CN102619086A - 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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- CN102619086A CN102619086A CN2012100997730A CN201210099773A CN102619086A CN 102619086 A CN102619086 A CN 102619086A CN 2012100997730 A CN2012100997730 A CN 2012100997730A CN 201210099773 A CN201210099773 A CN 201210099773A CN 102619086 A CN102619086 A CN 102619086A
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- alkyl
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- tetrol
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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 that is used for fiber art.
[background technology]
Along with the raising with living standards of the people that develops 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 human beings'health in serious threat.Infect the disease that produces by spread of germs, constituted a great society problem, cause extensive concern.Therefore the research of disinfectant seems particularly important.Guanidine class disinfectant is to use one type of more disinfecting, antimicrobial agent in recent years; While easy to use is owing to has a broad antifungal spectrum, low toxicity, non-stimulated; Its range of application more and more widely; Except that being applied to 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 discloses 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 to have the compound of the composition shown in the following formula and in the pyridine one or more: respectively do for oneself hydrogen or carbon number of R1, R2 is the alkyl of 1-8.
Chinese patent publication number CN 101565392A discloses a kind of methyl nitroguanidine machine preparation method.Invented technology equipment is simple.Easy to operate, to wait reaction yield high using sulfuric acid to make catalyst, and pollute for a short time, 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 the seventies in 20th century, 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, replaces halogen series with phosphorus nitrogen 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 chlorine bromo alkyl 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.
Chinese patent publication number CN 101701423A discloses the phosphorus flame retardant that is used for viscose.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, and the plant of using this fire retardant to handle has that good flame retardation effect, durability are done, intensity reduces outstanding advantages such as little.Figure below is the structural formula of fire retardant for this reason:
All was research both at home and abroad in recent years, and did not have and inquire into function is compound to single performance for disinfectant and fire retardant.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 objective of the invention is to overcome the deficiency of prior art, a kind of fire-retardant, antibiotic composite modifier its preparation method that is used for fiber art is provided.
The objective of the invention is to realize through following technical scheme:
A kind of fire-retardant, antibiotic composite modifier that is used for fiber art, its active component is alkyl phosphate, alkyl guanidine; The mol ratio of two components is 1: 1.
Described alkyl phosphate is an alkyl tetrol phosphoric acid hydrogen ester;
A kind of preparation method who is used for fire-retardant, the antibiotic composite modifier of 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 POCl3 POCl
3, be heated with stirring to vacuum distillation recovered solvent behind 70～80 ℃ of reaction 24h, dry and be recrystallized through glacial acetic acid and obtain intermediate product with washed with dichloromethane; In this intermediate product, add deionized water then, the mol ratio of water and alkyl tetrol is 1: 1～2, is warming up to 100 ℃, and under this temperature, reacts 2h, reduces to room temperature more naturally, and cooling and oven dry obtain alkyl tetrol phosphate B; Reaction equation is following:
(2) the alkyl tetrol phosphate B of amount of substance such as get, alkyl guanidine C, para Toluic Acid's alkyl nitrile D.Add the concentrated sulfuric acid, dicyclohexylcarbodiimide/N; N '-DIC (DCC/DIC) makes catalyst; The mass ratio of the concentrated sulfuric acid and alkyl tetrol phosphate B is 1: 2～4, and the mass ratio of DCC/DIC and alkyl guanidine C is 1: 2～5, is warming up to 70～200 ℃; Cold filtration is dry behind reaction 3～10h, obtains fire-retardant, the antibiotic composite modifier E of solid; Reaction equation is following:
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
1Be 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 satisfy high temperature process, the difficult degraded;
(3) composite of the present invention is obtained through 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 antiseptic of the present invention institute processing and preparing;
(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, fields such as water treatment.
[specific embodiment]
The present invention below is provided a kind of specific embodiment that is used for fire-retardant, the antibiotic composite modifier its preparation method of fiber art.
Embodiment 1
A kind of preparation method who is used for fire-retardant, the antibiotic composite modifier of fiber art, its concrete steps are:
(1) preparation of phosphate:
Get pentaerythrite 34g (0.28mol) and how much restrain POCl in filling
3There-necked flask in, stir, heat is to 75 ℃; Reaction 24h, cold filtration is used washed with dichloromethane; Be dried to constant weight and add in the there-necked flask of deionized water 200ml through glacial acetic acid recrystallization back, with 100 ℃ react 2h down, 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, the adding 16.8g concentrated sulfuric acid, 5.11gDCC/DIC make catalyst, are warming up to 70～200 ℃, and cold filtration is dry behind reaction 3～10h, obtains solid E.
The resulting composite of the present invention has following characteristic:
Wherein the prepared composite material has fire-retardant and antibiotic performance;
Wherein the prepared composite material adopts the polymerization methods of polycondensation, has avoided the inhomogeneities of blend, has improved reactivity worth to a great extent.
Performance characterization:
Investigating E sees shown in the table the fire-retardant index of PP:
| 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, the 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 the nutrient agar panel, evenly coat whole flat board.On flat board, put the Oxford cup, adding solubility soup 0.2mL final concentration in the cup of Oxford is 10mg/mL; Do not add soup in four control tube, in the 37C incubator, cultivate, survey antibacterial circle diameter behind the 24h, repeat 3 times.
2. minimal inhibitory concentration (MIC) is measured: adopt the standardization committee of the state-run clinical labororatory of the U.S. (National Committee for Clinical Laboratorystandards, the broth dilution method of NCCLS) recommending.
Table 1 antiseptic is to the antibiotic loop diameter (mm) of fungi, Gram-negative bacteria, gram-positive bacteria
Table 2 antiseptic is to minimal inhibitory concentration (MIC) mg/ml of fungi, Gram-negative bacteria, gram-positive bacteria
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (4)
1. fire-retardant, an antibiotic composite modifier that is used for fiber art is characterized in that its active component is alkyl phosphate, alkyl guanidine.
2. a kind of fire-retardant, antibiotic composite modifier that is used for fiber art as claimed in claim 1 is characterized in that described alkyl phosphate, alkyl guanidine mol ratio are 1: 1.
3. a kind of fire-retardant, antibiotic composite modifier that is used for fiber art as claimed in claim 1 is characterized in that described alkyl phosphate is an alkyl tetrol phosphoric acid hydrogen ester.
4. 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 phosphoric acid hydrogen ester
Get mol ratio and be 4～6: 1 alkyl tetrol A and POCl3 POCl
3, be heated with stirring to vacuum distillation recovered solvent behind 70～80 ℃ of reaction 24h, dry and be recrystallized through glacial acetic acid and obtain intermediate product with washed with dichloromethane; In this intermediate product, add deionized water then, the mol ratio of water and alkyl tetrol is 1: 1～2, is warming up to 100 ℃, and under this temperature, reacts 2h, reduces to room temperature more naturally, and cooling and oven dry obtain alkyl tetrol phosphate B; Reaction equation is following:
(2) the alkyl tetrol phosphate B of amount of substance such as get, alkyl guanidine C, para Toluic Acid's alkyl nitrile D; Add the concentrated sulfuric acid, dicyclohexylcarbodiimide/N; N '-DIC (DCC/DIC) makes catalyst; The mass ratio of the concentrated sulfuric acid and alkyl tetrol phosphate B is 1: 2～4, and the mass ratio of DCC/DIC and alkyl guanidine C is 1: 2～5, is warming up to 70～200 ℃; Cold filtration is dry behind reaction 3～10h, obtains fire-retardant, the antibiotic composite modifier E of solid; Reaction equation is following:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936786A (en) * | 2014-05-14 | 2014-07-23 | 青岛大学 | Preparation method of assistant with flame-retardant and antimicrobial functions |
| CN104846647A (en) * | 2015-04-28 | 2015-08-19 | 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 |
| CN109837759A (en) * | 2019-02-25 | 2019-06-04 | 朱建余 | A kind of denim fabric antibacterial flame-retardant finishing agent 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 |
-
2012
- 2012-04-03 CN CN2012100997730A patent/CN102619086B/en not_active Expired - Fee Related
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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936786A (en) * | 2014-05-14 | 2014-07-23 | 青岛大学 | Preparation method of assistant with flame-retardant and antimicrobial functions |
| CN104846647A (en) * | 2015-04-28 | 2015-08-19 | 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 |
| 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 |
| CN109837759A (en) * | 2019-02-25 | 2019-06-04 | 朱建余 | A kind of denim fabric antibacterial flame-retardant finishing agent and preparation method thereof |
| CN109837759B (en) * | 2019-02-25 | 2021-12-03 | 朱建余 | Antibacterial flame-retardant finishing agent for denim fabric and preparation method thereof |
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| CN102619086B (en) | 2013-11-20 |
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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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