CN106380660B

CN106380660B - A kind of antibacterial, deodorization, pest-resistant, mould proof composition and product and application

Info

Publication number: CN106380660B
Application number: CN201610784667.4A
Authority: CN
Inventors: 陈坛祥; 刘春燕
Original assignee: XIAMEN NASDA NON WOVEN Co Ltd
Current assignee: XIAMEN NASDA NON WOVEN Co Ltd
Priority date: 2016-08-31
Filing date: 2016-08-31
Publication date: 2018-09-18
Anticipated expiration: 2036-08-31
Also published as: CN106380660A

Abstract

The present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：The plastics of 50 80 parts by weight；The antiseptic of 10 30 parts by weight；The compatilizer of 0.1 5 parts by weight；The antiseptic is chitosan, BiVO₄And SiO₂Compound；The compatilizer is fluorine silicon resin, and antibacterial intensity is high, and deodorizing effect is good, and elongation at break is high.

Description

A kind of antibacterial, deodorization, pest-resistant, mould proof composition and product and application

Technical field

The present invention relates to a kind of antibacterial, deodorization, pest-resistant, mould proof compositions, more particularly to by antibacterial, deodorization, pest-resistant, mould proof The product that composition is prepared.

Background technology

In 20th century, microbiological industryization is just quite flourishing, and human use microorganism obtains various antibiotic, dimension Raw element and enzyme, and then produce fermentation food and chemicals etc..Into after 21 century, microorganism is finding antibiotics, biology Fuel and fine chemicals etc. play key player in fields.But then, the microorganisms such as bacterium bring to human society Harm also should not be underestimated.It is fairly common in the infection of the pathogenic bacteria of medicine and hygiene fields, including catheter, artificial blood vessel, doctor It treats equipment and transplantability operation is easily contaminated by bacterial.According to statistics in developed country, there are about 17.5 ten thousand patients because of bacterium every year Etc. microorganism infections and it is dead.In addition, the microorganisms such as bacterium in water resource with regard to necks such as purification system, food industry, domestic hygienes The harm in domain is also difficult to avoid that.Therefore, it can be said that the microorganisms such as bacterium are extremely serious to the harm of the mankind at this stage, microorganism is dirty Dye becomes the hot issue paid close attention to for world.It is domestic with the promotion of our people's living standard and health perception Antibacterial, deodorization, the development of deinsectization material reach its maturity.

Currently, antiseptic includes mainly inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and complex antimicrobials.It is inorganic Antiseptic has many advantages, such as that good safety, durability is good, heat resistance is strong, is less prone to drug resistance, but of high cost, preparation Technical sophistication, processing difficulties etc.；Organic antibacterial agent has many advantages, such as that bactericidal effect is notable, antibacterial range is wide, and there is also safeties And poor heat resistance, easily there is the shortcomings of drug resistance；Natural antibacterial agent is although safe, antibacterial range is wide, but is vulnerable to raw material The limitation of source and processing conditions and thermal stability are poor, it is difficult to mass market.

In view of the above-mentioned problems, the present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof composition, especially in daily life Rubber, plastics, fabric arts have excellent antibacterial, deodorization, pest-resistant, anti-mold effect, even if being frequently necessary to friction, washing feelings Under condition, still there is excellent performance.

Invention content

First aspect present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：

The plastics of 50-80 parts by weight；

The antiseptic of 10-30 parts by weight；

The compatilizer of 0.1-5 parts by weight；

The antiseptic is the chitosan/BiVO prepared by microwave method₄/SiO₂Compound；

The compatilizer is fluorine silicon resin.

As one embodiment of the present invention, the viscosity of the chitosan is 0.65~1Pas.

As one embodiment of the present invention, the viscosity of the chitosan is 0.75~0.9Pas.

As one embodiment of the present invention, the BiVO₄And SiO₂Weight ratio be (0.01-0.7)：1.

As one embodiment of the present invention, the BiVO₄And SiO₂Weight ratio be (0.1-0.5)：1.

As one embodiment of the present invention, the fluorine silicon resin is the fluorine silicon resin containing polar group.

As one embodiment of the present invention, the polar group of the fluorine silicon resin containing polar group is selected from carboxylic acid One kind in base, carboxylic acid derivatives, anhydride group, sulfonic group, phosphate, hydroxyl, amino, ester group.

As one embodiment of the present invention, the plastics are polyolefin plastics.

The second aspect of the present invention provides above-mentioned antibacterial, deodorization, pest-resistant, mould proof composition, be used for antibacterial, deodorization, Pest-resistant, mould proof field.

The third aspect of the present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof product, by above-mentioned antibacterial, deodorization, Pest-resistant, mould proof composition.

Specific implementation mode

The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.

As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.

Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body, It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.

Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end Value and all integers and score in the range.

Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.

In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component (i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.

" polymer " means the polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".

" copolymer " means the polymer prepared by polymerizeing at least two different monomers.Generic term " copolymer " includes (it is general with term " terpolymer " for term " copolymer " (its generally to refer to the polymer prepared by two kinds of different monomers) To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization manufactured by polymerization four or more monomer Object." blend " means the polymerization that two or more polymer is formed by mixing jointly by physics or chemical method Object.

The first aspect of the present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：

The plastics of 50-80 parts by weight；

The antiseptic of 10-30 parts by weight；

The compatilizer of 0.1-5 parts by weight；

The compatilizer is fluorine silicon resin.

Antiseptic

Currently, antiseptic includes mainly inorganic antiseptic, organic antibacterial agent, natural antibacterial agent and complex antimicrobials.It is inorganic Antiseptic has many advantages, such as that good safety, durability is good, heat resistance is strong, is less prone to drug resistance, but of high cost, preparation Technical sophistication, processing difficulties etc.；Organic antibacterial agent has many advantages, such as that bactericidal effect is notable, antibacterial range is wide, and there is also safeties And poor heat resistance, easily there is the shortcomings of drug resistance；Natural antibacterial agent is safe, antibacterial range is wide.

Inorganic antiseptic is primarily referred to as with antibiotic property metal (Ag, Hg, Cu, Zn etc.) and its compound and carrier combination shape At a kind of antiseptic, most common carrier includes activated carbon, montmorillonite, zeolite, silica gel, cotton fabric and ceramics etc..It is inorganic anti- Microbial inoculum includes mainly heavy metal classes antiseptic system and photocatalysis class antiseptic system.

Metal class antiseptic is to be introduced the metals such as Ag, Hg, Cu, Zn by the methods of ion exchange or physical absorption It is obtained in the carriers such as silica gel, activated carbon.

Photocatalysis class antiseptic mainly has TiO₂、WO₃、SnO₂, the conductor oxidates, wherein TiO such as CdS₂Class antiseptic Research is quite prominent.TiO₂The nano-particle of equal photocatalysis type oxide has high surface, high catalytic property and surface energy, and Has superpower anti-microbial property.It is held although such antiseptic has heat-resisting quantity, high-efficiency antimicrobial, environmental-friendly, photocatalytic activity Long feature, but anti-microbial property only can be just played when ultraviolet light irradiates, so that its application is restricted.

Organic antibacterial agent type is various, includes mainly quaternary ammonium (Phosphonium) salt, halogenated amine, guanidine, organic metal class, pyridine Class, imidazoles, organic aldehydes etc..Currently, commonly mainly having quaternary ammonium salt antiseptic, halogenated amine antiseptic, guanidine antibacterial Agent.Organic antibacterial agent and material are introduced material internal or surface by physical blending or covalent, can be resisted Bacterium material.

Natural antibacterial agent has the characteristics that nontoxic to human body, environmentally friendly, abundance, can be divided into plant according to source Source class, animal sources class, microbial source class and mineral sources class.Plant source class natural antibacterial agent has Chinese juniper oil, aloe, granatum, sweet Grass, argy wormwood, garlic, honeysuckle etc.；Animal sources class natural antibacterial agent mainly has natural peptides, macromolecular carbohydrate and protein-based； Microbial source class natural antibacterial agent mainly has bacteriocin, antibiotic；Mineral sources class natural antibacterial agent has blue stone, realgar etc..By day Right antiseptic is directly fixed on material surface, you can obtains the surface with anti-microbial property.

Inorganic-organic composite antibiotic agent has both respective advantage, and it is long to have both inorganic system's heat resistance, corrosion resistance, antimicrobial lifetime, Efficiently and the speciality such as broad spectrum antibacterial, thus complex antimicrobials development prospect is considerable for organic system.

In the present invention, the antiseptic is the chitosan/BiVO prepared by microwave method₄/SiO₂Compound.

Chitosan

Chitosan also known as chitosan, are product of the chitin through deacetylated processing, and chemical name is (Isosorbide-5-Nitrae) -2- ammonia Base -2- deoxidation-p-D- glucans, molecular formula are (C₆H₁₃NO₅) n, structure is amino-containing homogeneous state straight-chain polysaccharide, containing free Amino.In general, N- acetamidos slough 55% or more just be referred to as chitosan, N- deacetylations are 55%~70% It is low deacetylation chitosan, 70%~85% be middle deacetylation chitosan, and 85%~95% is high deacetylized shell Glycan, 95%~100% is chitosan with ultrahigh deacetylation degree, and N- takes off the extremely difficult preparation of chitosan of second phthalein degree 100%.It is usually viscous Degree is in l000 × 10^-3Pas's or more is decided to be high-viscosity chitosan, (1000-100) × 10^-3It is glued in being decided to be of Pas Degree chitosan, 100 × 10^-3Pas is below to be decided to be low viscosity chitosan.

As one embodiment of the present invention, the N- deacetylations of the chitosan are 30%~85%.

As one embodiment of the present invention, the N- deacetylations of the chitosan are 65%~80%.

The measurement of deacetylation：

The sample for taking 0.2-0.3g is dissolved in 30ml standard 0.01mol/L hydrochloric acid solutions, and 2-3 drop methyl orange benzene is added Amine indigo plant mixed indicator, the two volume ratio are 1：2, it is titrated with standard 0.01mol/L sodium hydroxide solutions.1 part of sample separately is taken, is set Drying to constant weight in 105 DEG C, measures moisture.Each sample is respectively surveyed 3 times.

Calculate amino content：

Deacetylation：

(C1 is the concentration of hydrochloric acid standard solution, unit mol/L in formula；C2 is the concentration of standard solution of sodium hydroxide, single Position is mol/L；The volume for the hydrochloric acid standard solution that V1 is added, ml；V2 is the volume for titrating handy standard solution of sodium hydroxide, ml；G is g in sample；The comparable amino amount of 1mol/L hydrochloric acid solutions of 0.016 and 1ml, g)

Viscosity test：

Instrument and reagent：With Ubbelohde viscometer (capillary inner diameter 0.57mm), thermometer, stopwatch, thermostat water bath, shell Glycan, solvent：NaCl the and 0.3mol/L acetic acid of 0.2mol/L.

Experimental method：

The washing of viscosimeter：First viscosimeter is impregnated with absolute ethyl alcohol, then several times with distilled water flushing, it is thin to flow scouring of wool repeatedly Tube portion is dried for standby after washed.

Temperature is adjusted：Regulating thermostatic bath temperature degree all covers upper rubber tube to 25 ± 0.05 DEG C, in the B pipes and C pipes of viscosimeter, so It is vertically put into thermostat afterwards, the water surface is made to be totally submerged C balls, sash weight is used in combination to check whether vertically.

The measurement of solution delivery time：It takes a certain amount of chitosan to be dissolved in solvent, is filtered with 3# sand core funnels, discarded just Filtrate about 1mL pipettes subsequent filtrate 15mL with pipette, injects constant temperature 15min in viscosimeter by A pipes, is measured.Assay method It is as follows：The C effective cycles of sixty years are clamped and are allowed to stuffiness, are evacuated to solution from F ball warp D balls, capillary, E balls with ear washing bulb at B pipes At C balls 2/3, solution goes C pipe clamps, and C pipes is allowed to ventilate, and the solution in D balls backs into F balls at this time, keeps the liquid of capillary or more outstanding It is empty.Liquid more than capillary falls, and when liquid level flows through a scales, starts between clocking by table immediately, when the page is down to b scales When, then stopwatch is pressed, it measures the liquid between scale a, b and flows through capillary required time.This operation at least 3 times is repeated, they Between be not much different in 0.3s, take 3 times average value be t₁.Then successively with the time for being measured in the same method every part of solution and flowing through capillary t₂、t₃、t₄。

The measurement of solvent delivery time：Viscosimeter is cleaned with distilled water, is washed 1-2 times with solvent, is then added about by A pipes 15ml solvents.With the time t for being measured in the same method solvent outflow₀,

By formula η=1.81 × 10⁵M^0.93Calculate average molecular weight.

As one embodiment of the present invention, the chitosan purchase is in the Henan bio tech ltd Xin Hongtai.

As one embodiment of the present invention, the chitosan can also be prepared via a method which：

Shrimp, crab shell are cleaned up, is impregnated in the hydrochloric acid of 4%-6%, decalcification, removes the shell of inorganic salts, is burnt 10% A period of time is boiled in lye, then in KMnO₄And NaHSO₄It cleans, bleach in solution, dry, obtain chitin；Chitin is existed A period of time is kept the temperature in high alkali liquid, is cleaned, is dried, obtains chitosan.

Chitosan is a kind of natural polymer antiseptic.Current many scholars all in the Antibacterial Mechanism of research chitosan, but Academia there is no final conclusion, and there are two types of viewpoints at present：It is positively charged that one is chitosan molecule chains, can adsorb negatively charged micro- Biological cell membrane hinders the activity of microorganism, is formed simultaneously a floor height molecular film, prevents nutriment into microbial cell Conveying, to play the role of restraining and sterilizing bacteria；Another mechanism is that chitosan is in cell to the target site of microorganism After chitosan is contacted with microbial cell, ribose subunit in cell body and intracellular is entered by certain approach by DNA 30S molecule fragments act on, and destroy the transcription from DNA to RNA in bacterial body, upset the normal breeding activity of cell, lead to bacterium Breeding terminates.But the anti-microbial property of chitosan is affected by ambient enviroment pH value and itself deacetylation.

Pucherite

Pucherite (BiVO₄) be commonly called as bismuth Huang, because its is nontoxic, bright color thus early stage as weld due to obtain extensively Using；In recent years find that it can be as a kind of novel semi-conductor photochemical catalyst with visible light activity, BiVO₄With band gap compared with The advantages that narrow (about 2.4eV), photochemical stability are preferably, redox ability is stronger and nontoxic, at low cost, answers more and more It is studied for visible light catalytic.In addition, BiVO₄Potential using value with ferroelasticity, photodissociation hydrogen manufacturing, oxygen processed makes it by wide General concern.BiVO₄The preparation method of nano material：Hydro-thermal or solvent-thermal process method, coprecipitation, microwave synthesis or ultrasonic wave Assist synthetic method, template, high-temperature solid phase reaction method, sol-gel method.

Microwave synthesizes and ultrasound synthesis is to react to prepare product one kind newly by microwave or ultrasonic wave auxiliary substance Method, wherein ultrasonic-assisted synthesis generate cavitation bubble in a liquid using ultrasonic wave, and bubble generate and be broken after energy Make that the nano particle diameter of generation is small, is evenly distributed；It is compared to traditional method, the crystallinity of product is high, and purity crystalline phase is more It is good.Wherein microwave synthesis has many advantages, such as that the used time is short, small without high temperature and Product size, purity is high.

Sol-gal process be it is a kind of use metal inorganic salt or metal organic alkoxide for raw material, by being dissolved into solution, shape At colloidal sol, gel, the method for finally preparing composite oxides and other solid particulate matters through flows such as Overheating Treatments.It is generally used for Prepare the inorganic material such as ceramics, glass, fiber membrane.Being using the advantages of sol-gal process nano materials can be relatively low Thermotonus lowly prepares the compound that purity is high, particle size distribution is narrow, while can regulate and control the microstructure of gel, grasps Facilitate.But also has apparent disadvantage, such as mostly use the more expensive organic matter raw material of price, and Organic Ingredients is to people Own bodies it is also harmful；The collosol and gel time is long, and sintering energy consumption is high.

For the above situation, pucherite is prepared using sol-gal process in the present invention.

Silica

Nano-meter SiO_2₂It is a kind of nontoxic, tasteless, free of contamination inorganic non-metallic material for unformed white powder.Through saturating Penetrate electron microscope test analysis, SiO₂Cotton-shaped or netted quasi- grain structure is obviously shown, particle size is small, specific surface area Greatly.Industrial SiO₂Referred to as white carbon is a kind of super-fine powder, light, and 0.3 micron of initial size is hereinafter, relative density 2.319~2.653,1750 DEG C of fusing point forms polymerization fine grained after the moisture absorption.Nano-meter SiO_2₂Bulk effect and quantum tunneling effect So that it is generated osmosis, can be deep near the pi bond of high-molecular compound, overlap with its electron cloud, forms space networks Shape structure, mechanical strength, toughness, wearability and resistance to ag(e)ing etc. to which high molecular material be greatly improved.

Up to the present, the production method of nano silicon dioxide can be mainly divided into two kinds of dry and wet.Dry method includes Vapor phase method and arc process, wet method have the precipitation method, sol-gel method, microemulsion method, hypergravity reaction method and hydrothermal synthesis method etc..

In the present invention, the chitosan/BiVO₄/SiO₂Compound is mainly prepared using template.Specific preparation side Method is as follows：

1. compound concentration is the bismuth nitrate solution of 0.1M, solvent is dust technology, and citric acid is added after solution clarification, adjusts PH value of solution is 7 or so, obtains mixed solution A, weighs ammonium metavanadate and citric acid is dissolved in boiling water, obtains the mixed of concentration 0.1M Solution B is closed, it is spare；

2. weighing the chitosan of 0.01mol, 10ml ethyl alcohol is added and is stirred, is then drained ethyl alcohol with Suction filtration device, It 2-4 times repeatedly, is drained with air stream；

3. the mixed solution A in the chitosan and step 1 in step 2 is slowly blended, stirring is after twenty minutes；Acutely stirring It mixes down, pours into mixed solution B, stir 5 minutes；

4. taking out the sample of step 3, washed respectively with pure water and ethyl alcohol, and dry in air；

5. repeating step 3, you can obtain deposited the chitosan of different-thickness pucherite precursor liquid；

6. by deposited the chitosan of pucherite precursor liquid, high-temperature calcination is carried out under 120 degree, you can obtain pucherite and The compound of chitosan；

7. by 46.5g ethyl orthosilicates, 90ml absolute ethyl alcohols and 10ml 0.1M hydrochloric acid and a certain number of silane coupling agents After evenly mixing, the compound of pucherite and chitosan in step 6 is added under stiring, constant temperature hydrolysis 6h is obtained at 5 DEG C Even transparent colloidal sol, then heating evaporation obtain gel, gel dries 17h under 80 DEG C of constant temperature and obtains final product.

As a kind of preferred embodiment of the present invention, the BiVO₄And SiO₂Weight ratio be 0.2：1.

Fluorine silicon resin

Organic siliconresin is that one kind forms skeleton by alternate silicon and oxygen atom, and different organic groups links with silicon atom again Polymer general designation.

The advantage and disadvantage of organic siliconresin are as follows：

(1) advantage：Silicone backbone is made of Si-O chain links, and side chain is then various other organic groups, therefore, organosilicon Existing organic structure in resin, and have inorganic structure.The relative electronegativies of two kinds of atoms differ greatly in Si-O keys, therefore Si-O Key polarity is big.Due to above, organic siliconresin has both the double grading of organic matter and inorganic matter, therefore, organic siliconresin With excellent weatherability, heat resistance, Acid Rain, resist staining, gloss retention, moisture resistance, water proofing property, chemical property stable and Electric insulating quality etc..

(2) disadvantage：Organic siliconresin Si-O key polarity is big, under the attack of electrophilic reagent or nucleopilic reagent, it is easy to The fracture of Si-O keys occurs, therefore the film forming of organic siliconresin is poor, solidification temperature is higher, and (solidification temperature is 150 DEG C~250 DEG C), it is poor to the adhesive force of ground, while its high-temperature anticorrosion ability is also very poor.

Organic fluorine has many excellent performances, occupies an important position in coatings industry.Contain in organic fluorine There is fluorine atom, the electronegativity of fluorine atom is maximum (4.0), and the C-F key bond distances of atomic radius very little (0.13nm), formation are short by (1.35 × 10-10m), bond energy is big (486KJ/mol), therefore assigns organic fluorine many excellent performances, it is made to be widely used in sea In the anticorrosive paint of gunship and large bridge.

The advantage and disadvantage of organic fluorine are as follows：

Advantage：Organic fluorine side group is short and small, structure saturation, thus has excellent chemical resistance and chemical stabilization Property；Organic fluorine totally nontoxic can be applied to medicine and food service industry；The larger imparting organic fluorine of cohesive force of segment Very strong surface self-cleaning.

Disadvantage：Organic fluorine has many excellent performances, but it also has some problems of own simultaneously.Organic fluoride Resin is poor to the wetability of color stuffing, dissolubility is bad in organic solvent.

Fluorine silicon resin is by organic siliconresin and organic fluorine structure also known as fluorine-silicon copolymer resin.

As a kind of preferred embodiment of the present invention, the fluorine silicon resin is It is 1 according to molar ratio:1:(2-6) is mixed with to obtain.

Wherein, R is polar group, in the present invention, as long as the polar group has other than carbon atom and hydrogen atom The group of atom, such as can be carboxylic acid group, carboxylic acid derivatives, anhydride group, isocyanate group, sulfonic group, phosphate, hydroxyl Base, amino, thiol base, ester group, cyano, silicyl etc..

Wherein, a kind of preferred embodiment as the present invention, the polar group are preferably carboxyl, hydroxyl and amino, more Preferably hydroxyl.

Specific preparation method is as follows：With 10 partsTo prepare monomer, it is added 11 ~16 distilled water, 0.001~0.003 part of chloroplatinic acid and Pt/C, react 4~7 hours under 50~60 DEG C of temperature condition, then It is addedReact 30min, you can.

As one embodiment of the present invention, the weight average molecular weight of the fluorine silicon resin is 1 × 10⁴-8×10⁵, more Further preferable weight-average molecular weight is 8 × 10⁴-5×10⁵。

In addition, the weight average molecular weight is to pass through：The chloroformic solution for preparing a concentration of 0.5 mass % of polyolefin, uses height Effect liquid phase chromatogram is measured, and is compared with polystyrene known to the weight average molecular weight measured under the same conditions, thus Calculated value.In addition, determination condition is as follows.

Column：GPC columns

Column temperature：40℃

Eluent：Chloroform

Flow velocity：1ml/ minutes

The mobility of resin is for example by utilizing JIS7210：Melt flow rate (MFR) (MFR, the list that method as defined in 1999 measures Position：G/10min it) indicates.

Plastics

Plastics are, by high-molecular compound made of addition polymerization or polycondensation polymerized, to be commonly called as plastics using monomer as raw material Or resin, it can freely change ingredient and body styles, by synthetic resin and filler, plasticizer, stabilizer, lubricant, colorant Equal additives composition.

The main component of plastics is resin.This noun of resin is initially the lipid secreted out of by animals and plants and gains the name, such as Rosin, shellac etc., resin refer to the high-molecular compound not yet mixed with various additives.Resin accounts for about plastics total weight 40%~100%.The basic performance of plastics depends mainly on the person's character of resin, but additive also plays an important role.Some modelings Material is substantially made of synthetic resin, and additive, such as organic glass, polystyrene are free of or contain less.

Plastic material be defined as it is a kind of with synthesis or natural high-molecular compound, can arbitrarily pinch into it is variously-shaped most The material or plastic material product of shape invariance can be kept afterwards.

Common plastics have polyethylene, polypropylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene, Polyvinyl chloride, General Purpose Polystyrenre, polystyrene foam, impact resistant polystyrene, polyethylene-propylene lonitrile copolymer, third Co-polymer, the poly terephthalic acid of alkene nitrile-butadiene-styrene copolymer, polymethacrylates, ethylene-vinyl acetate Glycol ester, polyamide, poly- carbonic acid resin, polyoxymethylene resin, polyphenylene oxide, polyphenylene sulfide, gathers PA polybutyleneterephthalate Urethanes, polystyrene etc..

As one embodiment of the present invention, heretofore described plastics are the plastics containing alkene, for example, it may be Polyolefin.

Heretofore described polyolefin is selected from least one of the group of the following terms composition：Homopolymerisation polyethylene and homopolymerization are poly- Homopolymer in the group of propylene composition；It selects one or more total in the group of free ethylene, propylene, butylene, hexene and octene composition The random copolymer of polycondensation monomer copolymerization.

Such as can be：The random copolymer of ethylene and propylene；The random copolymer of ethylene and butylene；Ethylene and hexene Random copolymer；The random copolymer of ethylene and octene；The random copolymer of propylene and butylene；The random copolymerization of propylene and hexene Object；The random copolymer of propylene and octene；The random copolymer of butylene and hexene；The random copolymer of butylene and octene；Ethylene, The random copolymer of propylene and butylene；The random copolymer of ethylene, propylene and hexene；The random copolymerization of ethylene, propylene and octene Object；The random copolymer of ethylene, butylene and hexene；The random copolymer of ethylene, butylene and octene；Propylene, butylene and hexene Random copolymer；The random copolymer of propylene, butylene and octene；The random copolymer of butylene, hexene and octene.

The polyolefin can be homopolypropylene, or by propylene monomer and 12mol% or less ethylene or be based on C4- The random copolymer of the monomer copolymerization of C10 alkene.

The polyolefin can be the copolymer of the vinyl monomer of the propylene monomer 1-12mol% of 88-99mol%.

Polyolefin refers to the polymer containing the monomeric unit from alkene.It can be such as：Polyethylene based polymers.

As polyethylene based polymers, polyethylene may be exemplified.It is not particularly limited, can use low close as polyethylene Spend polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene (HDPE) etc..

As polyethylene based polymers, the copolymer of ethylene and other alkene may be preferably exemplified.As " other in this Alkene " can be preferably propylene, butylene, hexene, octene etc..These " other alkene " can be used alone or be applied in combination Two or more.As polyethylene based polymers, more specifically, optimal ethylene-propylene copolymer, ethylene-hexene co-polymers, second Alkene-octene copolymer etc., wherein especially preferably ethylene-hexene co-polymers.

Heretofore described polyolefin can be that any type method well known by persons skilled in the art is prepared.Such as Prepare the copolymer of ethylene and propylene.

Ethylene and propylene mix in air accumulator in proportion in advance.It is aggregated in equipped with slotting bill kept on file body canal, outtake tube It is carried out in the tubular type there-necked flask of mechanical agitation 100ml.First polymerization bottle is vacuumized, logical monomer is so continuously replaced twice, connect It vacuum and bakes bottle 5 minutes.Reactor is led to as normal heptane, co-catalyst, external electron donor in water bath with thermostatic control, is once added Enter gaseous mixture continuous bubbling, after monomer reaches dissolution equilibrium, major catalyst is added and causes polymerization.With acidification after polymerization Ethyl alcohol terminates reaction, and polymer is dried under vacuum to constant weight at 60 DEG C, weighs through filtering, washing.

As one embodiment of the present invention, heretofore described plastics can also be the plastics such as ethene-vinyl acetate.

As a kind of preferred embodiment of the present invention, heretofore described plastics are low density polyethylene (LDPE), and the low-density About 106 DEG C of the fusing point of polyethylene, melt index are about 23g/10min (190 DEG C, 2.16kg).

Additive：

As long as the effect of the present invention is unaffected, so that it may which other different types of additives are mixed in the composition of the present invention In, the example of the additive has：Reinforcing filler in addition to fine silica, such as fumed titanium oxide；Non-reinforcing fillers, Such as silica flour, crystalline silica, diatomite, asbestos, aluminosilicate, zinc oxide and calcium carbonate；Hydrosilylation controlling agent Such as nitrogenous compound, acetylenic compound, phosphorus compound, nitro compound, carboxylate/ester, tin compound, mercury compound, acetylene series Compound such as ethynylcyclohexanol and sulphur compound；Heat-resistant agent such as iron oxide and cerium oxide；Slip agent, crosslinking agent, filling material Material, ultra-violet absorber, plasticizer, colorant, antistatic agent, heat stabilizer, antioxidant, light stabilizer, fire retardant, lubrication Agent, antioxidant, anti-aging agent, reaction promoter, reaction suppressor, resin etc..Phenol kind antioxidant, Phosphorus antioxidant etc. are various anti- Oxygen agent；Benzophenones ultra-violet absorber, Benzotriazole Ultraviolet Stabilizer, benzoate ultra-violet absorber etc. are various Ultra-violet absorber；The various dispersants such as bisamide class dispersant, paraffin class dispersant, organic metal salt dispersant；Talcum Powder, mica, clay, calcium carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, glass fibre, carbon fiber, silica, calcium silicates, The various inorganic fillers such as potassium titanate, wollastonite.

The second aspect of the present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof product, by above-mentioned antibacterial, deodorization, anti- Worm, mould proof composition are prepared.

Specific preparation method is as follows：

The first step：Plastics, antiseptic, compatilizer are weighed according to parts by weight proportioning；

Second step：It will be heated to 40-60 DEG C in plastics, antiseptic, compatilizer input reaction kettle, stirs 20-40min, so After rest additive is added, be warming up to 70-90 DEG C, stir 40-60min, be cooled to 20-40 DEG C；

Third walks：Mixed material is put into extruder and is squeezed out, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C of barrel temperature With 130 DEG C；

4th step：Compression molding, 40-60 DEG C of mold temperature, die pressure 0.6-1.0MPa, after being cooled to 20-40 DEG C i.e. It can.

As a preferred technical solution of the present invention：Mixing speed in the second step is 400-600 revs/min Clock.

As a preferred technical solution of the present invention：Extruder is double screw extruder in the third step.

As a preferred technical solution of the present invention：Temperature of charge is 15-35 DEG C when compression molding in 4th step.

As a preferred technical solution of the present invention：Dwell time 5-10s when compression molding in 4th step.

The third aspect of the present invention provides the antibacterial, deodorization, pest-resistant, mould proof composition, be used for antibacterial, deodorization, Pest-resistant, mould proof field.

Semiconductor has band structure, is generally made of the low energy valence band and empty higher energy conduction band for filling up electronics, energy band it Between there are forbidden band, forbidden band be not allow for electronics presence.Electronics is in filling preferentially from being filled out the low valence band of energy band.It is irradiated when using up When semiconducting compound, the light of not any wavelength can be absorbed and be generated excitation, and only photon energy is equal to or greatly It is acted in the light competence exertion of semiconductor energy gap energy, i.e.,：

E=hc/ λ >=Eg

In formula：H is Planck's constant, h=4.136 × 10^-15eV·s；

C is the light velocity in vacuum, c=2.998 × 10⁸m/s；

λ is the wavelength of light, nm.

Pucherite is low-gap semiconductor.

The position of energy band of semiconductor and the reduction potential of adsorbed material determine the ability of its light-catalyzed reaction.Thermodynamics Photochemical catalytic oxidation-reduction reaction of permission, it is desirable that receptor potential is lower than semiconductor conduction band potential (corrigendum), is led than partly to bulk potential Body valence band potential is high (more negative), and the current potential that the conduction band side of redox reaction namely semiconductor could occur represents its reduction Ability, energy level residing for valence band edge represent the oxidability of semiconductor.When semiconductor interface is more than energy gap (Eg) by energy Light irradiation when, the electronics in valence band is excited on conduction band, to generate high activity electronics (e on conduction band^-), valence band It is upper to generate positively charged hole (h⁺), the electron-hole pair of high activity is as a result produced in semiconductor surface.Valence band hole is The electronics of good oxidant, conduction band is good reducing agent.Most of photocatalysis oxidation reaction is directly or indirectly to utilize The oxidability in hole.Hole is had an effect with the hydrone and dissolved oxygen for being adsorbed on particle surface respectively with electronics, generates energy Amount is transmitted, and hydroxyl radical free radical (OH) and superoxide radical (- O with high activity and strong oxidizing property are ultimately formed₂ ^-).This A little free radicals can aoxidize most of organic compounds difficult to degrade, also deodorization, sterilization and can be used as self-cleaning material.

Mechanism is explained：

Chitosan, BiVO4 and the SiO2 being prepared in the present invention are due to foring tri compound structure, by chitosan packet It is rolled in internal layer, pucherite is in middle layer, and silica is in outermost layer, simultaneously because silica is in outermost layer, it is suppressed that crystal The surface migration of atom, and the growth of crystal is limited by the confined space, to stabilize tiny pucherite crystal, due to The composite construction remains the distinctive microstructure of chitosan and hyperfine size, improves pucherite under visible light Antibacterial, deinsectization ability.Simultaneously as the presence of the fluorin radical and polar group on compatilizer, due to the work of hydrogen bond and Coulomb force With improving compatibility, dispersibility and sterilization, the insecticidal properties of antiseptic.

Embodiment 1：The present invention provides a kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：

The plastics of 50-80 parts by weight；

The antiseptic of 10-30 parts by weight；

The compatilizer of 0.1-5 parts by weight；

The antiseptic is chitosan/BiVO₄/SiO₂Compound；

The compatilizer is fluorine silicon resin.

Embodiment 2：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the viscosity of the chitosan For 0.65~1Pas.

Embodiment 3：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the viscosity of the chitosan For 0.75~0.9Pas.

Embodiment 4：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the N- of the chitosan are de- Acetyl degree is 30%~85%.

Embodiment 5：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the N- of the chitosan are de- Acetyl degree is 65%~80%.

Embodiment 6：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the BiVO₄And SiO₂'s Weight ratio is (0.01-0.7)：1.

Embodiment 7：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the BiVO₄And SiO₂'s Weight ratio is (0.1-0.5)：1.

Embodiment 8：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the BiVO₄And SiO₂'s Weight ratio is 0.2：1.

Embodiment 9：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the fluorine silicon resin be containing The fluorine silicon resin of polarized group.

Embodiment 10：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the fluorine silicon resin areIt is 1 according to molar ratio:1:(2-6) is mixed with It arrives.

Embodiment 11：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, told R is polar group Group.

Embodiment 12：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the polar group R is only If the group with the atom other than carbon atom and hydrogen atom, such as can be carboxylic acid group, carboxylic acid derivatives, acid anhydrides Base, isocyanate group, sulfonic group, phosphate, hydroxyl, amino, thiol base, ester group, cyano, silicyl.

Embodiment 13：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the polar group R are excellent It is selected as carboxyl, hydroxyl and amino.

Embodiment 14：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the polar group R are excellent It is selected as hydroxyl.

Embodiment 15：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the fluorine silicon resin Weight average molecular weight is 1 × 10⁴-8×10⁵。

Embodiment 16：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the fluorine silicon resin Weight average molecular weight is 8 × 10⁴-5×10⁵。

Embodiment 17：Antibacterial, deodorization as described in embodiment 6, pest-resistant, mould proof composition, it is described to contain polar group Group fluorine silicon resin polar group be selected from carboxylic acid group, carboxylic acid derivatives, anhydride group, sulfonic group, phosphate, hydroxyl, amino, Ester group.

Embodiment 18：Antibacterial as tdescribed in embodiment 1, deodorization, pest-resistant, mould proof composition, the plastics be containing The plastics of alkene.

Embodiment 19：Embodiment 1-7 any one of them antibacterial, deodorization, pest-resistant, mould proof composition, are used to resist Bacterium, deodorization, pest-resistant field.

Embodiment 20：A kind of antibacterial, deodorization, pest-resistant product, by embodiment 1-7 any one of them antibacterial, are removed Smelly, pest-resistant, mould proof composition is prepared.

The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.

In addition, if without other explanations, it is raw materials used to be all commercially available, and number used in following material is weight Part.

Embodiment 1：A kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：

The plastics of 70 parts by weight；

The antiseptic of 15 parts by weight；

The compatilizer of 1 parts by weight；

The antiseptic is chitosan/BiVO₄/SiO₂Compound；

The compatilizer is fluorine silicon resin.

Wherein, the plastics are low density polyethylene (LDPE), and the fusing point of the low density polyethylene (LDPE) is 106 DEG C, melt index For 23g/10min (190 DEG C, 2.16kg).

The viscosity of the chitosan is 0.8Pas, the BiVO₄And SiO₂Weight ratio be 0.2：1,

Chitosan/the BiVO₄/SiO₂Compound preparation method is as follows：

2. weighing the chitosan of 0.01mol, 10ml ethyl alcohol is added and is stirred, is then drained ethyl alcohol with Suction filtration device, It 3 times repeatedly, is drained with air stream；

6. by deposited the chitosan of pucherite precursor liquid, high-temperature calcination is carried out at 120 DEG C, you can obtain pucherite and The compound of chitosan；

7. by 46.5g ethyl orthosilicates, the silane coupling agent of 90ml absolute ethyl alcohols and 10ml 0.1M hydrochloric acid and 0.05mol After evenly mixing, the compound of pucherite and chitosan in step 6 is added under stiring, constant temperature hydrolysis 6h is obtained at 5 DEG C Even transparent colloidal sol, then heating evaporation obtain gel, gel dries 17h under 80 DEG C of constant temperature and obtains final product.

The fluorine silicon resin isAccording to mole Than being 1:1:3 are mixed with to obtain, specific preparation method：

With 10 partsTo prepare monomer, be added 13 parts of distilled water, 0.002 part Chloroplatinic acid and Pt/C are reacted 6 hours under 50~60 DEG C of temperature condition, are then addedReaction 30min, you can.

The antibacterial, deodorization, the preparation method of pest-resistant product are as follows：

Second step：50 DEG C will be heated in plastics, antiseptic, compatilizer input reaction kettle, stir 30min, be then added Rest additive is warming up to 80 DEG C, stirs 50min, is cooled to 30 DEG C；

4th step：Compression molding, 50 DEG C, die pressure 0.8MPa of mold temperature, after being cooled to 30 DEG C.

Mixing speed in the second step is 500 revs/min.

Extruder is double screw extruder in the third step.

Temperature of charge is 20 DEG C when compression molding in 4th step.

Dwell time 10s when compression molding in 4th step.

Embodiment 2：Difference lies in the chitosan, BiVO with embodiment 1₄And SiO₂Without SiO in compound₂。

Embodiment 3：Difference lies in the BiVO with embodiment 1₄And SiO₂Weight ratio be 1：1.

Embodiment 4：Difference lies in the BiVO with embodiment 1₄And SiO₂Weight ratio be 0.009：1.

Embodiment 5：Difference lies in the viscosity of the chitosan is 0.6Pas with embodiment 1.

Embodiment 6：Difference lies in the chitosan, BiVO with embodiment 1₄And SiO₂Three is according to weight ratio object Reason is blended.

Embodiment 7：Difference lies in, the antibacterial, deodorization, pest-resistant, mould proof compositions without compatilizer with embodiment 1.

Embodiment 8：With embodiment 1 difference lies in, the fluorine silicon resin prepare raw material without

Embodiment 9：Difference lies in the compatilizer is KH570 with embodiment 1.

Embodiment 10：Difference lies in the chitosan/BiVO with embodiment 1₄/SiO₂The structure of compound is chitosan For internal layer, silica is middle layer, and pucherite is outer layer.

Embodiment 11：Difference lies in the chitosan/BiVO with embodiment 1₄/SiO₂Compound is without pucherite.

Embodiment 12：Difference lies in the chitosan/BiVO with embodiment 1₄/SiO₂Compound is without chitosan.

Test：

1. sterilization experiment：In about 0.5m²On product, product (or is placed on automatic washing machine mark by the product just made Quasi- washing, is washed 50 times) it is acted on 48 hours with natural bacteria, sterilizing rate=(average bacterium number after average bacterium number-experiment before experiment) × Average bacterium number before 100/ experiment.Test result is shown in Table 2.

2. being tested by sensory evaluation below, smell processing is carried out to product.

Operation：The sodium methyl mercaptide aqueous solution 5ml that a 5 weight % of drop are instilled into mortar, is then sprayed at system by aqueous solution On product；Then, it is covered with big bag and is escaped with anti-odour, by after ten minutes, removing covering, sense organ carried out to smell and is commented Valence.Evaluation criterion is as follows：

5- can be strongly felt the stink of methyl mercaptan；

4- can feel the stink of methyl mercaptan；

3- can slightly feel the stink of methyl mercaptan

2- is difficult the stink for feeling methyl mercaptan

The stink of the imperceptible methyl mercaptans of 1-.

Test result is shown in Table 2.

3. deinsectization is tested：The female mosquito in 50 3-4 days ages is exposed in sealing device made from product；After 24 hours, According to that can go out in sealing device, the mosquito for removing and benumbing calculates deinsectization rate.Test result is shown in Table 2.

4. the elongation at break of product is tested：Testing standard GB/T 1040.Test result is shown in Table 2.

5. fungicidal properties is tested：

The anti-mold effect of product is tested by moist chamber suspension method in the present invention, and specific method is：

(1) appliance material sterilizes

Cylindrical glass vessel (1200ml) plus detergent impregnate, and clear water rinses, and 75% ethanol is placed in superclean bench Ultraviolet disinfection, glassware prepare 2, respectively experimental group and control group；

The bottled 200ml distilled water high pressure sterilization of 250ml triangles (121 DEG C, 20min)；

250ml triangular flasks, test tube sky disappear；Pipette tips, test tube plug, sprayer sterilizing.

(2) spore suspension is prepared

In desinfection chamber or aseptic operating platform, by flame, the spore suspension (1*105-1* of single strain optimal dilution is prepared 107/ml), then all spore suspensions are mixed into (mixed in equal amounts, concentration are constant), it is fitted into sprayer.

(3) sample is placed

1,200ml sterile waters are poured into glassware respectively；

2, tested substrate-sprinkling spore suspension-is hung in first glassware to dry, as a control group；

3, tested substrate-sprinkling spore suspension-is hung in second glassware to dry.Product in the present invention is hanged It is hung on glassware central part (with tested substrate interval at least 1cm), as experimental group；

4, after the sealing of above-mentioned glassware 28d will be cultivated in constant temperature and humidity incubator, 28 DEG C, RH >=95%；

5, the central part in the glassware of control group does not place mould inhibitor, remaining step is same as described above；

6, when control group is mouldy serious, test is effective, otherwise must reform, the evaluation criterion of the mould proof grade of mould inhibitor Such as table 1.Test result is shown in Table 2.

The evaluation criterion of 1 mould proof grade of table

Test result：

The test of 2 product of table

As can be seen from the table, the composition in the present invention, is compared to containing specific structure antiseptic with compatilizer, is pressed down Bacterium intensity is high, and deodorizing effect is good, and elongation at break is high.

Example above-mentioned is merely illustrative, some features of the feature for explaining the disclosure.The attached claims It is intended to the range as wide as possible for requiring to be contemplated that, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is that the attached claims are not illustrated the present invention Feature exemplary selectional restriction.And the progress in science and technology will be formed language express inaccuracy due to and not The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended Claim covers.

Claims

1. a kind of antibacterial, deodorization, pest-resistant, mould proof composition, by weight, it includes：

The plastics of 50-80 parts by weight；

The antiseptic of 10-30 parts by weight；

The compatilizer of 0.1-5 parts by weight；

The antiseptic is chitosan/BiVO₄/SiO₂Compound；

Chitosan/the BiVO₄/SiO₂Compound is prepared using template, and specific preparation method is as follows：

(1) compound concentrations are the bismuth nitrate solution of 0.1M, and solvent is dust technology, and citric acid is added after solution clarification, adjusts molten Liquid pH is 7, obtains mixed solution A, weighs ammonium metavanadate and citric acid is dissolved in boiling water, obtain the mixed solution of concentration 0.1M B, it is spare；

(2) weighs the chitosan of 0.01mol, and 10ml ethyl alcohol is added and is stirred, is then drained ethyl alcohol with Suction filtration device, such as It this 2-4 times repeatedly, is drained with air stream；

(3) mixed solution A in the chitosan and step 1 in step 2 is slowly blended, and stirring is after twenty minutes；It is being vigorously stirred Under, mixed solution B is poured into, is stirred 5 minutes；

(4) takes out the sample of step 3, is washed respectively with pure water and ethyl alcohol, and dry in air；

(5) repeats step 3, you can obtains deposited the chitosan of different-thickness pucherite precursor liquid；

(6) will deposited the chitosan of pucherite precursor liquid, high-temperature calcination be carried out under 120 degree, you can obtain pucherite and shell The compound of glycan；

(7) is equal by 46.5g ethyl orthosilicates, 90ml absolute ethyl alcohols and 10ml 0.1M hydrochloric acid and a certain number of silane coupling agents After even mixing, the compound of pucherite and chitosan in step 6 is added under stiring, constant temperature hydrolysis 6h is obtained uniformly at 5 DEG C Transparent colloidal sol, then heating evaporation obtain gel, gel dries 17h under 80 DEG C of constant temperature and obtains final product；

The compatilizer is fluorine silicon resin, and the fluorine silicon resin is It is 1 according to molar ratio:1:3 are mixed with to obtain, specific preparation method：

With 10 partsTo prepare monomer, 13 parts of distilled water, 0.002 part of chlorine platinum is added Acid and Pt/C, react 6 hours under 50~60 DEG C of temperature condition, are then added30min is reacted, i.e., It can.

2. antibacterial described in claim 1, deodorization, pest-resistant, mould proof composition, which is characterized in that the plastics are polyolefin modeling Material.

3. a kind of antibacterial, deodorization, pest-resistant, mould proof product, by claim 1-2 any one of them antibacterial, deodorization, it is pest-resistant, Mould proof composition is prepared.