CN1182176C - Process for preparing antibiotic polyester - Google Patents
Process for preparing antibiotic polyester Download PDFInfo
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- CN1182176C CN1182176C CNB021515123A CN02151512A CN1182176C CN 1182176 C CN1182176 C CN 1182176C CN B021515123 A CNB021515123 A CN B021515123A CN 02151512 A CN02151512 A CN 02151512A CN 1182176 C CN1182176 C CN 1182176C
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- antibacterial
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Abstract
The present invention relates to a method for preparing antibacterial polyester, which belongs to the field of high molecular materials. The method comprises: reaction monomers carry out an esterification reaction and a polymerization reaction under the condition of a catalyst and a stabilizing agent, wherein the reaction monomers are refined terephthalic acid and antibacterial agents dispersed in dibasic alcohol for preparing a solution added to a reaction system. The antibacterial agents are zeolite, phosphate, titanium dioxide and inorganic ionexchange resin powder carrying argentum ions and zinc ions or oxides thereof, and the addition of the antibacterial agent solution is from 0.3% to 3% of the weight of polyester. The present invention has the advantages of simple technology, good product antibacterial performance, persistent antibacterial performance, washing resistance, good slice spinnability and no toxic side effect on human bodies, and the antibacterial ratio of the products to golden yellow staphylococci and colibacillus can reach more than 99.9%.
Description
(1) technical field
The present invention relates to a kind of preparation method of antibacterial polyester, belong to polymeric material field.
(2) background technology
Along with the needs of growth in the living standard and activity in production, people more and more pay attention to the health care function of clothes.Antibacterial fiber gains great popularity with its excellent antibacterial and deodouring function, and antibacterial fiber can be used for producing clothes such as underwear, socks, Sportswear, bedclothes, health dressing etc.Present antibacterial fiber and fabric mainly are to adopt back arrangement or master batch co-blended spinning to make, and also have by add antiseptic-germicide in polyester production process and make antibacterial polyester.Back arrangement is meant with antimicrobial fluid fiber or fabric to be flooded or apply and makes it have antibiotic effect.The antimicrobial product that this method makes is wash resistant not, and anti-microbial property is not lasting, pollutes big.The master batch method is meant with antiseptic-germicide and polyester carries out extruding pelletization on screw extrusion press, carry out co-blended spinning after making antibacterial matrices, makes antibacterial fiber, this method complex process, and antiseptic-germicide disperses irregular.Therefore, efficient, nontoxic, the wash fast antibacterial polyester of exploitation is the trend of antibacterial fiber development.No matter the back arrangement still be the antiseptic-germicide that adopted of master batch co-blended spinning and antibacterial polyester be organic antibacterial agent and inorganic antiseptic two classes basically.The organic antibacterial agent antibacterial effect is better, but non-refractory, high temperature easily decomposes, to the toxic effect of human body; Though the inorganic antiseptic antibacterial effect is weaker but high temperature resistant than organic antibacterial agent, human body is had no side effect, because inorganic antiseptic powder granule difficulty in spinning when big, particle Xiao Yi reunites, and is difficult to be uniformly dispersed, and influences spinning.
In production of polyester, add through the inorganic antiseptic of milled processed and produce the existing report of antibacterial polyester, though antiseptic-germicide through grinding, coacervate is still more, the product spinning property is poor, the silk that wafts during spinning, broken end are many, full-rolling rate is low, the unit consumption height.
(3) summary of the invention
At the deficiencies in the prior art, the invention provides that a kind of production technique is simple, the product anti-microbial property good, to human body have no side effect, the preparation method of the persistent antibacterial polyester of wash resistant anti-microbial property.
The inventive method comprises that reaction monomers carries out esterification, polyreaction in the presence of catalyzer, stablizer, oxidation inhibitor, and reaction monomers is pure terephthalic acid (hereinafter to be referred as PTA), and antiseptic-germicide is dispersed in to be made solution and add reaction system in the dibasic alcohol.
Described antiseptic-germicide is the inorganic powder that carries zeolite, phosphoric acid salt, titanium dioxide or the ion exchange resin of silver, zine ion or its oxide compound, and metal ion content calculates 3%～5% with weight ratio.
Described antimicrobial is inorganic antibiosis powder to be added dibasic alcohol be made into be weight percentage 5%～30% solution of concentration.
Above-mentioned antimicrobial was ground 3～5 hours with sand mill after high speed dispersor disperses 2～3 hours, handled 15～45 minutes with ultrasonic generator again.The solution of treated antiseptic-germicide is uniformly dispersed, and good stability is placed no sedimentation in 72 hours, and particle diameter is 0.05～0.3 micron, 0.1～0.25 micron of preferable particle size.
Above-mentioned antimicrobial adds in the reaction system before esterification finishes back, polyreaction, also can add in the reaction system before esterification.
Preferred antimicrobial agents solution of the present invention adds in the reaction system before esterification finishes back, polyreaction.
The add-on of above-described antiseptic-germicide is calculated as 0.3%～3% with the weight polyester ratio, and preferred 0.5%～1%.
Above-described dibasic alcohol can be an ethylene glycol, 1,4-butyleneglycol, 1, any in the ammediol.
Described catalyzer is antimonous oxide or tetrabutyl titanate, antimony glycol.
Described stablizer is trimethyl phosphite 99, triphenylphosphate or phosphoric acid.
Described oxidation inhibitor is four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, C
73H
108O
12, trade(brand)name AT-1010 or three (2, the 4-di-t-butyl) phenyl-phosphite, trade(brand)name CSFC186 is the article that can buy on the market.
The concrete steps of the inventive method are as follows:
(1) pre-treatment of antiseptic-germicide: being made into concentration with selected dibasic alcohol and inorganic antiseptic powder is 5%～30% suspension, after high speed dispersor disperses 2～3 hours, grinds 3～5 hours with sand mill, handles 15～45 minutes with ultrasonic generator again.
(2) esterification: esterification adopts the direct esterification method, the mol ratio of pure terephthalic acid and dibasic alcohol is 1: 1.1～1.3, catalyzer, stablizer, oxidation inhibitor add esterifying kettle with the pure terephthalic acid with the dibasic alcohol slurry, esterification is carried out under normal pressure, and temperature of reaction is 220 ℃～260 ℃.Aquifer yield reaches 95% of theoretical amount to be looked esterification when above and finishes.
(3) polyreaction: esterification will join in the reaction system through pretreated antiseptic-germicide suspension after finishing, and reaction was at first carried out precondensation 30 minutes under normal pressure, and temperature rises to 250 ℃; Set up rough vacuum afterwards, temperature rises to 280 ℃, enters high vacuum after one hour, and the temperature control is looked the polyreaction end at 288 ± 2 ℃ when power of agitator reaches the 8-17 kilowatt-hour, and nitrogen extrudes material, granulation gets antibacterial polyester.
Set up rough vacuum in the polyreaction: be evacuated to 1000Pa gradually by normal pressure, temperature rises to 280 ℃ gradually, and the time is 30 minutes.Enter high vacuum after 1 hour: be evacuated to 40Pa gradually by 1000Pa, temperature rises to 288 ℃ gradually, and the time is 30 minutes, keeps vacuum to be not more than 40Pa, and temperature is controlled at 288 ± 2 ℃.
The product performance of the present invention's preparation are good, and limiting viscosity can be controlled at 0.64-0.68 deciliter/gram (dl/g) as required, and fusing point is not less than 250 ℃, and form and aspect b value is less than 2.5.
The product of the present invention preparation can spinning on conventional spinning equipment, and good spinnability, waft silk, little breakage, and unit consumption is low.The product anti-microbial property is good, to human body have no side effect, wash resistant, the preparation method of the persistent antibacterial polyester of anti-microbial property.The product of the present invention's preparation can carry out high-speed spinning, 48 hours after filter pressure of spinning rising 1MPa in addition.
The antibacterial polyester that the inventive method is produced can satisfy the requirement of spinning long or short filament, and short silk can be used for various bedclothes, furnishing fabric, health dressing, medical operation clothes, patient's gown, hospital's sheet etc., the special-purpose clothes of food service industry; Long filament can be widely used in underwear, socks, Sportswear, sock, filtration fabrics, carpet etc.Along with the batch process of antibacterial fiber, its range of application will be more and more wider.
The fiber that product spins and the antibacterial fabric of the present invention preparation are functional, and greater than 99.9%, and anti-microbial property does not descend after 100 standards are washed to the bacteriostasis rate of intestinal bacteria, staphylococcus aureus for it.
(4) embodiment
The invention will be further described below by specific embodiment.
Embodiment 1.
Get the 22.70Kg silver-loaded zirconium phosphate and be added in the 100Kg ethylene glycol, stirred 2 hours with high speed dispersor, ground 4 hours with sand mill then, ground slurries are used ultrasonication 40 minutes, and are stand-by.
In the making beating still, add 2000Kg pure terephthalic acid and 950Kg ethylene glycol, 0.68Kg antimonous oxide, 0.12Kg trimethyl phosphite 99,0.23Kg oxidation inhibitor three (2, the 4-di-t-butyl) phenyl-phosphite, back immigration esterifying kettle stirs, carry out esterification under the normal pressure, temperature of reaction is controlled at 220-260 ℃, aquifer yield is during greater than 410L, and esterification finishes.The slurry of esterification is moved into polymeric kettle, in polymeric kettle, add the pretreated antimicrobial of 122.7Kg, carried out precondensation under the normal pressure 30 minutes, and temperature risen to 250 ℃ gradually, set up rough vacuum then: be evacuated to 1000Pa gradually by normal pressure, temperature rises to 275 ℃ gradually, time is 30 minutes, enters high vacuum afterwards: be evacuated to 40Pa gradually by 1000Pa, temperature rises to 288 ℃ gradually, time is 30 minutes, keep vacuum to be not more than 40Pa, temperature is controlled at 288 ± 2 ℃, finishes polymerization when power of agitator reaches 15Kw, nitrogen extrudes material, granulation obtains antibacterial polyester section, its performance index such as table 1.
Embodiment 2.
Get the 18.20Kg zeolite with carrying silver and be added to 110.0Kg1, in the 4-butyleneglycol, stirred 2 hours with high speed dispersor, ground 4 hours with sand mill then, ground slurries are used ultrasonication 20 minutes, and are stand-by.
In the making beating still, add 2000Kg pure terephthalic acid and 1317Kg1,4-butyleneglycol, 0.79Kg tetrabutyl titanate, 0.32Kg triphenylphosphate, 0.37Kg oxidation inhibitor four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, back immigration esterifying kettle stirs, carry out esterification under the normal pressure, temperature of reaction is controlled at 220～260 ℃, and aquifer yield is during greater than 410L, and esterification finishes.The slurry of esterification is moved into polymeric kettle, in polymeric kettle, add the antiseptic-germicide that 98.2Kg handles well, carried out precondensation under the normal pressure 30 minutes, and temperature risen to 250 ℃ gradually, set up rough vacuum then: be evacuated to 1000Pa gradually by normal pressure, temperature rises to 275 ℃ gradually, time is 30 minutes, enters high vacuum afterwards: be evacuated to 40Pa gradually by 1000Pa, temperature rises to 288 ℃ gradually, time is 30 minutes, keep vacuum to be not more than 40Pa, temperature is controlled at 288 ± 2 ℃, finishes polymerization when power of agitator reaches 13Kw, nitrogen extrudes material, granulation obtains antibacterial polyester section, its performance index such as table 1.
Embodiment 3.
Get 40.0Kg argentiferous 0.5%, contain zinc 1.2% carry silver, the zinc zirconium phosphate is added to 440Kg1, in the ammediol, stirs 2 hours with high speed dispersor, grinds 3 hours with sand mill then, ground slurries were with ultrasonication 15-45 minute, and are stand-by.
In the making beating still, add 2000Kg pure terephthalic acid and 1660Kg1, ammediol, 0.80Kg tetrabutyl titanate, 0.12Kg trimethyl phosphite 99,0.23Kg oxidation inhibitor three (2, the 4-di-t-butyl) phenyl-phosphite, back immigration esterifying kettle stirs, carry out esterification under the normal pressure, temperature of reaction is controlled at 220-260 ℃, and aquifer yield is during greater than 410L, and esterification finishes.The slurry of esterification is moved into polymeric kettle, in polymeric kettle, add the antiseptic-germicide that 290.0Kg handles, carried out precondensation under the normal pressure 30 minutes, and temperature risen to 250 ℃ gradually, set up rough vacuum then: be evacuated to 1000Pa gradually by normal pressure, temperature rises to 275 ℃ gradually, time is 30 minutes, enters high vacuum afterwards: be evacuated to 40Pa gradually by 1000Pa, temperature rises to 288 ℃ gradually, time is 30 minutes, keep vacuum to be not more than 40Pa, temperature is controlled at 288 ± 2 ℃, finishes polymerization when power of agitator reaches 10Kw, nitrogen extrudes material, granulation obtains antibacterial polyester section, its performance index such as table 1.
Table 1 antibacterial polyester performance index
| Viscosity | Fusing point | Form and aspect b value | To the staphylococcus aureus antibiotic rate | To the intestinal bacteria antibiotic rate | |
| Embodiment 1 | 0.676 | 258 | 1.6 | 99.99 | 99.98 |
| Embodiment 2 | 0.650 | 252 | 2.2 | 99.99 | 99.98 |
| Embodiment 3 | 0.642 | 252 | 1.8 | 99.99 | 99.98 |
Claims (7)
1, a kind of preparation method of antibacterial polyester, comprise that reaction monomers carries out esterification, polyreaction in the presence of catalyzer, stablizer, oxidation inhibitor, antiseptic-germicide is dispersed in and makes solution adding reaction system in the dibasic alcohol, it is characterized in that, reaction monomers is the pure terephthalic acid, and antimicrobial is to be that 0.05～0.3 micron antiseptic-germicide inorganic powder adds dibasic alcohol and is made into the be weight percentage solution of 5%-30% of concentration with particle diameter; Described antiseptic-germicide is one of following:
(1) zeolite of the oxide compound of the oxide compound of carrying silver ion, zine ion, silver or zinc,
(2) phosphoric acid salt of the oxide compound of the oxide compound of carrying silver ion, zine ion, silver or zinc,
(3) titanium dioxide of the oxide compound of the oxide compound of carrying silver ion, zine ion, silver or zinc,
(4) silver-colored zinc with arbitrarily than compound zeolite, phosphoric acid salt or titanium dioxide,
Metal ion content is 1%～5% of an antiseptic-germicide weight in the antiseptic-germicide.
2, the preparation method of antibacterial polyester as claimed in claim 1 is characterized in that, described dibasic alcohol is an ethylene glycol, 1, ammediol or 1, any in the 4-butyleneglycol.
3, the preparation method of antibacterial polyester as claimed in claim 1, it is characterized in that, described antimicrobial is with dibasic alcohol and antiseptic-germicide inorganic powder wiring solution-forming, after high speed dispersor disperses 2～3 hours, ground 3～4 hours, handle obtaining in 15～45 minutes again with ultrasonic generator with sand mill.
4, the preparation method of antibacterial polyester as claimed in claim 1 is characterized in that, described antimicrobial adds in the reaction system before esterification.
5, the preparation method of antibacterial polyester as claimed in claim 1 is characterized in that, the add-on of described antimicrobial is in weight polyester 0.3%-3% weight percent.
6, the preparation method of antibacterial polyester as claimed in claim 1 is characterized in that, the add-on of described antimicrobial is in weight polyester 0.5%-1% weight percent.
7, the preparation method of antibacterial polyester as claimed in claim 1 is characterized in that, described esterification and polyreaction concrete operations are as follows:
(1) esterification adopts pure terephthalic acid's direct esterification method, the mol ratio of pure terephthalic acid and dibasic alcohol is 1: 1.1～1.3, catalyzer, stablizer, oxidation inhibitor add esterifying kettle with the pure terephthalic acid with the dibasic alcohol slurry, esterification is carried out under normal pressure, and temperature of reaction is 220 ℃-260 ℃; Antimicrobial is pressed 0.3%～3% of weight polyester per-cent add reactor;
(2) polyreaction was at first carried out precondensation 30 minutes under normal pressure, and temperature rises to 250 ℃; In the rough vacuum condition, temperature rises to 280 ℃ afterwards, enters high vacuum after one hour, and the temperature control is at 288 ± 2 ℃, and polyreaction finishes; Nitrogen extrudes material, granulation gets antibacterial polyester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021515123A CN1182176C (en) | 2002-12-27 | 2002-12-27 | Process for preparing antibiotic polyester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021515123A CN1182176C (en) | 2002-12-27 | 2002-12-27 | Process for preparing antibiotic polyester |
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|---|---|
| CN1425704A CN1425704A (en) | 2003-06-25 |
| CN1182176C true CN1182176C (en) | 2004-12-29 |
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|---|---|---|---|
| CNB021515123A Expired - Fee Related CN1182176C (en) | 2002-12-27 | 2002-12-27 | Process for preparing antibiotic polyester |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7052765B2 (en) | 2004-07-22 | 2006-05-30 | Taiwan Textile Research Institute | Method for manufacturing antibacterial polyester master batches and fibers both containing nano-silver particles |
| US9149558B2 (en) * | 2005-05-19 | 2015-10-06 | Ethicon, Inc. | Antimicrobial polymer compositions and the use thereof |
| CN102399419B (en) * | 2010-09-16 | 2013-07-03 | 中国石油化工股份有限公司 | Antibiotic poly(ethylene terephthalate) composition and preparation method thereof |
| CN103524720B (en) * | 2013-09-16 | 2015-07-15 | 厦门翔鹭化纤股份有限公司 | Production method of antibacterial polyester material |
| CN103570923B (en) * | 2013-10-14 | 2015-10-28 | 嘉兴学院 | The preparation method of antibacterial polyester material |
| CN104558558B (en) * | 2014-11-18 | 2016-09-07 | 厦门翔鹭化纤股份有限公司 | A kind of preparation method of antibacterial poly terephthalic acid 1,3-propylene glycol ester |
| CN105088388A (en) * | 2015-07-30 | 2015-11-25 | 浙江恒逸高新材料有限公司 | Preparation method for hydrophilic antibacterial polyester chips and fibers |
| CN108285531B (en) * | 2018-02-02 | 2019-11-26 | 东华大学 | A kind of preparation method of antibacterial polyester |
| CN109251309B (en) * | 2018-02-02 | 2020-01-24 | 东华大学 | Long-acting antibacterial polyester and preparation method thereof |
| CN108726531A (en) * | 2018-07-02 | 2018-11-02 | 洛阳建龙微纳新材料股份有限公司 | A kind of Zn ion modifications zeolite molecular sieve and its preparation method and application |
| CN112342691B (en) * | 2019-10-25 | 2022-09-09 | 福建冠泓工业有限公司 | Elastic antibacterial non-woven fabric and manufacturing process thereof |
| CN111253719B (en) * | 2019-11-18 | 2022-03-15 | 厦门翔鹭化纤股份有限公司 | Organic zinc antibacterial PET granules and preparation method thereof |
| CN115636930A (en) * | 2021-07-19 | 2023-01-24 | 中国石油天然气股份有限公司 | Antimicrobial polyethylene terephthalate composite material and preparation method thereof |
| CN115636929A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | Method for continuously producing antibacterial PET composite material, antibacterial PET film and preparation method thereof |
| CN113831517A (en) * | 2021-09-09 | 2021-12-24 | 万凯新材料股份有限公司 | Preparation method of antibacterial and uvioresistant polyester |
| CN114277483A (en) * | 2021-12-24 | 2022-04-05 | 上海亮丰新材料科技有限公司 | Temperature-adjusting fabric with lasting antibacterial and anti-mite functions and production method thereof |
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2002
- 2002-12-27 CN CNB021515123A patent/CN1182176C/en not_active Expired - Fee Related
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