阅读说明：本技术 一种抗菌阻燃纤维素及其制备和应用 (A kind of antibacterial flame-retardant cellulose and its preparation and application ) 是由 吴德群 赵文静 李娜 李发学 王学利 俞建勇 于 2019-08-08 设计创作，主要内容包括：本发明涉及一种抗菌阻燃纤维素及其制备和应用,原料组分包括：纤维素、3-(异丁烯酰氧)丙基三甲氧基硅烷KH、聚乙烯亚胺PEI、乙烯基膦酸VA、抗菌剂、引发剂。本发明改性后的纤维素与原纤维素材料相比,其最大热释放速率可下降至原来的50％左右,总热释放量可下降至原材料的67％左右；对革兰氏阴性和阳性细菌均具有优良的抗菌效果,在30次洗涤后仍具有98％的抑菌率。(The present invention relates to a kind of antibacterial flame-retardant cellulose and its preparation and application, raw material components include: cellulose, 3- (isobutene acyl-oxygen) propyl trimethoxy silicane KH, polyethyleneimine PEI, vinyl phosphonic acid VA, antibacterial agent, initiator.The modified cellulose of the present invention is compared with fibrinogen cellulosic material, and maximum heat release rate can drop to original 50% or so, and total heat release can drop to 67% of raw material or so；Excellent antibacterial effect is all had to Gram-negative and positive bacteria, and still there is 98% bacteriostasis rate after 30 washings.)

1. a kind of antibacterial flame-retardant cellulose, which is characterized in that in parts by weight, raw material components include: 1 part of cellulose, 0.15- 0.5 part of 3- (isobutene acyl-oxygen) KH, 0.03-0.09 parts of propyl trimethoxy silicane PEI, 0.05-0.2 parts of polyethyleneimine ethylene VA, 0.02-0.05 parts of antibacterial agents of base phosphonic acids, 0.001-0.003 parts of initiators.

2. cellulose according to claim 1, which is characterized in that the molecular size range of the PEI is 600.

3. cellulose according to claim 1, which is characterized in that the antibacterial agent be antibacterial agent with siloxane group or Person has the antibacterial agent of double bond；Initiator is radical polymerization initiator.

4. cellulose according to claim 3, which is characterized in that the antibacterial agent can be N, N- dimethyl-N-(3- (three Methoxy silane) propyl) dodecane -1- ammonium chloride CDMA, methacrylic acid anhydride modification poly (hexamethylene) hydrochloride One or more of MAPHMG；Initiator is persulfate initiator, in hydrogen peroxide initiator, water-soluble azo initiator It is one or more of.

5. cellulose according to claim 1, which is characterized in that 1 part, 0.5 part 3- (isobutene acyl-oxygen) third of the cellulose Base trimethoxy silane KH, 0.07 part of polyethyleneimine PEI, 0.2 part of vinyl phosphonic acid VA, 0.05 part of antibacterial agent, 0.003 part draw Send out agent.

6. a kind of preparation method of antibacterial flame-retardant cellulose, comprising:

(1) it disperses cellulose in lye, KH and PEI is added, 12-24h is reacted at 30-50 DEG C, wash, drying obtains Product A；

(2) the product A in step (1) is submerged in water and adjust pH=2-3, KH, VA, antibacterial agent, 60 DEG C of initiator is added 6-8h is reacted, washing is dried to get antibacterial flame-retardant cellulose.

7. preparation method according to claim 6, which is characterized in that the additional amount of KH is cellulose material in the step (1) The 10-40wt% of amount.

8. a kind of antibacterial flame-retardant cellulose of claim 6 the method preparation.

9. a kind of fabric based on antibacterial flame-retardant cellulose described in claim 1.

10. the application of antibacterial flame-retardant cellulose described in a kind of claim 1.

Technical field

The invention belongs to functional fiber element and its preparation and application field, in particular to a kind of antibacterial flame-retardant cellulose and It is prepared and application.

Background technique

As society is constantly progressive, science and technology is maked rapid progress, demand of the people to material is no longer limited to clothes, home textile Etc. traditional fields, and require used in material have certain specific functions to meet the needs of generating in use process, example Such as mould proof, antibacterial, filtering, absorption, uvioresistant, radiation protection, Waterproof Breathable, antistatic, dust-proof, antifouling, fire-retardant function.

In addition, environmental problem caused by scarcity and chemical fibre class reject product with fossil resource is got worse, utilize The fibrous material of natural reproducible becomes particularly important, therefore the functionalization of cellulose family textile product is very important research Direction.

On the one hand, textile has loose porous characteristic, easily becomes numerous bacteriums during daily use The carrier of propagation, the adherency growth of these microorganisms not only result in fibre and discoloration, mouldy, brittle degradation occur, and Abnormal stimulation can be generated to human skin and may induce skin disease, there is unfavorable shadow to wearer and textile itself It rings.With the progress of science and technology and the improvement of people's living standard, people propose the anti-microbial property of textile higher It is required that.Has the textile of anti-microbial property at present, application field is being gradually expanded, and mainly includes medical textile (such as hand Art suture, mask, surgical glove etc.), household textiles (such as mattress, carpet, curtain) and fabrics for industrial use are (as filtered Cloth, automobile interior decoration, national defense industry lining etc.).Therefore, prepare anti-bacterial fibre cellulose fiber has in functionalization textile material field Very important realistic meaning and wide application prospect.

On the other hand, more textile is inflammable product at present, and limit oxygen index (LOI) is lower, in big compression ring It easily burns in border, according to incomplete statistics, China casualties and is built caused by almost all occurring every year because of fire incident Damage is built, causes immeasurable loss to the development of the national economy and people's lives and properties.Wherein, many fire are exactly As caused by textile.As it can be seen that the research and development of flame retarding function textile are indispensable for the harm for reducing fire.It is worth mentioning , cellulose fibre compared with synthetic fibers in burning without molten drop phenomenon, therefore fire-retardant cellulose is compared with flame retardant synthetic fibers, It is smaller that secondary hazards probability occurs.

Summary of the invention

Technical problem to be solved by the invention is to provide a kind of antibacterial flame-retardant cellulose and its preparation and application, the present invention It is middle to have fire-retardant, anti-microbial property functional group using the hydroxyl grafting of cellulose, therefore can be used for natural or regenerated cellulose Antibacterial flame-retardant is modified, it can also be used to which the finished product antibacterial flame-retardant of cellulose material is modified.

A kind of antibacterial flame-retardant cellulose of the invention, in parts by weight, raw material components include: 1 part of cellulose, 0.15- 0.50 part of 3- (isobutene acyl-oxygen) KH, 0.03-0.09 parts of propyl trimethoxy silicane PEI, 0.05-0.2 parts of polyethyleneimine second VA, 0.02-0.05 parts of antibacterial agents of alkenyl phosphonic acid, 0.001-0.003 parts of initiators.

The structural formula of KH containing element silicon is

The structural formula of the PEI of Nitrogen element are as follows:Wherein PEI is Branched polyethylene imine, molecular weight 600.

The structural formula of the VA of phosphorus element-containing are as follows:The antibacterial agent is the antibacterial agent with siloxane group Or the antibacterial agent with double bond；Initiator is radical polymerization initiator.The antibacterial agent is N, N- dimethyl-N-(3- (three Methoxy silane) propyl) dodecane -1- ammonium chloride CDMA, methacrylic acid anhydride modification poly (hexamethylene) hydrochloride One or more of MAPHMG；

Initiator be one or more of persulfate initiator, hydrogen peroxide initiator, water-soluble azo initiator, into Preferably, initiator is ammonium persulfate APS, potassium peroxydisulfate, hydrogen peroxide to one step.

Further, it is preferable to the cellulose 1 part, 0.4 part 3- (isobutene acyl-oxygen) propyl trimethoxy silicane KH, 0.07 Part polyethyleneimine PEI, 0.2 part of vinyl phosphonic acid VA, 0.05 part of antibacterial agent, 0.003 part of initiator.

A kind of preparation method of antibacterial flame-retardant cellulose of the invention, comprising:

(1) it disperses cellulose in lye, KH and PEI is added, 12-24h is reacted at 30-50 DEG C, wash, drying, Obtain product A；

(2) the product A in step (1) is submerged in water and adjust pH=2-3, KH, VA, antibacterial agent, initiator is added 60 DEG C of reaction 6-8h, washing are dried to get antibacterial flame-retardant cellulose.

The additional amount of KH is the 10-40wt% of cellulose quality in the step (1).

Lye is the NaOH solution that pH is 11-12 in the step (1).

Dilute HCl is added in the step (2) and adjusts pH in 2-3.

Lead to nitrogen in the step (2) in reaction process.

Above-mentioned preparation method is further:

Step 1: cellulose is dispersed in the NaOH aq that pH is 11-12, be added thereafter a certain amount of KH and PEI, In 12-24h is reacted at 30-50 DEG C, with the hydroxyl of cellulose hydrolysis-condensation reaction, PEI can occur for KH in acid or alkaline environment On amino can carry out Micheal addition reaction under alkaline environment with the double bond on KH, therefore can by chemical method by it is siliceous, Nitrogenous monomer grafts on cellulose surface, after reaction, is cleaned by ultrasonic the modified cotton fiber of 10min, and use deionization The substance that water elution, sufficiently removal are not chemically grafted to fiber surface, cleaning, which is placed in 60 DEG C of convection oven, dries；

Step 2: the cellulose by KH, PEI grafting is submerged in water, dilute HCl is added and adjusts pH between 2-3, then A certain amount of KH, VA, antimicrobial moiety and radical polymerization initiator are sequentially added, 60 DEG C of reaction 6-8h are heated to, is reacted Process leads to nitrogen, after reaction, same to be cleaned by ultrasonic the modified cotton fiber of 10min, and is eluted with deionized water, sufficiently removes It is not chemically grafted to the substance of fiber surface, cleaning, which is placed in 60 DEG C of convection oven, dries, to obtain by antibacterial, resistance Fire modified cellulose.

Antibacterial agent used in it can be the antibacterial agent with siloxane group or the antibacterial agent with double bond, equally Antibacterial agent is grafted on into cellulose pendant hydroxyl group, such as N, N- dimethyl-N-using hydrolysis-condensation reaction or Raolical polymerizable (3- (trimethoxy silane base) propyl) dodecane -1- ammonium chloride (CDMA), acrylic modified poly (hexamethylene) Hydrochlorate (MAPHMG) etc..

It is 100wt% calculating according to cellulose quality, prepares each component additive amount quality hundred of antibacterial flame-retardant cellulose Fraction representation, each reactant additive amount of the first step are as follows: the PEI of the KH of 10-40wt%, 3-9wt%；Each reactant addition of second step Amount are as follows: the antibacterial agent of the VA of the KH of 5-10wt%, 5-20wt%, 2-5wt%, the radical polymerization initiator of 0.1-0.3wt%.

A kind of fabric based on the antibacterial flame-retardant cellulose.

The present invention provides a kind of antibacterial flame-retardant cellulose of the method preparation.

The present invention also provides a kind of applications of antibacterial flame-retardant cellulose, such as can be widely applied to home textile, industry is used, army The fields such as work, such as household use carpet and curtain textile, the decorative textile product that the public places such as hotel, movie theatre use, The seat interior trim of the vehicles such as train, aircraft, ship, the work clothes of the industries such as fire-fighting and hot-working.

Beneficial effect

(1) chemical principle of the invention are as follows: with the hydroxyl of cellulose water can occur for KH in acid or alkaline environment Condensation reaction is solved, the amino on PEI can carry out Micheal addition reaction with the double bond on KH under alkaline environment, and VA can be with KH Raolical polymerizable is carried out under conditions of initiator；Second, antimicrobial moiety, such as benefit is added while flame-retardant modified With the hydrolysis-condensation reaction of siliconization quaternary ammonium salt, for another example by the antibacterial agent with double bond of preparation in Raolical polymerizable Step is added, to prepare while have the cellulosic material of antibiotic property, anti-flammability；

(2) it the present invention provides a kind of preparation method of cellulosic material simultaneously with antibiotic property and anti-flammability, utilizes The organic chemical reagent easily obtained is modified cellulose, and the scope of application includes all using cellulose as the material of constituent Material；

(3) present invention utilizes carbon-carbon double bond (C=in the hydrolysis-condensation reaction of siloxanes in KH and cellulose pendant hydroxyl group, KH C) with the Raolical polymerizable of C=C in C=C and VA in the Micheal addition reaction of amino in PEI and KH by KH, PEI, Tri- kinds of monomer chemistries containing ignition-proof element of VA graft on cellulose hydroxyl group, so that cellulose be made to obtain certain anti-flammability；

(4) being grafted on antibacterial components in the present invention includes two methods on cellulose hydroxyl group: using C=C in KH and being resisted Antibacterial agent is grafted on cellulose pendant hydroxyl group by the Raolical polymerizable of C=C in microbial inoculum；Or utilize siloxanes and hydroxyl in antibacterial agent The direct chemical graft of base hydrolytic condensation；

(5) Antibacterial Mechanism of modified cellulosic materials of the invention belongs to non-stripping property antibacterial, and it is safe and efficient lasting to have The characteristics of antibacterial, carries out antibiotic property test to prepared fiber using concussion method, as a result according to GB-T 20944.3-2008 The fiber of display preparation all has excellent antibacterial effect, modified fibre prepared by the present invention to Gram-negative and positive bacteria The bacteriostasis rate of element can reach 100%, and bacteriostasis rate is 98% or more after repeatedly washing；

(6) flame-retardant composition of the invention includes KH, nitrogen content high PEI, phosphorous VA containing element silicon, our legal system Standby modified cellulose rate of body weight gain has good flame retardant effect below 13%, and maximum heat release rate can decline fibrinogen Cellulosic material 50% or so, total heat release can decline 30% or so.

Detailed description of the invention

Fig. 1 is the schematic diagram that antibacterial flame-retardant modified cellulose is prepared in the embodiment of the present invention 1；

Fig. 2 is the infrared comparison spectrogram with fibrinogen cellulosic material of product (II) in the embodiment of the present invention 1；

Fig. 3 is the schematic diagram that antibacterial flame-retardant modified cellulose is prepared in the embodiment of the present invention 2；

Fig. 4 is the miniature calorimeter test result with fibrinogen cellulosic material of product (II) in the embodiment of the present invention 3, wherein Figure a is the heat release rate curve of rear cellulose before modified, and figure b is the Heat liberation unit curve of rear cellulose before modified；

Fig. 5 is that the product (II) prepared in the embodiment of the present invention 4 imitates the quantitative antibacterial of golden staphylococci and Escherichia coli Fruit figure；Wherein being modified a, b is respectively bacteriostasis rate test result of the cellulose to staphylococcus aureus and Escherichia coli before modified (picture for being diluted to the 4th agar plate), i.e. control group；C, d respectively indicate modified cellulose to staphylococcus aureus and The bacteriostasis rate test result of Escherichia coli.

Specific embodiment

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.

Primary raw material and source are as follows:

Cotton fiber is provided by Xiajin Renhe textile technology Co., Ltd.γ-(methacryloxy) propyl trimethoxy Silane (KH), 97%, Sa En chemical technology (Shanghai) Co., Ltd.；Branched polyethylene imine (PEI, M=600), 99%, Shanghai Mike's woods biochemical technology Co., Ltd；Vinyl phosphonic acid (VA), 97%, Sigma-Aldrich China；Sodium hydroxide (NaOH), Analyze pure, ammonium persulfate (APS), excellent pure grade, Sinopharm Chemical Reagent Co., Ltd..Antibacterial agent is self-control antibacterial agent, raw material Including 1,6 hexamethylene diamine (AR), guanidine hydrochloride (AR), buy in Sinopharm Chemical Reagent Co., Ltd.；2- methacrylic anhydride (95%) it is purchased from Sa En chemical technology Co., Ltd；Dodecyl Dimethyl Amine (DMDA) and γ-r-chloropropyl trimethoxyl silicon Alkane (CPTMS) is technical grade, is bought in Shanghai Kai Sai Chemical Co., Ltd..