CN117069626A - Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester - Google Patents

Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester Download PDF

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CN117069626A
CN117069626A CN202311344522.9A CN202311344522A CN117069626A CN 117069626 A CN117069626 A CN 117069626A CN 202311344522 A CN202311344522 A CN 202311344522A CN 117069626 A CN117069626 A CN 117069626A
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antibacterial
esterification
reactive
formula
reaction
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马正升
马逸凡
赵亮东
董红霞
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Shanghai Guofan Chemical New Material Co ltd
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Shanghai Guofan Chemical New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C07C309/58—Carboxylic acid groups or esters thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • 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
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Textile Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a reactive antibacterial component, a synthesis method thereof, application of the reactive antibacterial component in preparation of antibacterial polyester and application of the antibacterial polyester in production of medical surgical products, and mainly solves the defect of poor washing resistance and antibacterial performance of the conventional antibacterial polyester fiber, the reactive antibacterial component is prepared by esterification reaction of a substance shown in the following formula 3 and glycol, Q is a quaternary ammonium group containing long-chain hydrocarbon groups, the number of carbon atoms in the long-chain hydrocarbon groups is 6-20, ar is an aromatic ring, and the glycol is ethylene glycol and 1, 4-cyclohexanedimethanol:

Description

Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester
Technical Field
The invention relates to a reactive antibacterial component, a synthesis method thereof, application of the reactive antibacterial component in preparation of antibacterial polyester and application of the antibacterial polyester in production of medical surgical articles.
Background
Polyester fibers are a large variety of synthetic fibers and are widely applied to home textiles, clothing, industrial textiles and the like. Bacterial infection is one of the main threats to human health, and the development of polyester fiber with an antibacterial function is beneficial to blocking the transmission of bacteria, reducing the risk of bacterial infection, reducing the use of antibiotics and improving the health level of people, and has very important significance. At present, the antibacterial polyester fiber is mainly prepared by physically blending inorganic antibacterial agents such as nano silver, nano zinc oxide and the like, but the antibacterial performance of the antibacterial polyester fiber is derived from the diffusion release of the antibacterial agents, the antibacterial performance of the antibacterial polyester fiber is lost along with the release of the antibacterial agents, particularly, the antibacterial polyester fiber has the problem of serious loss in the daily washing and other processes, and the antibacterial polyester fiber does not have long-acting antibacterial capability. Meanwhile, the inorganic antibacterial agent has larger biotoxicity, and textile used close to the human body can cause skin allergy and the like, so that the application range is limited. The most common method for synthesizing commercial polyester fibers on a large scale at present is to melt-condense and polymerize dicarboxylic acid and dihydric alcohol and then melt-spin and form the polyester fibers. The organic ecological antibacterial agent is covalently bonded to the main chain of the polyester in a copolycondensation mode, so that the lasting antibacterial property of the polyester can be endowed, the biotoxicity of the antibacterial agent can be effectively reduced, and the development direction of the antibacterial polyester fiber is realized.
Disclosure of Invention
One of the technical problems to be solved by the invention is the defect of poor washing resistance and antibacterial performance of the existing antibacterial polyester fiber, and the invention provides a novel reactive antibacterial component which endows the antibacterial performance of the antibacterial polyester fiber with the advantage of washing resistance.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
the reactive antibacterial component is prepared by esterification reaction of a substance shown in the following formula 3 and glycol:
formula 3;
q is a quaternary ammonium group containing long-chain hydrocarbon groups, the number of carbon atoms in the long-chain hydrocarbon groups is 6-20, and Ar is an aromatic ring.
The antibacterial polyester prepared by the reactive antibacterial component has more washing-resistant antibacterial performance compared with the antibacterial component shown in the formula 3.
In the above-mentioned embodiments, ar is preferably a benzene ring or naphthalene ring.
The second technical problem to be solved by the invention is to provide a synthesis method of the reactive antibacterial component.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the synthesis method of the reactive antibacterial component comprises the following steps:
(1) Subjecting compound 1 and compound 2 to ion exchange reaction in solvent to obtain intermediate 3;
compound 1 corresponds to the structure shown in formula 1:
the method comprises the steps of 1,
compound 2 corresponds to the structure shown in formula 2:
2, the number of the active ingredients in the liquid crystal layer,
intermediate 3 corresponds to the structure shown in formula 3;
x is Cl or Br; m is an alkali metal;
(2) And (3) carrying out esterification reaction on the intermediate product 3 and glycol to obtain the reactive antibacterial component.
In the above technical solution, the solvent in step (1) is preferably water.
The ion exchange reaction equation in step (1) is expressed as follows:
when water is used as the ion exchange reaction solvent, the intermediate product 3 is precipitated in a reaction system in a form of precipitation, and is very convenient to separate from the reaction system.
As non-limiting examples of compound 1, there are exemplified but not limited to benzalkonium chloride, hexyltrimethylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, N-hexylpyridine chloride, N-octylpyridine chloride, N-decylpyridine chloride, N-dodecylpyridine chloride, N-tetradecylpyridine chloride, N-octadecylpyridine chloride, 1-hexa-3-methylimidazole bromide, 1-octaalkyl-3-methylimidazole, 1-decaalkyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole bromide, 1-octadecyl-3-methylimidazole bromide, bishexaalkyl dimethylammonium chloride, bisoctaalkyl dimethylammonium chloride, bisdecaalkyl dimethylammonium chloride, bisdodecyl dimethylammonium chloride, bistetradecyldimethylammonium chloride, bishexadecyldimethylammonium chloride or bisoctadecyldimethylammonium chloride.
In the above technical scheme, the optional compound 1 conforms to the structure shown in formula 1 a:
formula 1a;
R 1 long chain hydrocarbyl radicals R 1 The number of carbon atoms is 6-20;
R 2 ~R 4 is a short chain hydrocarbon group, R 2 ~R 4 Independently preferably C1-C2 alkyl.
By way of non-limiting example, R 1 The number of carbon atoms is, but not limited to, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, etc. R is R 1 May be alkyl, alkenyl or aryl.
In the above technical scheme, it is preferable that compound 2 corresponds to the structure shown in formula 2 a:
formula 2a.
By way of example only, compound 2 in the examples of the present invention employed an alkali metal salt of isophthalic acid-5-sulfonic acid.
In the above technical scheme, the ion exchange reaction is rapid and rapid, the reaction is complete, and the ion exchange reaction is similar to the inorganic ion exchange reaction, and therefore, the specific process conditions of the ion exchange reaction are not particularly limited, and the process conditions commonly used in the field can be adopted. By way of example only, for example, compound 1 may be dissolved in an aqueous solution having a concentration of 1 to 10% by weight (e.g., but not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) and added to the reaction system, and for example, compound 2 may be dissolved in an aqueous solution having a concentration of 1 to 10% by weight (e.g., but not limited to 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.) and added to the reaction system. The reaction temperature is not particularly required, and the reaction can be smoothly carried out at room temperature. The reaction time is not particularly limited, and the ion exchange reaction is rapid, but the time for maintaining the reaction condition, namely the apparent reaction time, is prolonged within a certain range, so that the precipitated substances obtained by the ion exchange reaction can be better in a precipitation aggregation form, and the subsequent washing separation is facilitated, for example, the apparent reaction time can be 1.5-3 hours. The apparent reaction time is mainly the aging time of the ion exchange product in the reaction system, because the ion exchange reaction itself can be completed instantaneously.
In the above embodiment, the diol in step (2) preferably comprises a diol selected from the group consisting of 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 4-cyclohexanedimethanol and OCH-based diols 2 CH 2 At least one of the group consisting of diols of the units; OCH-based 2 CH 2 The diol of the unit corresponds to formula 4:
the present invention relates to a method for manufacturing a semiconductor device4；
Preferably based on OCH 2 CH 2 The number average molecular weight of the diol of the unit is greater than the molecular weight of ethylene glycol and less than 4000 g/mol, and m is a value required to meet the desired molecular weight.
Such as but not limited to OCH-based 2 CH 2 The diols of the units are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 500, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, polyethylene glycol 1500, polyethylene glycol 2000, polyethylene glycol 2500, polyethylene glycol 3000, polyethylene glycol 3500, polyethylene glycol 4000, and the like. The numbers following the polyethylene glycol represent the number average molecular weight according to the naming convention of the polyethylene glycol designation.
We have found that when the diol used in step (2) has a greater impact on the antimicrobial properties of the antimicrobial polyester than when the diol used in step (2) is 1, 4-cyclohexanedimethanol, the antimicrobial properties are significantly better than if the diol used is ethylene glycol, 1, 3-propanediol, 1, 4-butanediol or polyethylene glycol.
We have also found that when the glycol employed in step (2) is a mixed alcohol of ethylene glycol and 1, 4-cyclohexanedimethanol, the ethylene glycol and 1, 4-cyclohexanedimethanol have a synergistic effect in improving the antibacterial properties of the antibacterial polyester. In this case, the ratio of ethylene glycol to 1, 4-cyclohexanedimethanol is not particularly limited, and comparable synergy can be obtained. By way of example only, the molar ratio of ethylene glycol to 1, 4-cyclohexanedimethanol is 0.1 to 10, more specifically by way of non-limiting example, the molar ratio is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, etc. More preferably 0.2 to 5.
In the above technical solution, the molar ratio of the diol to the intermediate 3 in the step (2) is preferably greater than 1 and less than 2, more preferably 1.1 to 1.5, such as but not limited to 1.05, 1.1, 1.15, 1.20, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, and the like.
In the above technical scheme, the esterification reaction in the step (2) is preferably performed until the esterification rate is 95% -99%, for example, but not limited to, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.
In order to achieve the esterification rate, a person skilled in the art can reasonably select the esterification temperature and the esterification time according to the practical conditions such as the operation conditions allowed by the reaction equipment, and the higher the esterification temperature and the longer the esterification time are, as a general rule, beneficial to improving the esterification rate.
By way of non-limiting example only, the esterification temperature in step (2) may be selected from 150 to 250 ℃, more specific non-limiting examples being 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, and the like. In this temperature range, in the case of continuously separating out water produced by the esterification reaction, the desired esterification rate can be achieved by the esterification reaction time of 0.5 to 2 hours, even without using a catalyst as in the examples of the present invention. Of course, an esterification catalyst may be used for the esterification reaction, and the esterification reaction speed is faster when the esterification catalyst is used.
The esterification reaction of the step (2) can be carried out under the autogenous pressure of the reaction, or inert gas such as nitrogen is filled into the reaction system and is carried out under the pressure higher than the autogenous pressure, and the esterification reaction of the step (2) is liquid-phase reaction, so that the pressure has no obvious influence on the progress of the esterification reaction.
The third technical problem to be solved by the invention is the application of the reactive antibacterial component in the preparation of antibacterial polyester.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
use of a reactive antimicrobial component according to any one of the technical solutions of the above technical problems or a reactive antimicrobial component obtained by the synthetic method according to any one of the technical solutions of the second technical solutions of the above technical problems in the preparation of an antimicrobial polyester.
The technical key of the invention is to provide the reactive antibacterial component, after the reactive antibacterial component is disclosed, the reactive antibacterial component is adopted for preparing the antibacterial polyester, and the technical conditions can be reasonably selected by the skilled in the art, so that comparable technical effects can be obtained without creative labor.
However, it is known to those skilled in the art that the preparation of polyesters may include an esterification stage, a pre-polycondensation stage, and a final polycondensation stage in that order; we have found that the antibacterial polyester obtained by adding the reactive antibacterial component of the present invention in the pre-polycondensation stage has a far better antibacterial effect than the antibacterial polyester obtained by adding the reactive antibacterial component of the present invention in the esterification stage. Therefore, we propose a fourth technical problem to be solved by the invention, and provide a better preparation method of the antibacterial polyester.
In order to solve the fourth technical problem, the technical scheme of the invention is as follows:
a process for preparing an antimicrobial polyester comprising:
(i) Esterification reaction is carried out on dihydric alcohol and dibasic acid to obtain an esterified material I;
(ii) The esterification material I is mixed with the reactive antibacterial component in any one of the technical proposal of the technical problems, and the pre-polycondensation reaction is carried out to obtain a pre-polycondensation product;
(iii) And (3) carrying out final polycondensation reaction on the pre-polycondensation product to obtain the antibacterial polyester.
Compared with the components shown in the formula 3 which are directly esterified in the step (i), or the antibacterial performance of the antibacterial polyester obtained by the preparation method of the antibacterial polyester has better washing resistance although the reactive antibacterial component is added into the step (i) for esterification.
In the above embodiment, preferably, the glycol in the step (i) includes at least one selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol and 1, 4-cyclohexanedimethanol. In the embodiment of the invention, ethylene glycol is generally adopted by the same ratio.
In the above embodiment, it is preferable that the dibasic acid in the step (i) includes at least one selected from the group consisting of terephthalic acid, succinic acid, adipic acid, isophthalic acid and furandicarboxylic acid. Terephthalic acid is commonly used in the examples of the present invention by comparison only.
In the above technical scheme, in the step (i), the molar ratio of the dihydric alcohol to the dibasic acid is preferably 1.1-1.5. Such as, but not limited to, a molar ratio of glycol to diacid of 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, etc.
In the above technical scheme, the esterification rate of the esterification reaction in the step (i) is preferably 95% -99%, for example, but not limited to, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, etc.
In order to achieve the esterification rate, a person skilled in the art can reasonably select the esterification temperature and the esterification time according to the practical conditions such as the operation conditions allowed by the reaction equipment, and the higher the esterification temperature and the longer the esterification time are, as a general rule, beneficial to improving the esterification rate.
By way of non-limiting example only, the esterification temperature in step (i) may be selected from 150 to 250 ℃, more specific non-limiting examples being 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and the like. In this temperature range, in the case of continuously separating out water produced by the esterification reaction, the desired esterification rate can be achieved by the esterification reaction time of 0.5 to 2 hours, even without using a catalyst as in the examples of the present invention. Of course, an esterification catalyst may be used for the esterification reaction, and the esterification reaction speed is faster when the esterification catalyst is used.
The esterification reaction of the step (i) can be carried out under the autogenous pressure of the reaction, or inert gas such as nitrogen is filled into the reaction system and is carried out under the pressure higher than the autogenous pressure, and the esterification reaction of the step (i) is liquid-phase reaction, so that the pressure has no obvious influence on the progress of the esterification reaction.
In the above technical scheme, in the step (ii), the mass ratio of the reactive antibacterial component (calculated by N contained therein) to the esterified material I calculated by the diacid required for preparing the reactive antibacterial component and the esterified material I is preferably t:100, and t is more than 0 and less than 4. Such as but not limited to t being 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, etc.
In the above technical solution, in the step (ii), the pressure is preferably 400 to 600pa, for example, but not limited to, 410 Pa, 420 Pa, 430 Pa, 440 Pa, 450 Pa, 460 Pa, 470 Pa, 480 Pa, 490 Pa, 500Pa, 510 Pa, 520 Pa, 530 Pa, 540 Pa, 550 Pa, and the like.
In the above-mentioned technical scheme, in the step (ii), the reaction temperature is preferably 255 to 265 ℃, for example, but not limited to 256 ℃, 257 ℃, 258 ℃, 259 ℃, 260 ℃, 261 ℃, 262 ℃, 263 ℃, 264 ℃, and the like.
In the above technical scheme, in the step (ii), the reaction time is preferably 30 to 60 minutes, for example, but not limited to 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, and the like.
In the above embodiment, in the step (iii), the reaction pressure is preferably 100Pa or less, for example, but not limited to, 5 Pa, 10 Pa, 20 Pa, 30 Pa, 40 Pa, 50Pa, 60 Pa, 70 Pa, 80 Pa, 90 Pa, and the like.
In the above-mentioned technical scheme, in the step (iii), the reaction temperature is preferably 270 to 285 ℃, for example, but not limited to 271 ℃, 272 ℃, 273 ℃, 274 ℃, 275 ℃, 276 ℃, 277 ℃, 278 ℃, 279 ℃, 280 ℃, 281 ℃, 282 ℃, 283 ℃, 284 ℃, and the like.
Those skilled in the art will recognize that both lowering the reaction pressure and increasing the reaction temperature in step (iii) are advantageous in promoting the final polycondensation reaction and in increasing the intrinsic viscosity of the final polycondensation product. After the pressure of the reaction and the temperature of the reaction in step (iii) are determined, the intrinsic viscosity of step (iii) tends to increase as the reaction time increases. In the above embodiment, the step (iii) is preferably carried out until the intrinsic viscosity is 0.60 to 0.75dl/g. Only the same ratio was found to be 0.68dl/g in each of the examples and comparative examples.
In the above technical scheme, step (iii) can achieve the above desired intrinsic viscosity range under the above reaction temperature and reaction pressure conditions, with a typical reaction time of 1.5 to 3.0 hours.
Those skilled in the art will recognize that the esterification reaction is easily performed in the step (2) and the step (i), and may be performed with or without a catalyst. However, the prepolymerization and the final polymerization of step (ii) and step (iii) have a limited activity of the reactive groups with increasing molecular chains, and usually require a polymerization catalyst which can be added in the esterification stage of step (2) and/or step (i) and which, together with the esterification product, is fed into the polycondensation stage of step (ii) and step (iii), or into the prepolymerization stage of step (ii) and/or the final polymerization stage of step (iii), with comparable technical results and without the need for inventive labour. To facilitate the dispersion of the catalyst in step (ii) and step (iii) for a more uniform catalytic action, it is preferred to add it in the esterification stage of step (2) and/or step (i) above. The polymerization catalysts in the examples of the present invention were all added in step (i) above by comparison only.
Regarding the polymerization catalyst, those known to those skilled in the art such as, but not limited to, antimony-based polymerization catalysts (e.g., but not limited to, antimony trioxide, antimony acetate, antimony glycolate), titanium-based polymerization catalysts, etc., are not limited thereto, and can achieve comparable technical effects. By way of comparison only, the polymerization catalysts employed in the examples all employ antimony-based catalysts, the amount of antimony-based catalyst being expressed as antimony and by weight relative to the terephthalic acid charged in step (i) in the range of 100 to 300ppmw (e.g., without limitation, 110 ppmw, 120 ppmw, 130 ppmw, 140 ppmw, 150 ppmw, 160 ppmw, 170 ppmw, 180 ppmw, 190 ppmw, 200ppmw, 210 ppmw, 220 ppmw, 230 ppmw, 240 ppmw, 250 ppmw, 260 ppmw, 270 ppmw, 280 ppmw, 290 ppmw, etc.). The antimony-based polymerization catalysts used in the examples were ethylene glycol antimony, only in the same ratio.
Regarding the concept of the esterification rate in the above step (2) and step (i), those skilled in the art know that the esterification rate is used to monitor the completion of the esterification reaction, and is defined as the fraction of the number of carboxyl groups moles forming ester groups to the number of carboxyl groups in the feed material. The esterification rate can be controlled by metering and collecting the water generated and distilled by the esterification reaction, and the measurement method of the esterification rate is obtained by comparing the weight of water actually generated by the esterification reaction with the weight of water generated by the complete esterification of carboxyl in the assumed reaction raw materials, and is specifically calculated according to the following formula:
the esterification ratio = (weight of water actually produced by the esterification reaction/weight of water produced by the complete esterification of carboxyl groups in the reaction raw materials) x 100%.
The fifth technical problem to be solved by the invention is to provide an antibacterial polyester.
In order to solve the fifth technical problem, the technical scheme of the invention is as follows:
an antibacterial polyester obtained by the production method according to any one of the fourth technical problems.
The antibacterial polyester obtained by the invention can be used for producing medical surgical articles due to the antibacterial effect, and the obtained surgical articles can contact human bodies such as eyes, auditory meatus, oral cavity and nasal cavity due to the antibacterial effect.
The sixth technical problem to be solved by the invention is to provide the application of the antibacterial polyester in the production of antibacterial polyester fibers.
In order to solve the sixth technical problem, the technical scheme of the invention is as follows:
the fifth technical scheme of the technical problem is that the antibacterial polyester is applied to the production of antibacterial polyester fibers.
The technical key of the invention is the selection of the antibacterial components (the corresponding technical key is the selection of antibacterial polyester), and the production process of the specific antibacterial fiber is not particularly limited, and the technical key can be reasonably selected and adjusted in the common process and process conditions by the person skilled in the art, so that comparable technical effects can be obtained. The processes and process conditions referred to below are only non-limiting examples. Namely, the seventh technical problem to be solved by the invention is to provide a production method of the antibacterial polyester.
In order to solve the technical problem, the technical scheme of the invention is as follows:
a method of producing an antimicrobial fiber comprising: (a) Blending the spinning grade PET polyester with the antibacterial polyester in the fifth technical scheme of the technical problem, or blending the spinning grade PET polyester with the antibacterial polyester obtained by the preparation method in any one of the fourth technical scheme of the technical problem, and obtaining the nascent fiber through melt spinning;
(b) The as-spun fiber is thermally drawn.
For example, but not limited to, the mass ratio of the antibacterial polyester (based on N contained therein) to the spinning grade PET polyester in step (a) is q:100, q is greater than 0 and less than 0.2, more specifically, by way of non-limiting example, q is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, etc., more preferably 0.02 to 0.15. By way of comparison only, q of 0.04 is generally employed in the examples.
For example, but not limited to, the intrinsic viscosity of the spinning grade PET polyester in step (a) is 0.60 to 0.70dl/g. By way of non-limiting example, for example, but not limited to, spinning grade PET polyesters have an intrinsic viscosity of 0.61 dl/g, 0.62 dl/g, 0.63 dl/g, 0.64 dl/g, 0.65 dl/g, 0.66 dl/g, 0.67dl/g, 0.68dl/g, 0.69 dl/g, and the like. For comparison only, the commercial spun polyethylene terephthalate (abbreviated as commercial spun-grade PET) used in the specific embodiment of the invention is SB500 type of China petrochemical industry, chemical fiber Limited, and has an intrinsic viscosity of 0.67dl/g and an actual measured intrinsic viscosity of 0.68dl/g.
For example, but not limited to, filament or short filament can be produced by melt spinning, the filament can be FDY, POY or DTY prepared by POY texturing, and the specification of the filament can be 50-300D (for example but not limited to 50D, 60D, 70D, 80D, 90D, 100D, 110D, 120D, 130D, 140D, 150D, 160D, 170D, 180D, 190D, 200D); the length of the staple can be 38-76 mm, and the fineness can be 0.5-3.0D. No matter the filaments or the short filaments are produced, no matter the specifications are the same, and no matter the process is adopted for production, the comparable technical effect can be achieved. For comparison purposes only, the filaments were produced by the FDY process in the embodiments of the invention, and the filaments were all 150D in specification.
In the above technical scheme, the temperature of the drafting in the step (b) is preferably 120-160 ℃. Such as, but not limited to 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, just for comparison, the draft temperature in the embodiment of the present invention is 140 ℃.
In the above technical solution, the draft ratio of the draft in the step (b) is preferably 3.0 to 5.0. Such as, but not limited to, 3.1 times, 3.2 times, 3.3 times, 3.4 times, 3.5 times, 3.6 times, 3.7 times, 3.8 times, 3.9 times, 4.0 times, 4.1 times, 4.2 times, 4.3 times, 4.4 times, 4.5 times, 4.6 times, 4.7 times, 4.8 times, 4.9 times, 5.0 times, and the draft multiple is 4.0 times in embodiments of the present invention for comparison purposes only.
The measuring method of the intrinsic viscosity is carried out by adopting a method A in section 5.1.1 in GB/T14190-2017 (fiber grade Polyester (PET) slice test method), and the adopted solvent is a mixture of phenol and 1, 2-tetrachloroethane in a mass ratio of 50:50.
The nitrogen content in the specific embodiments of the invention is measured by a Kai-type nitrogen determination method.
The antibacterial performance durability evaluation of the antibacterial polyester fiber is carried out according to the 'GBT 209444.3-2008 textile antibacterial performance evaluation part 3 vibration method', and the fiber product is washed for 50 times according to the method 10.1.2 in the standard before testing. The test strain is staphylococcus aureusStaphylococcus aureus(ATCC 6538). The higher the antibacterial rate measured by washing 50 times by the method, the better the antibacterial performance and the durability of the antibacterial performance of the fiber product are shown.
The present invention will be described in detail with reference to the following embodiments.
Detailed Description
[ example 1 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
Adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
Mixing ethylene glycol and the product in the step 1.1 according to the mol ratio of 1.3:1 to obtain a reaction raw material, esterifying at 180 ℃, and metering and collecting water generated by esterification until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.43% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.73% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the bacteriostasis rate is 89.1%.
[ comparative example 1 ]
The main difference with example 1 is that the compound of formula 3 is added directly in the esterification stage in the preparation of the antibacterial polyester, in particular:
1. obtained as a compound of formula 3 (same as in example 1: 1)
Adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Mixing terephthalic acid, the product of the step 1, ethylene glycol antimony and ethylene glycol (wherein the molar ratio of the ethylene glycol to (the sum of the product of the step 1 and terephthalic acid) is 1.2, the mass ratio of the product of the step 1 and terephthalic acid is 1.2:100 by nitrogen, the amount of the ethylene glycol antimony is 200ppmw corresponding to the weight of the terephthalic acid by antimony) as a reaction raw material, carrying out esterification reaction at 200 ℃, and metering and collecting water generated by the esterification until the esterification rate is 97%, thus obtaining an esterified material I.
2.2 precondensation
The esterified material I of step 2.1 was polycondensed at an absolute pressure of 500Pa and at 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.73% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the antibacterial rate is 76.8%.
[ comparative example 2 ]
1. Synthesis of reactive antibacterial component
The same as in example 1, specifically:
1.1, compound of formula 3
Adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
Mixing ethylene glycol and the product in the step 1.1 according to the mol ratio of 1.3:1 to obtain a reaction raw material, esterifying at 180 ℃, and metering and collecting water generated by esterification until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.43% by weight.
2. Preparation of antibacterial polyester
The difference from example 1 is mainly that the product of step 1.2 is added in the esterification step in the preparation of the antibacterial polyester, in particular:
2.1 esterification
Mixing terephthalic acid, the product obtained in the step 1.2, ethylene glycol antimony and ethylene glycol (the molar ratio of the ethylene glycol to the terephthalic acid is 1.2, the mass ratio of the product obtained in the step 1.2 to the terephthalic acid is 1.2:100, the amount of the ethylene glycol antimony is 200ppmw corresponding to the weight of the terephthalic acid in terms of antimony) as a reaction raw material, carrying out esterification reaction at 200 ℃, and metering and collecting water generated by the esterification until the esterification rate is 97%, thus obtaining an esterified material I.
2.2 precondensation
The esterified material I of step 2.1 was polycondensed at an absolute pressure of 500Pa and at 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.73% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the antibacterial rate is 82.9%.
[ example 2 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
The same as in step 1.1 of example 1, specifically:
adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
The main difference with example 1, step 1.2 is that the diol is 1, 4-butanediol, in particular:
mixing 1.4-butanediol with the product of the step 1.1 according to the mol ratio of 1.3:1 to obtain a reaction raw material, esterifying at 180 ℃, and metering and collecting water generated by esterification until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.27% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.72% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the antibacterial rate is 87.6%.
[ example 3 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
The same as in step 1.1 of example 1, specifically:
adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
The main difference from example 1, step 1.2 is that the glycol is polyethylene glycol 400, specifically:
polyethylene glycol 400 and the product of the step 1.1 are mixed according to the mol ratio of 1.3:1 to be used as reaction raw materials, esterification is carried out at 180 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that the reactive antibacterial component is obtained. The nitrogen content of the product was determined to be 1.37% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.59% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the bacteriostasis rate is 90.9%.
[ example 4 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
The same as in step 1.1 of example 1, specifically:
adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
The main difference from step 1.2 of example 1 is that the diol is 1, 4-cyclohexanedimethanol, in particular:
1, 4-cyclohexanedimethanol and the product of the step 1.1 are mixed according to the mol ratio of 1.3:1 to be used as reaction raw materials, the esterification is carried out at 180 ℃ and the water generated by the esterification is metered and collected until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.03% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.69% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the bacteriostasis rate is 95.3%.
[ example 5 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
The same as in step 1.1 of example 1, specifically:
adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
The main differences from example 1, step 1.2 are that the diols are ethylene glycol and 1, 4-cyclohexanedimethanol, in particular:
mixing ethylene glycol, 1, 4-cyclohexanedimethanol and the product of the step 1.1 (wherein the mol ratio of the ethylene glycol to the 1, 4-cyclohexanedimethanol is 1:1, (the sum of the ethylene glycol and the 1, 4-cyclohexanedimethanol) and the mol ratio of the product of the step 1.1 is 1.3:1) as reaction raw materials, esterifying at 180 ℃ and metering and collecting water generated by the esterification until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.21% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.71% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the bacteriostasis rate is 99.7%.
[ example 6 ]
1. Synthesis of reactive antibacterial component
1.1, compound of formula 3
The same as in step 1.1 of example 1, specifically:
adding hexadecyl trimethyl ammonium chloride aqueous solution (weight concentration is 5.6%) into isophthalic acid-5-sodium sulfonate aqueous solution (weight concentration is 5.0%) with stirring, stirring for 2 hours, standing for layering, filtering, washing the filter cake with water three times, using water of the same volume as the filter cake each time, and drying the filter cake at 80 ℃ for 5 hours to obtain a compound dried product shown in formula 3. The nitrogen content of the product was determined to be 2.64% by weight.
1.2, reactive antibacterial component
The main differences from example 1, step 1.2 are that the diols are ethylene glycol and 1, 4-cyclohexanedimethanol, in particular:
mixing ethylene glycol, 1, 4-cyclohexanedimethanol and the product of the step 1.1 (wherein the mol ratio of the ethylene glycol to the 1, 4-cyclohexanedimethanol is 4:1 and the mol ratio of the ethylene glycol to the 1, 4-cyclohexanedimethanol is 1.3:1) as reaction raw materials, esterifying at 180 ℃ and metering and collecting water generated by the esterification until the esterification rate is 97%, thus obtaining the reactive antibacterial component. The nitrogen content of the product was determined to be 2.34% by weight.
2. Preparation of antibacterial polyester
2.1 esterification
Terephthalic acid, ethylene glycol antimony and ethylene glycol are mixed (the molar ratio of ethylene glycol to terephthalic acid is 1.2, the amount of ethylene glycol antimony is equal to 200ppmw of the weight of terephthalic acid calculated by antimony) as reaction raw materials, esterification reaction is carried out at 200 ℃, and water generated by esterification is metered and collected until the esterification rate is 97%, so that an esterified material I is obtained.
2.2 precondensation
The product of step 1.2 is mixed with the esterified material I of step 2.1 in a weight ratio of 1.2:100 by weight of the nitrogen-containing, esterified material I of step 2.1 based on the weight of terephthalic acid required for its preparation, and polycondensed at an absolute pressure of 500Pa and 260℃for 45min.
2.3 final polycondensation
And (3) carrying out polycondensation reaction on the material obtained in the step (2.2) at the absolute pressure of 50Pa and the temperature of 280 ℃ until the intrinsic viscosity is 0.68dl/g, thus obtaining the antibacterial polyester. The nitrogen content of the antibacterial polyester is 0.72% by weight.
3. Antibacterial fiber production
3.1 melt spinning
The antibacterial polyester (calculated by N contained in the antibacterial polyester) in the step 2.3 and commercial spinning grade PET are blended and melt-spun according to the weight ratio of 0.040:100 to obtain the primary fiber, wherein the melt-spinning temperature is 280 ℃.
3.2 drafting
And (3) carrying out hot drawing on the nascent fiber obtained by melt spinning, wherein the drawing multiple is 4.0 times, and the drawing temperature is 140 ℃. And spinning to obtain FDY fiber with the specification of 150D.
4. Antibacterial polyester fiber test
The test shows that the bacteriostasis rate is 98.5%.

Claims (12)

1. The reactive antibacterial component is prepared by esterification reaction of a substance shown in the following formula 3 and glycol:
formula 3;
q is a quaternary ammonium group containing long-chain hydrocarbon groups, the number of carbon atoms in the long-chain hydrocarbon groups is 6-20, and Ar is an aromatic ring; the diol is ethylene glycol and 1, 4-cyclohexanedimethanol.
2. The reactive antibacterial composition of claim 1, wherein the molar ratio of ethylene glycol to 1, 4-cyclohexanedimethanol is 0.1 to 10.
3. The reactive antibacterial composition of claim 1, wherein the molar ratio of ethylene glycol to 1, 4-cyclohexanedimethanol is 0.2 to 5.
4. The reactive antibacterial component of claim 1 wherein Ar is a benzene ring or naphthalene ring.
5. The method for synthesizing the reactive antibacterial component of claim 1, comprising the steps of:
(1) Subjecting compound 1 and compound 2 to ion exchange reaction in solvent to obtain intermediate 3;
compound 1 corresponds to the structure shown in formula 1:
the method comprises the steps of 1,
compound 2 corresponds to the structure shown in formula 2:
2, the number of the active ingredients in the liquid crystal layer,
intermediate 3 corresponds to the structure shown in formula 3;
x is Cl or Br; m is an alkali metal;
(2) And (3) carrying out esterification reaction on the intermediate product 3 and glycol to obtain the reactive antibacterial component.
6. The method of claim 5, wherein the solvent is water.
7. The synthetic method according to claim 5, wherein the compound 1 corresponds to the structure represented by formula 1 a:
formula 1a;
R 1 is a long chain hydrocarbon group, R 1 The number of carbon atoms is 6-20;
R 2 ~R 4 is a short chain hydrocarbon group.
8. The synthesis method according to claim 7, wherein R 2 ~R 4 Independently is C1-C2 alkyl.
9. The synthetic method according to claim 5, wherein the compound 2 corresponds to the structure represented by formula 2 a:
formula 2a.
10. The synthetic method according to claim 5, wherein the molar ratio of diol to intermediate 3 in step (2) is greater than 1 and less than 2; and/or the esterification reaction in the step (2) is carried out until the esterification rate is 95% -99%; and/or the esterification temperature in the step (2) is 150-250 ℃.
11. The synthesis method according to claim 10, wherein the molar ratio of the diol to the intermediate 3 in the step (2) is 1.1 to 1.5.
12. An application of a reactive antibacterial component in the preparation of antibacterial polyester, which is characterized in that the reactive antibacterial component is the reactive antibacterial component in any one of claims 1-4.
CN202311344522.9A 2023-10-18 2023-10-18 Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester Pending CN117069626A (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57119924A (en) * 1981-01-16 1982-07-26 Nippon Ester Co Ltd Manufacture of polyester
JPH0369665A (en) * 1989-08-04 1991-03-26 Unitika Ltd Production of antimicrobial fiber structure
JPH03227408A (en) * 1990-01-29 1991-10-08 Kuraray Co Ltd Conjugate fiber of core-sheath type
JPH09324070A (en) * 1996-06-05 1997-12-16 Toyobo Co Ltd Antibacterial composion
JPH11222723A (en) * 1997-12-05 1999-08-17 Toyobo Co Ltd Antibacterial fiber
JP2000119348A (en) * 1998-10-16 2000-04-25 Toyobo Co Ltd Production of antibacterial/antifungal resin and water dispersion of the same
JP2001026086A (en) * 1999-07-13 2001-01-30 Toyobo Co Ltd Laminating film of antibacterial resin
JP2003334412A (en) * 2002-05-20 2003-11-25 Toyobo Co Ltd Filter medium
WO2007068460A1 (en) * 2005-12-13 2007-06-21 Dsm Ip Assets B.V. Biocidal coatings
JP2012112050A (en) * 2010-11-19 2012-06-14 Teijin Fibers Ltd Polyester fiber
CN114057615A (en) * 2021-11-11 2022-02-18 浙江大学 High-temperature-resistant polymerizable antibacterial agent, preparation thereof and application thereof in synthesis of antibacterial polyester

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57119924A (en) * 1981-01-16 1982-07-26 Nippon Ester Co Ltd Manufacture of polyester
JPH0369665A (en) * 1989-08-04 1991-03-26 Unitika Ltd Production of antimicrobial fiber structure
JPH03227408A (en) * 1990-01-29 1991-10-08 Kuraray Co Ltd Conjugate fiber of core-sheath type
JPH09324070A (en) * 1996-06-05 1997-12-16 Toyobo Co Ltd Antibacterial composion
JPH11222723A (en) * 1997-12-05 1999-08-17 Toyobo Co Ltd Antibacterial fiber
JP2000119348A (en) * 1998-10-16 2000-04-25 Toyobo Co Ltd Production of antibacterial/antifungal resin and water dispersion of the same
JP2001026086A (en) * 1999-07-13 2001-01-30 Toyobo Co Ltd Laminating film of antibacterial resin
JP2003334412A (en) * 2002-05-20 2003-11-25 Toyobo Co Ltd Filter medium
WO2007068460A1 (en) * 2005-12-13 2007-06-21 Dsm Ip Assets B.V. Biocidal coatings
JP2012112050A (en) * 2010-11-19 2012-06-14 Teijin Fibers Ltd Polyester fiber
CN114057615A (en) * 2021-11-11 2022-02-18 浙江大学 High-temperature-resistant polymerizable antibacterial agent, preparation thereof and application thereof in synthesis of antibacterial polyester

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