CN102504264B - Preparation method of flame retarding antibacterial agent - Google Patents
Preparation method of flame retarding antibacterial agent Download PDFInfo
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- CN102504264B CN102504264B CN 201110308395 CN201110308395A CN102504264B CN 102504264 B CN102504264 B CN 102504264B CN 201110308395 CN201110308395 CN 201110308395 CN 201110308395 A CN201110308395 A CN 201110308395A CN 102504264 B CN102504264 B CN 102504264B
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- flame retarding
- antibacterial agent
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Abstract
The invention relates to a preparation method of a flame retarding antibacterial agent. The preparation method comprises the following steps: adding distilled water in 3-aminopropyltriethoxysilane for conducting hydrolysis reaction, then conducting polycondensation, adding dicyandiamide into the obtained ivory-white emulsion, conducting condensation and backflow on the mixture, then adding phosphorus pentoxide and finally obtaining colorless and transparent solution. The main product of the colorless and transparent solution is the flame retarding antibacterial agent. The flame retarding antibacterial agent can perform finishing to the cotton fabrics, so that the fabrics have double functions of bacteria resistance and flame retarding; and the obtained flame retarding antibacterial agent is safe and environment-friendly and is a novel dyeing and finishing auxiliary.
Description
Technical field:
The present invention relates to a kind of preparation method of flame retarding antibacterial agent, belong to the development technique field of novel dyeing and finishing auxiliary agent.Can be used as the functional finishing agent of cotton fabric, give the pure cotton fabric dual-functionality.
Background technology:
It is raw material that the present invention adopts 3-aminopropyl triethoxysilane and Dyhard RU 100, is hydrolyzed to phosphoric acid with Vanadium Pentoxide in FLAKES and makes esterifying agent, synthetic siliceous antimicrobial form flame-retardant compound.Both contain the ignition-proof elements such as silicon, phosphorus, nitrogen in synthetic compound, and contained again the guanidine molecular structure of anti-microbial property, thereby obtain a kind of multifunction finishing agent, and given antibacterial fabric fire-retardant dual-use function.
The research of present domestic fire retardant has turned to the without halide fire retardant gradually, have higher flame retardant properties although contain halogenated flame retardant, and addition is few, is used widely for a long time.But when presence of fire, the decomposition of these materials and burning can produce a large amount of irritant and corrosive hydrogen halides, not only seriously hinder personnel's evacuation and fire fighting, also corrode instrument and equipment, cause " secondary disaster ", and products of combustion has very long atmospheric lifetime, major polluting atmosphere environment, even damage the ozone layer, simultaneously the Halogen based flame retardant may be emitted halogenation hexichol dioxin and dibenzofuran at fire with when burning, and immunity and the regeneration system rapidly of human body damaged.Therefore this based flame retardant progressively is eliminated, by halogen-free flame retardants is substituted.
Thermostability, oxidative stability and good snappiness that the silicon based flame retardant is high because silicon-containing group has, utilize polymerization, grafting, crosslinking technological they can be imported the position such as main chain, side chain of fiber, and the decomposes after product is mainly carbonic acid gas, water vapor and silicon-dioxide, so organic silicon fibre retardant is considered to efficiently, ecological friendly, anti-molten drop and press down the non-halogen fire retardant of new generation of cigarette.The ignition-proof elements such as the silicon of introducing in the present invention, phosphorus, nitrogen meet the trend of China's fire retardant exploitation.
Guanidine class antiseptic-germicide is the environment-friendly type antibiotic agent of a class product having enhanced antibacterial action, because most of organic antibacterial agent has toxic side effect, can cause tetter, harmful, (even some monomer has carcinogenesis), poor heat resistance, easy decomposition, scent of, work-ing life is short, and guanidine class antiseptic-germicide process on textiles after not only nontoxic (there is not carinogenicity in human body, causes sex change and teratogenecity), tasteless, nonirritant, high temperature resistant, germ resistance good, and washing fastness is also fine, and antibacterial effect is lasting.Guanidine radicals group in guanidine compound is effective active group, can with microbe in group or element interact, destroy its normal matter and energy metabolism, be considered to use at present antibacterial finishing agent preferably.The guanidine structure of introducing in the present invention meets the trend of antiseptic-germicide development as the method for antiseptic elements, belong to the exploitation of environmentally friendly reagent.
Along with people reach functional concern the raising that the textiles serviceability requires, textiles is more and more to multi-functional future development, and polycomponent, functionalization have become the main flow of current textile product research and development.Also do not have up to now a kind of fiber can be enough to satisfy people to multi-level, the multi-functional demand of fabric, therefore novel multifunctional clothes has become a kind of trend with the research and development of weaving face fabric comprehensively.Involved in the present invention to synthetic product belong to the agent of response type antibacterial flame-retardant, good endurance meets at present domestic present Research about the antibacterial flame-retardant agent, and pure cotton fabric is carried out can giving antibacterial fabric fire-retardant dual-use function after finishing functions.
At present, patent and document are not yet reported preparation and the adjustment method of the flame retardant type guanidine class antiseptic-germicide that the present invention relates to both at home and abroad, and this finishing composition is with a wide range of applications and prospect aspect textile finishing.
Summary of the invention:
The invention reside in the dyeing and finishing auxiliaries of synthetic a kind of Multifunction, provide the synthetic of a kind of flame retarding antibacterial agent and to the adjustment method of cotton fabric, can providing cotton fabric antibiotic and fire-retardant dual-use function.
The synthetic method of flame retarding antibacterial agent of the present invention, operation as follows:
1, get the 3-aminopropyl triethoxysilane of 1 times of molar weight, put into there-necked flask, the distilled water that adds 4.4 times of molar weights under ice-water bath (temperature 0-5 ℃), drip dilute acetic acid and regulate PH=4-5, uniform stirring makes its reaction that is hydrolyzed, reaction times 20min, obtain colourless transparent liquid A, be warming up to gradually room temperature, add 1M NaOH solution to regulate PH=8-9, add the buffer reagent CaCO of 0.05 times of molar weight
3Protection silicon hydroxyl carries out polycondensation, and reaction times 120min obtains milky emulsion, and its primary product is B.The principal reaction equation is as follows:
2, regulate the PH=7 of product B solution, take the Dyhard RU 100 of 2 times of molar weights, add in above-mentioned there-necked flask and stir; be fixed in thermostat water bath with iron stand; under nitrogen protection, the water-bath temperature remains on 60 ℃, after condensing reflux 60min; the Vanadium Pentoxide in FLAKES that adds 4 times of molar weights; constantly stir in reaction process, reaction is evenly carried out, reaction times 50min; obtain water white solution, its primary product is the flame retarding antibacterial agent of C.Main reaction equation is as follows:
3, the flame retarding antibacterial agent that is C with synthetic primary product is applied to pure cotton fabric as dressing liquid and arranges, the pure cotton fabric of 1 weight part is immersed in the dressing liquid of 50 weight parts, constantly stir with glass stick, cotton fibre and dressing liquid are fully reacted, treatment time is 30min, then use the electronic laboratory mangle roll compacting of table type air pressure, regulating padding machine pressure is 0.4Mpa, making pick-up is 80%, two soak two rolls, at the drying in oven 3min of 80 ℃, then be placed under 160 ℃ of conditions and bake 4min, oven dry again after the taking-up washing.Can give antibacterial fabric fire-retardant dual-use function after arrangement.
Embodiment
Embodiment 1:
1, fix three mouthfuls of 200ml flasks with iron stand; the nitrogen circulation protector is installed, is got the 3-aminopropyl triethoxysilane of 10ml (0.04mol), put into there-necked flask; the distilled water that adds 40ml under ice-water bath (temperature 0-5 ℃); drip dilute acetic acid and regulate PH=4-5, uniform stirring makes its reaction that is hydrolyzed, reaction times 20min; obtain colourless transparent liquid A; be warming up to gradually room temperature, drip 1M NaOH solution and regulate PH=8-9, add the buffer reagent CaCO of 0.2g
3Protection silicon hydroxyl carries out polycondensation, and reaction times 120min obtains milky emulsion, and its primary product is B.
2, regulate the PH=7 of product B solution, take the Dyhard RU 100 of 6.8g, add in above-mentioned there-necked flask and stir; be fixed in thermostat water bath with iron stand; under nitrogen protection, the water-bath temperature remains on 60 ℃, after condensing reflux 60min; the Vanadium Pentoxide in FLAKES that adds 17.0g; constantly stir in reaction process, reaction is evenly carried out, reaction times 50min; obtain water white solution, its primary product is the flame retarding antibacterial agent of C.
3, the flame retarding antibacterial agent that is C with synthetic primary product is applied to pure cotton fabric as dressing liquid and arranges; bath raio is 1: 50 (mass ratio of fabric and dressing liquid); constantly stir with glass stick; cotton fibre and dressing liquid are fully reacted; the treatment time is 30min; then use the electronic laboratory mangle roll compacting of table type air pressure; regulating padding machine pressure is 0.4Mpa; making pick-up is 80%; two soak two rolls; at the drying in oven 3min of 80 ℃, then is placed under 160 ℃ of conditions and bakes 4min, oven dry again after the taking-up washing.
4, the limiting oxygen index(LOI) of fabric after test arranges according to GB/T5455-1997 Fire-proof Finishing Agents for Textile performance test oxygen index method.Evaluation method test anti-microbial property according to GB/T20944.1-2007 antibacterial textile performance.
Anti-microbial property test (qualitative):
H＝(D-d)/2
The antibacterial bandwidth of H-----;
The antibacterial mean value with external diameter of D-----;
The d------specimen finish.
Can find out from data, use the Gram-negative intestinal bacteria to arranging rear sample testing, antibacterial bandwidth H=1～1.5mm.The antibacterial bandwidth H=1mm of sample after the Gram-positive streptococcus aureus is processed.According to GB/T 20944.1-2007, antibacterial bandwidth is more than or equal to 1mm, and there is no bacterial reproduction below sample, shows good anti-bacterial effect.
| Bacteriostasis rate | |
| Intestinal bacteria | 97％ |
| Streptococcus aureus | 96％ |
Evaluation part 2 according to GB/T20944.2-2007 antibacterial textile performance: absorption process, use the Gram-negative intestinal bacteria to arranging rear sample testing, bacteriostasis rate is 97%.After the Gram-positive streptococcus aureus is processed, the bacteriostasis rate of sample is 96%.
The flame retardant properties test:
According to GB/T 5454-1997, when the nonflammable material that belongs to of LOI 〉=26%, the limiting oxygen index(LOI) LOI=45.7% of sample after arranging, after illustrating that use auxiliary agent of the present invention is processed cotton fabric, fabric has higher flame retardant properties.
Embodiment 2:
1, fix three mouthfuls of 200ml flasks with iron stand; the nitrogen circulation protector is installed, is got the 3-aminopropyl triethoxysilane of 10ml (0.04mol), put into there-necked flask; the distilled water that adds 40ml under ice-water bath (temperature 0-5 ℃); drip dilute acetic acid and regulate PH=4-5, uniform stirring makes its reaction that is hydrolyzed, reaction times 20min; obtain colourless transparent liquid A; be warming up to gradually room temperature, drip 1M NaOH solution and regulate PH=8-9, add the buffer reagent CaCO of 0.2g
3Protection silicon hydroxyl carries out polycondensation, and reaction times 120min obtains milky emulsion, and its primary product is B.
2, regulate the PH=7 of product B solution, take the Dyhard RU 100 of 6.8g, add in above-mentioned there-necked flask and stir; be fixed in thermostat water bath with iron stand; under nitrogen protection, the water-bath temperature remains on 60 ℃, after condensing reflux 60min; the Vanadium Pentoxide in FLAKES that adds 8.5g; constantly stir in reaction process, reaction is evenly carried out, reaction times 50min; obtain water white solution, its primary product is the flame retarding antibacterial agent of C.
3, the flame retarding antibacterial agent that is C with synthetic primary product is applied to pure cotton fabric as dressing liquid and arranges; bath raio is 1: 50 (mass ratio of fabric and finishing composition); constantly stir with glass stick; cotton fibre and dressing liquid are fully reacted; the treatment time is 30min; then use the electronic laboratory mangle roll compacting of table type air pressure; regulating padding machine pressure is 0.4Mpa; making pick-up is 80%; two soak two rolls; at the drying in oven 3min of 80 ℃, then is placed under 160 ℃ of conditions and bakes 4min, oven dry again after the taking-up washing.
4, the limiting oxygen index(LOI) of fabric after test arranges according to GB/T5455-1997 Fire-proof Finishing Agents for Textile performance test oxygen index method.Evaluation method test anti-microbial property according to GB/T20944.1-2007 antibacterial textile performance.
Anti-microbial property test (qualitative):
H＝(D-d)/2
The antibacterial bandwidth of H-----;
The antibacterial mean value with external diameter of D-----;
The d------specimen finish.
Can find out from data, use the Gram-negative intestinal bacteria to arranging rear sample testing, antibacterial bandwidth H=1～1.25mm.The antibacterial bandwidth H=1mm of sample after the Gram-positive streptococcus aureus is processed.According to GB/T20944.1-2007, antibacterial bandwidth is more than or equal to 1mm, and there is no bacterial reproduction below sample, shows good anti-bacterial effect.
| Bacteriostasis rate | |
| Intestinal bacteria | 95％ |
| Streptococcus aureus | 94％ |
Evaluation part 2 according to GB/T20944.2-2007 antibacterial textile performance: absorption process, use the Gram-negative intestinal bacteria to arranging rear sample testing, bacteriostasis rate is 95%.After the Gram-positive streptococcus aureus is processed, the bacteriostasis rate of sample is 94%.
The flame retardant properties test:
| Sample after arranging | Blank textile sample | |
| LOI | 30％ | 19％ |
| The length of glowing | 20mm | After-flame |
According to GB/T 5454-1997, when the nonflammable material that belongs to of LOI 〉=26%, the limiting oxygen index(LOI) LOI=30% of sample after arranging, after illustrating that use auxiliary agent of the present invention is processed cotton fabric, fabric has higher flame retardant properties.
Claims (1)
1. the preparation method of a flame retarding antibacterial agent is characterized in that:
The first step: the 3-aminopropyl triethoxysilane of getting 1 times of molar weight, put into there-necked flask, the distilled water that adds 4.4 times of molar weights under 0 ℃ of ice-water bath, drip dilute acetic acid and regulate pH=4-5, uniform stirring makes its reaction that is hydrolyzed, reaction times 20min, obtain colourless transparent liquid A, be warming up to gradually room temperature, add 1M NaOH solution to regulate pH=8-9, add the buffer reagent CaCO of 0.05 times of molar weight
3Protection silicon hydroxyl carries out polycondensation, and reaction times 120min obtains milky emulsion, and its primary product is B; The principal reaction equation is as follows:
Second step: regulate the pH=7 of product B solution, take the Dyhard RU 100 of 2 times of molar weights, add in above-mentioned there-necked flask and stir, be fixed in thermostat water bath with iron stand, under nitrogen protection, the water-bath temperature remains on 60 ℃, after condensing reflux 60min, the Vanadium Pentoxide in FLAKES that adds 4 times of molar weights, constantly stir in reaction process, reaction is evenly carried out, reaction times 50min, obtain water white solution, its primary product is the flame retarding antibacterial agent of C; Main reaction equation is as follows:
The 3rd step: the synthetic primary product flame retarding antibacterial agent that is C is applied to pure cotton fabric as dressing liquid arranges, the pure cotton fabric of 1 weight part is immersed in the dressing liquid of 50 weight parts, constantly stir with glass stick, cotton fibre and dressing liquid are fully reacted, treatment time is 30min, then use the electronic laboratory mangle roll compacting of table type air pressure, regulating padding machine pressure is 0.4Mpa, making pick-up is 80%, two soak two rolls, at the drying in oven 3min of 80 ℃, then be placed under 160 ℃ of conditions and bake 4min, oven dry again after the taking-up washing.
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| CN 201110308395 CN102504264B (en) | 2011-10-08 | 2011-10-08 | Preparation method of flame retarding antibacterial agent |
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| CN 201110308395 CN102504264B (en) | 2011-10-08 | 2011-10-08 | Preparation method of flame retarding antibacterial agent |
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| CN102504264A CN102504264A (en) | 2012-06-20 |
| CN102504264B true CN102504264B (en) | 2013-06-12 |
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Families Citing this family (6)
| 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 |
| CN104177618B (en) * | 2014-09-15 | 2016-09-28 | 青岛大学 | A kind of preparation method of the auxiliary agent with water-repellent and flame-retardent function |
| CN104211966B (en) * | 2014-09-16 | 2016-09-28 | 青岛大学 | A kind of preparation method of phosphor-containing flame-proof silicone oil |
| TWI607067B (en) * | 2015-09-25 | 2017-12-01 | 立得光電科技股份有限公司 | Anti-bacterial and anti-mould surface coating, and manufacturing method thereof |
| CN107868254B (en) * | 2017-12-14 | 2020-07-14 | 成都硅宝科技股份有限公司 | Multifunctional plastic additive and preparation method thereof |
| CN111501340A (en) * | 2020-05-29 | 2020-08-07 | 江苏雷鸟伪装纺织新材料有限公司 | Preparation process of flame-retardant antibacterial coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314797A (en) * | 2008-07-15 | 2008-12-03 | 四川大学 | High-fire-retardancy aminoresin nano-complex-function tanning agent |
| CN101367942A (en) * | 2008-07-11 | 2009-02-18 | 黄山市强力化工有限公司 | Preparation method for branched chain type amino-long chain alkyl co-modified silicone oil and its microemulsion, and uses thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367942A (en) * | 2008-07-11 | 2009-02-18 | 黄山市强力化工有限公司 | Preparation method for branched chain type amino-long chain alkyl co-modified silicone oil and its microemulsion, and uses thereof |
| CN101314797A (en) * | 2008-07-15 | 2008-12-03 | 四川大学 | High-fire-retardancy aminoresin nano-complex-function tanning agent |
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Address after: 266071 Shandong city of Qingdao province Ningxia City Road No. 308 Applicant after: Qingdao University Address before: 266071 Hongkong East Road, Laoshan District, Shandong, China, No. 7, No. Applicant before: Qingdao University |
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Effective date of registration: 20180110 Address after: 215228 Shengze Town, Suzhou City, Jiangsu Province, science and Technology Road (Group 11 of San Tang Village) Patentee after: Wujiang HTC thread Co. Ltd. Address before: 266071 Shandong city of Qingdao province Ningxia City Road No. 308 Patentee before: Qingdao University |
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