under the pressure of 100Pa, and the mixture is cooled and discharged to obtain the antibacterial modified polyester.
Example 4
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxyl-terminated polyethylene terephthalate prepolymer (with the number average molecular weight of 22000), 32g of compound of formula (I) and 0.2g of antimonous oxide are added into the reaction kettle, the reaction is carried out for 2 hours at the temperature of 200 ℃ and the pressure of 1kPa, the reaction is carried out for 1.5 hours at the temperature of 280 ℃ and the pressure of 80Pa, and the antibacterial modified polyester is obtained after cooling and discharging.
Comparative example 1
Comparative example 1 the compound of formula (I) in example 1 was replaced with p-hydroxybenzoic acid, the remainder being as in example 1.
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxy-terminated polyethylene terephthalate prepolymer (with the number average molecular weight of 22000), 30g of p-hydroxybenzoic acid and 0.5g of tetraisopropyl titanate are added into the reaction kettle, the mixture is reacted for 2 hours at the pressure of 1kPa and the temperature of 220 ℃, the reaction is carried out for 1 hour at the pressure of 100Pa and the temperature of 280 ℃, and the mixture is cooled and discharged to obtain the antibacterial modified polyester.
Comparative example 2
Comparative example 2 the compound of formula (I) in example 2 was replaced with p-hydroxybenzoic acid, the remainder being as in example 2.
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxy-terminated polytrimethylene terephthalate prepolymer (with the number average molecular weight of 25000), 35g of p-hydroxybenzoic acid and 0.25g of antimonous oxide are added into the reaction kettle, the mixture is reacted for 2 hours at the pressure of 1kPa and the temperature of 200 ℃, then the mixture is reacted for 1 hour at the pressure of 100Pa and the temperature of 280 ℃, and the mixture is cooled and discharged to obtain the antibacterial modified polyester.
Comparative example 3
Comparative example 3 the compound of formula (I) in example 3 was replaced with p-hydroxybenzoic acid, the remainder being as in example 3.
Preparation of antibacterial modified polyester: air in the reaction kettle is replaced by nitrogen, 1000g of hydroxyl-terminated polybutylene terephthalate prepolymer (with the number average molecular weight of 18000), 40g of parahydroxybenzoic acid and 0.4g of tetraisopropyl titanate are added into the reaction kettle, the mixture is reacted for 2 hours at the temperature of 210 ℃ under the pressure of 1kPa, the mixture is reacted for 2 hours at the temperature of 250 ℃ under the pressure of 100Pa, and the mixture is cooled and discharged to obtain the antibacterial modified polyester.
The antibacterial modified polyester prepared in the above examples and comparative examples is melt-spun to obtain polyester fiber, and the polyester fiber is made into a fabric, and then the fabric is subjected to the evaluation of antibacterial properties of textiles according to the standard GB/T20944.2-2007 part 2: the antibacterial property of the fabric was measured by the absorption method, and the results are shown in Table 1.
TABLE 1 determination of antibacterial Properties
The fabrics prepared from the antibacterial modified polyesters of examples 1-4 were washed 30 times according to the standard FZ/T73023-2006 test method for washing test of antibacterial fabrics in annex C for antibacterial knitwear, and the antibacterial rate against Escherichia coli, staphylococcus aureus and Candida albicans was not less than 99%, indicating good water-washing resistance and strong antibacterial durability.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. An antibacterial polyester copolymerization modification process is characterized in that: performing polycondensation reaction on the hydroxyl-terminated polyester oligomer and a compound with a structure shown in a formula (I) in the presence of a catalyst to obtain antibacterial modified polyester;
the polyester oligomer is one or more of polyethylene terephthalate prepolymer, polypropylene terephthalate prepolymer and polybutylene terephthalate prepolymer;
the mass ratio of the polyester oligomer to the compound of the formula (I) is 1000 (5-50).
2. The antibacterial polyester copolymerization modification process according to claim 1, wherein: the number average molecular weight of the polyester oligomer is 10000-50000.
3. The antibacterial polyester copolymerization modification process according to claim 1, wherein: the catalyst is antimony trioxide, antimony acetate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate or tetraisopropyl titanate.
4. The antibacterial polyester copolymerization modification process according to claim 3, wherein: the catalyst is antimony trioxide or tetraisopropyl titanate.
5. The antibacterial polyester copolymerization modification process according to claim 1, wherein: the absolute pressure of the polycondensation reaction is less than or equal to 1kPa, and the temperature is 200-280 ℃.
6. The antibacterial polyester copolymerization modification process according to claim 1, wherein: the compound of the formula (I) is prepared by substitution reaction of 4,4' -dichlorobenzophenone and glycine in the presence of an acid binding agent.
7. The antibacterial polyester copolymerization modification process according to claim 6, wherein: the acid binding agent is triethylamine or pyridine.
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| CN107400206B (en) * | 2017-07-20 | 2020-05-15 | 汕头大学 | Long-acting antibacterial polyester copolymer and preparation and application thereof |
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