CN102619086B - Flame retardant anti-bacterial composite modifier used in fiber field and preparation method thereof - Google Patents
Flame retardant anti-bacterial composite modifier used in fiber field and preparation method thereof Download PDFInfo
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- CN102619086B CN102619086B CN2012100997730A CN201210099773A CN102619086B CN 102619086 B CN102619086 B CN 102619086B CN 2012100997730 A CN2012100997730 A CN 2012100997730A CN 201210099773 A CN201210099773 A CN 201210099773A CN 102619086 B CN102619086 B CN 102619086B
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Abstract
The invention relates to a flame retardant anti-bacterial composite modifier used in the fiber field and a preparation method thereof. The active components of the flame retardant anti-bacterial modifier are alkyl phosphate and alkyl guanidine; and the preparation method of the flame retardant anti-bacterial composite modifier comprises the following steps of: (1) preparing alkyl tetrol phosphoric acid ester; and (2) taking alkyl tetrol phosphate ester B, alkyl guanidine C and p-benzoic acid alkyl nitrile D which have the equal amount of substance, adding concentrated sulfuric acid and dicyclohexylcarbodiimide/N, N'-diisopropyl carbodiimide (DCC/DIC) as catalysts, wherein the mass ratio of the concentrated sulfuric acid to the alkyl tetrol phosphate ester B is 1:2-4, the mass ratio of DCC/DIC to the alkyl guanidine C is 1:2-5, rising the temperature to 70 to 200 DEG C, after reacting for 3-10h, cooling, filtering and drying to obtain the solid composite modifier E. The flame retardant anti-bacterial composite modifier has the advantages of having the flame retardant anti-bacterial performance, good thermal stability, being capable of meeting the high temperature processing requirement and being not easy to degrade; and products machined and prepared by using the composite modifier are not easy to oxidize and change color; and the flame retardant anti-bacterial composite modifier is widely applied.
Description
[technical field]
The present invention relates to technical field of function materials, specifically, is a kind of fire-retardant, antibiotic composite modifier its preparation method for fiber art.
[background technology]
Along with the raising with living standards of the people of developing rapidly of industry, particularly to the consciousness of health also in continuous enhancing.Because harmful bacteria is very extensive in distributed in nature, and of a great variety, quantity is huge, and the mankind's health in serious threat.Infected the disease that produces by spread of germs, formed a great society problem, cause extensive concern.Therefore the research of disinfectant seems particularly important.Guanidine class disinfectant is to apply in recent years a more class disinfection antibacterial agent, while easy to use is due to has a broad antifungal spectrum, low toxicity, non-stimulated, its range of application is more and more extensive, except being applied to the industrial disinfection such as food and alcoholic beverage, also can be used for the sterilization of fibre paper, food and daily living article (towel, sweater, mouth mask).
The Chinese patent of CN 101595880A, disclose complex antimicrobials and antimicrobial coating composition and antimicrobial coating material.Described inorganic antiseptic is slaine and/or the metal oxide with anti-microbial property, and described organic antibacterial agent is that to have respectively do for oneself hydrogen or carbon number of the compound of the composition shown in following formula and one or more in pyridine: R1, R2 be the alkyl of 1-8.
China Patent Publication No. CN 101565392A discloses a kind of methyl nitroguanidine machine preparation method.Invented technology equipment is simple.Easy to operate, to wait reaction yield high having used sulfuric acid to make catalyst, and pollute littlely, and product purity is generally more than 98%.
Along with the extensive use of macromolecular material, the security of its goods more and more comes into one's own.Since 20 century 70s, external fire proofing develops rapidly, to the also increase day by day of demand of fire retardant.China also becomes more and more important to the developmental research of fire proofing.At present, the development trend of organic fire-retardant is low cigarette, halogen, with phosphorus nitrogen series, replaces halogen series.
A kind of BACN phosphate flame retardant of phosphorus---nitrogenous,---pentaerythrite diphosphate two hydrogen ester melamine salts.Has low cigarette, efficient.The characteristics of Heat stability is good.
Li Huiling has synthesized the reactive flame retardant bromo-chloro-alky phosphate that contains P, N, three kinds of elements of Cl and contain hydroxyl, and the part of hydroxyl compound in the alternative polyester unsaturated monomer of using, anti-flammability (colloid and polymer, 18 (4): 2000) with wide application prospect.
China Patent Publication No. CN 101701423A, disclose and be used for phosphorus flame retardant of viscose and its production and use.Fire retardant of the present invention is the phosphorus flame retardant that contains phosphorus, sulphur, nitrogen cooperative flame retardant, does not contain halogen element, and during thermal decomposition, contaminated environment is little, uses plant that this fire retardant is processed to have the outstanding advantages such as good flame retardation effect, durability are done, strength decreased is little.Figure below is the structural formula of fire retardant for this reason:
For disinfectant and fire retardant, be both at home and abroad all research for single performance in recent years, do not inquire into function is compound.And the present invention is with good disinfectant---guanidine compound carries out copolymerization with the alkyl phosphate with fine fire resistance, and the material that therefore makes has antibiotic and sterilizing and fire resistance concurrently.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of fire-retardant, antibiotic composite modifier its preparation method for fiber art is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of fire-retardant, antibiotic composite modifier for fiber art, its active component is alkyl phosphate, alkyl guanidine; The mol ratio of two components is 1: 1.
Described alkyl phosphate is alkyl tetrol phosphoric acid hydrogen ester;
A kind of preparation method of fire-retardant, the antibiotic composite modifier for fiber art, its concrete steps are:
(1) preparation of alkyl tetrol phosphoric acid hydrogen ester
Get mol ratio and be 4～6: 1 alkyl tetrol A and phosphorus oxychloride POCl
3, be heated with stirring to vacuum distillation recovered solvent after 70～80 ℃ of reaction 24h, dry and through glacial acetic acid, be recrystallized and obtain intermediate product with washed with dichloromethane; Then add deionized water in this intermediate product, the mol ratio of water and alkyl tetrol is 1: 1～2, is warming up to 100 ℃, and reacts 2h at this temperature, more naturally is down to room temperature, and cooling and oven dry obtains alkyl tetrol phosphate B; Reaction equation is as follows:
(2) the alkyl tetrol phosphate B of amount of substance, alkyl guanidine C, para Toluic Acid's alkyl nitrile D such as get.Add the concentrated sulfuric acid, dicyclohexylcarbodiimide/N, N '-DIC (DCC/DIC) is made catalyst, the mass ratio of the concentrated sulfuric acid and alkyl tetrol phosphate B is 1: 2～4, the mass ratio of DCC/DIC and alkyl guanidine C is 1: 2～5, be warming up to 70～200 ℃, after reaction 3～10h, cold filtration is dry, obtains fire-retardant, the antibiotic composite modifier E of solid; Reaction equation is as follows:
The structural formula of alkyl tetrol A:
Wherein, R
1, R
2, R
3, R
4Carbon number is the alkyl of 1-10 separately, can be identical or different.R
1For the minimum alkyl of carbon number.
The structural formula of alkyl tetrol phosphate B:
The structural formula of alkyl guanidine C:
Wherein, R is hydrogen or alkyl, and R ' is hydrogen or alkyl.
The structural formula of para Toluic Acid's alkyl nitrile D:
Wherein, R " be alkyl.
Compared with prior art, good effect of the present invention is:
(1) the antibiotic and fire-retardant performance of composite material concurrent of the present invention;
(2) good thermal stability can meet high temperature process, the difficult degraded;
(3) composite of the present invention is obtained by copolymerization by anti-flaming function group and antibacterial functions group, makes fire-retardant and antibiotic group be difficult for migration, and effect is more lasting;
(4) be difficult for oxidized and variable color through actual observation with the product of preparation that antiseptic of the present invention is processed;
(5) the flesh family macromolecule type antiseptic of the present invention's preparation can be widely used in plastics, coating, and powdery paints, rubber, wood is moulded, rubber and plastic, weaving, the fields such as water treatment.
[specific embodiment]
The present invention below is provided a kind of specific embodiment of fire-retardant, the antibiotic composite modifier its preparation method for fiber art.
Embodiment 1
A kind of preparation method of fire-retardant, the antibiotic composite modifier for fiber art, its concrete steps are:
(1) preparation of phosphate:
Get pentaerythrite 34g (0.28mol) in filling how many gram POCl
3There-necked flask in, stir, heat is to 75 ℃, reaction 24h, cold filtration, use washed with dichloromethane, be dried to constant weight and add in the there-necked flask of deionized water 200ml after glacial acetic acid recrystallization, with 100 ℃ under react 2h, filtration drying obtains solid B0.28mol (50.4g).
(2) preparation of fire-retardant, antimicrobial composite material:
Get in B, C, D and the there-necked flask of 0.28mol, add the 16.8g concentrated sulfuric acid, 5.11gDCC/DIC to make catalyst, be warming up to 70～200 ℃, after reaction 3～10h, cold filtration is dry, obtains solid E.
The resulting composite of the present invention has following characteristics:
Wherein prepared composite has fire-retardant and antibiotic performance;
The polymerization methods of prepared composite material by adopting polycondensation wherein, avoided the inhomogeneities of blend, improved to a great extent reactivity worth.
Performance characterization:
Investigate E to the fire-retardant index of PP in Table shown in:
| PP/g | Fire retardant (B)/g | Oxygen index (OI)/OI | Self-ignition point/℃ | Self-extinguishing time | Combustion characteristics |
| 30 | 0 | 17.5 | 454 | Afterflame | Cigarette is arranged |
| 30 | 3 | 23.4 | 462 | 1min | Few cigarette |
| 30 | 6 | 28.8 | 481 | 0 | Smokelessly |
| 30 | 9 | 34.1 | 483 | 0 | Smokelessly |
Investigate the anti-microbial property of E, result is as shown in the table:
1. bacteriostatic test plate: 4 kinds of each 0.2mL of bacterium liquid (1 Os CFU/mL) through hatching 6-18h are inoculated in respectively on nutrient agar panel, evenly coat whole flat board.Put the Oxford cup on flat board, adding solubility liquid 0.2mL final concentration in the cup of Oxford is 10mg/mL; Do not add liquid in four control tube, cultivate in the 37C incubator, survey antibacterial circle diameter after 24h, repeat 3 times.
2. minimal inhibitory concentration (MIC) is measured: the broth dilution method that adopts the U.S. standardization committee of state-run clinical labororatory (National Committee for Clinical Laboratorystandards, NCCLS) to recommend.
The antibiotic loop diameter (mm) of table 1 antiseptic to fungi, Gram-negative bacteria, gram-positive bacteria
Minimal inhibitory concentration (MIC) mg/ml of table 2 antiseptic to fungi, Gram-negative bacteria, gram-positive bacteria
The above is only the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (1)
1. a preparation method who is used for fire-retardant, the antibiotic composite modifier of fiber art, is characterized in that, its concrete steps are:
(1) preparation of alkyl tetrol phosphate
Getting mol ratio is alkyl tetrol A and the phosphorus oxychloride POCl of 4～6:1
3, be heated with stirring to vacuum distillation recovered solvent after 70～80 ℃ of reaction 24h, dry and through glacial acetic acid, be recrystallized and obtain intermediate product with washed with dichloromethane; Then add deionized water in this intermediate product, the mol ratio of water and alkyl tetrol is 1:1～2, is warming up to 100 ℃, and reacts 2h at this temperature, more naturally is down to room temperature, and cooling and oven dry obtains alkyl tetrol phosphate B; Reaction equation is as follows:
(B)
(2) the alkyl tetrol phosphate B of amount of substance, alkyl guanidine C, para Toluic Acid's alkyl nitrile D such as get; Add the concentrated sulfuric acid,
N, N '-Dicyclohexylcarbodiimide/N, N'-DIC (DCC/DIC) is made catalyst, the mass ratio of the concentrated sulfuric acid and alkyl tetrol phosphate B is 1:2～4, the mass ratio of DCC/DIC and alkyl guanidine C is 1:2～5, be warming up to 70～200 ℃, after reaction 3～10h, cold filtration is dry, obtains fire-retardant, the antibiotic composite modifier E of solid; Reaction equation is as follows:
（E） 。
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100997730A CN102619086B (en) | 2012-04-03 | 2012-04-03 | Flame retardant anti-bacterial composite modifier used in fiber field and preparation method thereof |
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| CN2012100997730A CN102619086B (en) | 2012-04-03 | 2012-04-03 | Flame retardant anti-bacterial composite modifier used in fiber field and preparation method thereof |
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| CN102619086B true CN102619086B (en) | 2013-11-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936786B (en) * | 2014-05-14 | 2015-10-07 | 青岛大学 | A kind of preparation method with the auxiliary agent of flame-proof antibiotic function |
| CN104846647B (en) * | 2015-04-28 | 2017-04-12 | 中国科学院合肥物质科学研究院 | Fabric with flame-retardant function and anti-bacterial function and manufacturing method of fabric |
| CN109837759B (en) * | 2019-02-25 | 2021-12-03 | 朱建余 | Antibacterial flame-retardant finishing agent for denim fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004332187A (en) * | 2003-04-18 | 2004-11-25 | Toray Ind Inc | Flame-retardant polyester-based synthetic fiber structure and method for producing the same |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
| CN101857805A (en) * | 2010-05-13 | 2010-10-13 | 中国地质大学（武汉） | P-N type flame retardant and synthesis method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004332187A (en) * | 2003-04-18 | 2004-11-25 | Toray Ind Inc | Flame-retardant polyester-based synthetic fiber structure and method for producing the same |
| CN101230274A (en) * | 2007-12-27 | 2008-07-30 | 南京师范大学 | Method for preparing annular phosphonate or annular phosphate flame retardant |
| CN101857805A (en) * | 2010-05-13 | 2010-10-13 | 中国地质大学（武汉） | P-N type flame retardant and synthesis method thereof |
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Inventor after: Wu Zhenshan Inventor after: He Wei Inventor after: Xiang Feng Inventor after: Gu Yueqiang Inventor after: Sun Guojun Inventor after: Zhang Jian Inventor after: Fu Hongzhi Inventor after: Wang Chaosheng Inventor after: Qin Dan Inventor after: Wang Qiong Inventor after: Zuo Pingan Inventor before: Zuo Pingan Inventor before: He Wei Inventor before: Xiang Feng Inventor before: Zhang Jian Inventor before: Fu Hongzhi Inventor before: Wang Chaosheng Inventor before: Qin Dan Inventor before: Wang Qiong |
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Free format text: CORRECT: INVENTOR; FROM: ZUO PINGAN HE WEI XIANG FENG ZHANG JIAN FU HONGZHI WANG CHAOSHENG QIN DAN WANG QIONG TO: WU ZHENSHAN GU YUEQIANG SUN GUOJUN ZHANG JIAN FU HONGZHI WANG CHAOSHENG QIN DAN WANG QIONG ZUO PINGAN HE WEI XIANG FENG |
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