CN107779124B

CN107779124B - A kind of method preparing modified butadiene-styrene latex, thus obtained modified butadiene-styrene latex and its application

Info

Publication number: CN107779124B
Application number: CN201711063030.7A
Authority: CN
Inventors: 蔡辉; 江一明; 董巍; 伍云俊
Original assignee: Xinhui (china) New Material Co Ltd
Current assignee: Xinhui (china) New Material Co Ltd
Priority date: 2017-11-02
Filing date: 2017-11-02
Publication date: 2019-08-13
Anticipated expiration: 2037-11-02
Also published as: CN107779124A

Abstract

The present invention relates to a kind of method for preparing modified butadiene-styrene latex, the emulsion polymerization needs that this method is related to carry out in the presence of the aqueous dispersions of the inorganic nanometer oxide with antibacterial and antimildew function, and are carried out by pre-emulsification semi-continuous seed emulsion polymerization method.Modified butadiene-styrene latex prepared by the present invention not only itself has excellent antimildew and antibacterial performance, but also itself also has excellent antimildew and antibacterial performance while with excellent adhesion strength by products such as its regenerative leather, cardboards as adhesive production.Therefore, the invention further relates to the products that the modified butadiene-styrene latex prepared by the method for the invention and the modified butadiene-styrene latex are produced as the purposes of adhesive and the modified butadiene-styrene latex as adhesive, such as regenerative leather and/or cardboard.

Description

A kind of method preparing modified butadiene-styrene latex, thus obtained modified butadiene-styrene latex and It is applied

Technical field

The present invention relates to a kind of method for preparing modified butadiene-styrene latex, which is inorganic nanometer oxide The modified butylbenzene hydridization latex of grain.The invention further relates to the modified butadiene-styrene latex obtained by the method for the invention and its applications.Institute Stating modified butadiene-styrene latex can be used as the production for the product that adhesive is easy to go mouldy applied to regenerative leather, cardboard etc..

Technical background

Regenerative leather is leatherware fabric very versatile now.It is by crushing corium leftover pieces or regenerated leather raw material At the hide fiber of certain size, then it is uniformly mixed with natural rubber or synthetic latex, water and other raw materials again, through being demulsified After be pressed into certain thickness lamella, then final products obtained after drying, embossing and surface treatment.The manufacture work of cardboard Skill is similar to regenerative leather manufacturing process, and the manufacture raw material of cardboard is log slurry or the mixture of itself and secondary stock, these raw materials By impregnating certain density Heveatex or synthetic latex, extra latex is then squeezed out by technique requirement, is finally dried, is pressed Final products are obtained after flower and surface treatment.Heveatex is applied in regenerative leather and production always.But Heveatex It is easy aging, interlaminar strength is low, and price is more expensive, and Heveatex is in addition used to store as the regenerated leather product that adhesive produces " burning skin " phenomenon is easy to happen in journey；It uses Heveatex also to have similar situation as the cardboard that adhesive is produced, stores process In it some times happens that " spontaneous combustion " phenomenon.This is because Heveatex contains compared with polyprotein, product during accumulation deposit, It is influenced by temperature and humidity, microbes mass propagation on leather and cardboard, airtight due to accumulating, heat distributes not It goes out, eventually leads to " burning skin " and " spontaneous combustion " phenomenon.This not only makes scrap of the product, but also can even generate fire, gives enterprise's band Carry out heavy losses.Therefore, a kind of synthetic latex that can substitute Heveatex is found, is the certainty of regenerated leather and production field Trend.

Since the mechanical property of styrene-butadiene latex, processing performance and product service performance are all close to Heveatex, wearability, The performances such as heat resistance, resistance to ag(e)ing are also advantageous over Heveatex, thus styrene-butadiene latex slowly replaces Heveatex to become manufacture regeneration The main product of leather and cardboard.However, the adhesion strength of traditional styrene-butadiene latex is poor, the regenerative leather produced is in tensile strength There is obvious deficiency in aspect, and do not have antimildew and antibacterial performance, can only supply low-end market.Middle and high end regenerative leather can only use Other synthetic latexes have many patents that (such as CN1330181, CN104822876A, CN104822877A etc.) has been reported.With biography The deficiencies of that there is also interlaminar strengths is low for the cardboard produced of system styrene-butadiene latex, and cardboard subjective antisepsis performance is poor, is not able to satisfy Market demands.For this purpose, people develop paperboard grade (stock) synthetic latex, such as patent CN104911948A, CN101688370 Deng.However, these patents do not involve how to the phenomenon that preventing leather " burning skin " and cardboard " spontaneous combustion ".

Summary of the invention

In view of the above-mentioned state of the art, the present inventor has carried out extensively and has goed deep into styrene-butadiene latex field for many years Research, to develop a kind of new styrene-butadiene latex, the styrene-butadiene latex while improving adhesion strength, and assign latex oneself Body and product prepared therefrom such as leather and cardboard are with mould proof anti-microbial property, to prevent leather " burning skin " and cardboard " spontaneous combustion " The phenomenon that.The inventors discovered that when the preparation of styrene-butadiene latex is in the water comprising the inorganic nanoparticles with antimycotic antiseptic function By pre-emulsification semi-continuous seed emulsion polymerization come when carrying out in the presence of dispersion liquid, the modified butadiene-styrene latex so prepared not only from Body has excellent antimildew and antibacterial performance, and by products such as its regenerative leather, cardboards as adhesive production with excellent While different adhesion strength, itself also there is excellent antimildew and antibacterial performance.The present invention is based on aforementioned discovery and is achieved.

Therefore, it is an object of the present invention to provide a kind of methods for preparing modified butadiene-styrene latex.This method preparation changes Property styrene-butadiene latex not only itself have excellent antimildew and antibacterial performance, but also by its as adhesive produce regenerative leather, paper The products such as plate itself also have excellent antimildew and antibacterial performance while with excellent adhesion strength.

It is a further object to provide the modified butadiene-styrene latexes obtained by the method for the invention.The modification butadiene-styrene rubber Cream has high bond strength and excellent antimildew and antibacterial performance.

Purposes it is also another object of the present invention to provide modified butadiene-styrene latex of the present invention as adhesive.The modification butylbenzene Latex has high bond strength and excellent antimildew and antibacterial performance as adhesive.

Final object of the present invention is to provide the product prepared using modified butadiene-styrene latex of the present invention as adhesive. The product not only has high bond strength, but also has excellent antimildew and antibacterial performance.It is glued when the modified butadiene-styrene latex is used as When mixture produces regenerative leather, cardboard, the phenomenon that leather " burn skin " and cardboard " spontaneous combustion " can be prevented.

Realize that the technical solution of above-mentioned purpose of the present invention can be summarized as follows:

1. a kind of method for preparing modified butadiene-styrene latex, this method comprises the following steps:

Aqueous dispersions, the part initiator of inorganic nanometer oxide comprising softened water, with antibacterial and antimildew function are provided With the bottom material of partial emulsifier, when using redox initiation system, the initiator for including in the bottom material draws for redox All or part of oxidant constituents in hair system；

There is provided include styrene, softened water and residual emulsifier monomer emulsion, when use redox initiation system It and also include redox initiation system in the monomer emulsion when Oxidant section of the initiation system is added in bottom material In remainder oxidant constituents, the oxidation added in the oxidant constituents added in preferred bottom material at this time and monomer emulsion The weight ratio of agent component is 2:7-4:1, preferably 1:2-3:2；

Initiator solution of the remaining initiator in softened water, initiation when using redox initiation system are provided The initiator that agent aqueous solution includes is the reducing agent component in redox initiation system；

A part of monomer emulsion is uniformly mixed in the reactor under an inert atmosphere with the bottom material, by gained After mixture is warming up to 60-75 DEG C, respectively simultaneously by the remaining monomer emulsion, butadiene and the initiator solution It is continuously added to, temperature remains 60-95 DEG C during charging, and charging, which finishes, further to be polymerize to get modified butadiene-styrene latex is arrived.

2. according to the 1st method, wherein the aqueous dispersions of the inorganic nanometer oxide with antibacterial and antimildew function include Nano granular of zinc oxide, titanium dioxide nanoparticle and/or nano ceric oxide particle；Inorganic with antibacterial and antimildew function receives The aqueous dispersions of rice oxide also include the inorganic nanometer oxide without antibacterial and antimildew function, such as nano silica Grain and/or nano-aluminium oxide particle；And/or the average grain diameter of inorganic nanometer oxide particle is less than 100nm, preferably 20-90nm。

3. according to the 1st or 2 method, wherein the dosage of each material in parts by weight is as follows:

Total soft water: 100 parts；

Inorganic nanometer oxide in the aqueous dispersions of inorganic nanometer oxide with antibacterial and antimildew function: 0.5-8 parts, And if there is the inorganic nanometer oxide without antibacterial and antimildew function in aqueous dispersions, amount is no more than inorganic nano 50 weight % of oxide aggregate；

Butadiene: 25-70 parts；

Styrene: 20-75 parts；With

Emulsifier: 0.5-5 parts；

Preferable amount is as follows:

Total soft water: 100 parts；

Inorganic nanometer oxide in the aqueous dispersions of inorganic nanometer oxide with antibacterial and antimildew function: 0.8-5 parts, And if there is the inorganic nanometer oxide without antibacterial and antimildew function in aqueous dispersions, amount is no more than inorganic nano 50 weight % of oxide aggregate；

Butadiene: 35-60 parts；

Styrene: 40-50 parts；With

Emulsifier: 0.6-4 parts.

4. according to any one of 1-3 methods, wherein the emulsifier is anion emulsifier, nonionic emulsifier Or the compound emulsifying agent of anion emulsifier and nonionic emulsifier；Preferably, anion emulsifier is in being selected from the group It is one or more: C₁₀-C₁₈Alkyl sulphate type emulsifier, C₈-C₁₈Fatty alcohol ether sulphate type emulsifier, C₁₀-C₁₈Alkylbenzene Sulfonate type emulsifier, C₈-C₁₈Fatty alcohol ether benzene sulfonic acid salt form emulsifier, C₁₀-C₁₈Alkyl sulfonic acid salt form emulsifier, C₈-C₁₈Rouge Fat alcohol ether sulfonate type emulsifier, such as lauryl sodium sulfate, neopelex, fatty alcohol-ether sodium sulfate, isomery Tridecanol ether sodium sulfate, C₁₂-C₁₄Fatty alcohol-ether sodium sulfate and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, and/or, nonionic Emulsion Agent is one of to be selected from the group or a variety of: Polyoxyethylene Ether, PO-EO block polymer type, polyoxyethylene (20) dehydration It is Span, sorbitan fatty acid ester, especially octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, different Structure decyl alcohol polyoxyethylene ether, modified fatty alcohol polyethenoxy ether, fatty alcohol polyoxyethylene ether, PO-EO block polymer, primary alconol are poly- Ether, Tween-60 and/or Arlacel-80.

5. wherein also including chelating agent, pH buffer and/or pH tune in bottom material according to any one of 1-4 methods Save agent；Preferably, chelating agent is one of to be selected from the group or a variety of: ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, second Four sodium of ethylenediamine tetraacetic acid (EDTA), especially disodium ethylene diamine tetraacetate, and/or, pH buffer is one of to be selected from the group or a variety of: Bicarbonate, carbonate and phosphate, such as their own alkali metal salt and ammonium salt, such as sodium salt and sylvite, preferably bicarbonate Salt, especially sodium bicarbonate and ammonium hydrogen carbonate, and/or, pH adjusting agent is sodium hydrate aqueous solution and/or ammonia spirit.

6. wherein the dosage of chelating agent is 0.05-1 parts according to the 5th method, preferably 0.1-0.5 parts, it is based on 100 weights Measure the softened water of part；And/or the dosage of pH buffer be 0.1-2 parts, preferably 0.2-1 parts, the softened water based on 100 parts by weight.

7. wherein also including esters of unsaturated carboxylic acids, unsaturation in monomer emulsion according to any one of 1-6 methods Carboxylic acid, cross-linking monomer and/or molecular weight regulator；Preferably, esters of unsaturated carboxylic acids is the C of (methyl) acrylic acid₁-C₈Alkyl The hydroxyl C of ester or (methyl) acrylic acid₁-C₈Or mixtures thereof Arrcostab, such as methyl acrylate, ethyl acrylate, acrylic acid fourth Ester, 2-ethylhexyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, methacrylic acid second Ester, butyl methacrylate, hydroxyethyl methacrylate and its any mixture, and/or, unsaturated carboxylic acid is in being selected from the group It is one or more: acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and its any mixture, and/or, crosslinking Monomer is one of to be selected from the group or a variety of: divinylbenzene, bis- (methyl) acrylic acid glycol esters, diallyl maleate And its any mixture, and/or, molecular weight regulator is one of to be selected from the group or a variety of: lauryl mercaptan, sulfydryl third Acid butyl ester, thiuram-disulfide and two isothiocyanic acid esters, preferably lauryl mercaptan.

8., wherein the softening water inventory based on 100 parts by weight, the dosage of esters of unsaturated carboxylic acids is not according to the 7th method More than 10 parts, preferably 0-6 parts；And/or the dosage of unsaturated carboxylic acid is no more than 5 parts, preferably 0-4 parts；And/or cross-linking monomer Dosage is no more than 4 parts, preferably 0-3 parts；And/or the dosage of molecular weight regulator is 0-2 parts, preferably 0.1-0.5 parts.

9. according to any one of 1-8 methods, the wherein emulsifier in bottom material and the emulsifier in monomer emulsion Weight ratio be 1:9-8:2, preferably 4:6-7:3；And/or the initiator in bottom material and monomer emulsion and initiator it is water-soluble The weight ratio of initiator in liquid is 1:9-7:3, preferably 3:7-5:5.

10. according to any one of 1-9 methods, wherein initiator is one of to be selected from the group or a variety of: peroxide Compound type initiator and redox type initiator；Preferably, initiation when using Peroxide type initiator, in bottom material Agent may be the same or different with the initiator in initiator solution.

11. wherein latex solid content is 30-60 weight %, preferably 45-55 weight according to any one of 1-11 methods Measure %；And/or the average grain diameter of the emulsion particle in latex is 50-500 nanometers, preferably 80-300 nanometers.

12. the modified butadiene-styrene latex obtained by the method as required by any one of 1-12.

13. use of the modified butadiene-styrene latex obtained by the method as required by any one of 1-12 as adhesive On the way, preferably as the purposes of production regenerative leather and/or the adhesive of cardboard.

14. using the modified butadiene-styrene latex obtained by the method as required by any one of 1-12 as adhesive The product of production, preferably regenerative leather and/or cardboard.

These and other purposes, features and advantages of the present invention are readily able to be common after combining the hereafter consideration present invention Technical staff understands.

Specific embodiment

According to the first aspect of the invention, a kind of method for preparing modified butadiene-styrene latex is provided, this method includes such as Lower step:

There is provided include styrene, softened water and residual emulsifier monomer emulsion, when use redox initiation system It also include redox initiation system in the monomer emulsion and when the Oxidant section of the initiation system is added in bottom material In remainder oxidant constituents；

Initiator solution of the remaining initiator in softened water is provided, when using redox initiation system, this draws The initiator that hair agent aqueous solution includes is the reducing agent component in redox initiation system；

The method of the present invention can be referred to as pre-emulsification semi-continuous seed emulsion polymerization method, be a kind of synthesis side of polymer emulsion Method.So-called " pre-emulsification " refer to polymerization before by styrene, softened water, partial emulsifier and when use Redox Initiator body It may also include partial oxidation agent component when being, be first uniformly mixed, be dispersed in water monomer in the form of monomer droplet, formed single Body emulsion.It is so-called it is " semicontinuous " refer in the course of the polymerization process, first bottom material and partial monosomy emulsion are added in reactor Reaction, is continuously added to after reacting and reaching certain conversion ratio, then by remaining monomer emulsion, butadiene and initiator solution It is polymerize into reactor.So-called " seeded emulsion polymerization " refers to i.e. routinely emulsion polymerization is made part styrene first Then remaining monomer (i.e. butadiene and residual styrene) and other components are added to containing seed emulsion by seed latex again Emulsion polymerization is carried out in polymerizer.

In the methods of the invention, emulsion polymerization needs the water dispersion in the inorganic nanometer oxide with antibacterial and antimildew function It is carried out in the presence of liquid.These inorganic nanometer oxides with antibacterial and antimildew function are equably finely divided in fourth after emulsion polymerization In benzene latex particle, antibacterial and mouldproof effect is effectively played.In the present invention, " inorganic nanometer oxide " and " inorganic nano oxygen Compound particle " had not only included surface chemically modified inorganic nanometer oxide and inorganic nanometer oxide particle, but also including surface Not chemically modified inorganic nanometer oxide and inorganic oxide particles.Surprisingly, even if " inorganic nano oxygen Compound " and any chemical modification of surface free of " inorganic nanometer oxide particle " by the method for the invention can also be by these Nano-oxide particles uniform subdivision dissipates in styrene-butadiene latex particle, effectively plays antibacterial and mouldproof effect, while also can be improved viscous Knotting strength.As the inorganic nanometer oxide with antibacterial and antimildew function, it can be mentioned that nano zine oxide, nano-titanium dioxide and Nano ceric oxide.Thus it is preferred that the aqueous dispersions of inorganic nanometer oxide include nano granular of zinc oxide, nanometer two Titan oxide particles and/or nano ceric oxide particle.For this purpose, nano zine oxide aqueous dispersions, nano-titanium dioxide water can be used Any mixture of dispersion liquid, nano ceric oxide aqueous dispersions or these aqueous dispersions.The moisture of the inorganic nanometer oxide Dispersion liquid also may include other inorganic nanometer oxides without antibacterial and antimildew function, such as three oxygen of nano silica or nanometer Change two aluminium.For this purpose, nano silica aqueous dispersions, nano-aluminium oxide aqueous dispersions or these aqueous dispersions can be used Any mixture.By with antimycotic antiseptic function inorganic nanometer oxide aqueous dispersions with it is inorganic without antimycotic antiseptic function Nano-oxide aqueous dispersions are used in compounding, and can effectively reduce production cost, and the adhesive property of lotion and anti-microbial property are basic Do not reduce.When the aqueous dispersions of inorganic nanometer oxide include the inorganic nanometer oxide without antimycotic antiseptic function, The amount for not having the inorganic nanometer oxide of antimycotic antiseptic function is typically not greater than the inorganic nanometer oxide in aqueous dispersions 50 weight % of total amount.In the present invention, inorganic nanometer oxide particle in inorganic nanometer oxide aqueous dispersions is averaged Partial size is usually less than 100nm, preferably 20-90nm.

The additive amount of the aqueous dispersions of inorganic nanometer oxide is with the poidometer of inorganic nanometer oxide therein, addition Amount is usually 0.5-8 parts, preferably 0.8-5 parts, softens water inventory based on 100 parts by weight.

In the present invention, " softening water inventory " it is total to refer to that emulsion polymerization obtains all softened waters used in styrene-butadiene latex Amount, including the softened water in bottom material, the softened water in monomer emulsion, the softened water in initiator solution and all other Softened water included in raw material.

Modified butadiene-styrene latex of the invention is obtained by emulsion polymerization in order to realize, it is desirable to provide comprising softened water, have The bottom material of the aqueous dispersions of the inorganic nanometer oxide of antibacterial and antimildew function, part initiator and partial emulsifier.In order to provide The bottom material, usually by aqueous dispersions, part initiator and the portion of softened water, inorganic nanometer oxide with antibacterial and antimildew function Divide emulsifier mixing.

As initiator, any emulsion polymerization being able to achieve between butadiene and styrene can be used and obtain styrene-butadiene latex Free radical type initiator.The free radical type initiator that can be used is preferably Peroxide type initiator and/or redox Type initiator.For Peroxide type initiator, including potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, different phenylpropyl alcohol hydrogen peroxide, Tert-butyl hydroperoxide, two different phenylpropyl alcohol hydrogen peroxide etc..For redox type initiator, wherein oxidant constituents may include Potassium sulfate, sodium peroxydisulfate, ammonium persulfate, different phenylpropyl alcohol hydrogen peroxide, tert-butyl hydroperoxide, two different phenylpropyl alcohol hydrogen peroxide etc.；Its Middle reducing agent component may include ferrous sulfate, frerrous chloride, sodium hydrogensulfite, potassium bisulfite, mercaptan etc..Total use of initiator Amount is 0.3-5 weight %, preferably the 0.5-4 weight % of all total monomer weights of emulsion polymerization, more preferable 1-3 weight %.? In side of the present invention, initiator a part is added in bottom material, and a part is configured to initiator solution with water.Optionally, one Divide initiator to can also reside in monomer emulsion, initiator is not included in preferred monomers emulsion.Typically, bottom material and list The weight ratio of the initiator in initiator and initiator solution in body emulsion is 1:9-7:3, preferably 3:7-5:5.When When using Peroxide type initiator, the initiator in bottom material can be identical with the initiator in initiator solution, Can be different, it is preferably completely identical.When using redox type initiator, oxidant constituents can all be added to bottom material In, it can also partially be added in bottom material and remainder is added in monomer emulsion, and reducing agent component is all added to In initiator solution.

As emulsifier, any emulsion polymerization being able to achieve between butadiene and styrene can be used and obtain styrene-butadiene latex Emulsifier.The emulsifier that can be used, including anion emulsifier, nonionic emulsifier or anion emulsifier and it is non-from The compound emulsifying agent of sub- emulsifier.Anion emulsifier can be one of to be selected from the group or a variety of: C₁₀-C₁₈Alkylsurfuric acid Salt form emulsifier, C₈-C₁₈Fatty alcohol ether sulphate type emulsifier, C₁₀-C₁₈Alkyl benzene sulphonate salt form emulsifier, C₈-C₁₈Fatty alcohol Ether benzene sulfonate type emulsifier, C₁₀-C₁₈Alkyl sulfonic acid salt form emulsifier, C₈-C₁₈Fatty alcohol ether sulfonate type emulsifier, such as Lauryl sodium sulfate, neopelex, fatty alcohol-ether sodium sulfate (LH12, Sol dimension), isomery tridecane alcohol ether sulphur Sour sodium (BES20, BASF), C₁₂-C₁₄Fatty alcohol-ether sodium sulfate (FES993, BASF), disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate (2A1, DOW Chemical) etc..Nonionic emulsifier can be one of to be selected from the group or a variety of: polyoxyethylene ether (or be known as Ethoxylate) type, PO-EO block polymer type, polyoxyethylene (20) sorbitan fatty acid ester (TWEEN Series), dehydration Span (such as Span series).As example, octyl phenol polyoxyethylene ether (TX-10, Jiangsu Hai'an petroleum can be mentioned that Chemical plant), nonylphenol polyoxyethylene ether (TX-9, Jiangsu Hai'an petrochemical plant), isomery decyl alcohol polyoxyethylene ether (TO12, bar Si Fu), modified fatty alcohol polyethenoxy ether (A1080, BASF), fatty alcohol polyoxyethylene ether (BCH9, Sol dimension), PO-EO Block polymer (PE6100, BASF), primary alconol polyethers (SA-9, DOW Chemical), Tween-60, Arlacel-80 etc..Emulsifier one Part is added in bottom material, and remainder is added in monomer emulsion.Typically, the emulsifier in bottom material and monomer emulsify The weight ratio of emulsifier in liquid is 1:9-8:2, preferably 4:6-7:3.When using two kinds or more of emulsifier, in bottom material Emulsifier can be identical with the emulsifier in monomer emulsion, can also be different, it is preferably completely identical.Emulsifier it is total Dosage is usually 0.5-5 parts, and preferably 0.6-4 parts, the softening water inventory based on 100 parts by weight.

As bottom material involved in the method for the present invention, it also may include chelating agent.In some cases, reaction mixture can It can be because the reasons such as container, pipeline, raw material bring the emulsion polymerization of some retardances or polymerization inhibitor butadiene and styrene to extend The metal impurities of polymerization time, such as magnesium, calcium and iron ion.Addition chelating agent can remove foregoing impurities to the unfavorable shadow of polymerization It rings.Chelating agent is for example including ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, preferably ethylenediamine tetraacetic Acetic acid disodium.The additive amount of chelating agent be 0.05-1 parts, preferably 0.1-0.5 parts, the softening water inventory based on 100 parts by weight.

As bottom material involved in the method for the present invention, it also may include pH buffer.In some cases, draw for specific Hair system, it is more sensitive to pH, only it could effectively cause the lotion between butadiene and styrene in particular range Polymerization.In order to which pH is stably maintained within the scope of the pH that suitable initiator system causes, it usually needs addition pH buffer, with Exempt the larger fluctuation of reaction mixture pH.The substance that can be used as pH buffer has bicarbonate, carbonate, phosphate etc., example Such as their own alkali metal salt and ammonium salt, such as sodium salt and sylvite, preferably bicarbonate, especially sodium bicarbonate and bicarbonate Ammonium.Typically, the additive amount of pH buffer be 0.1-2 parts, preferably 0.2-1 parts, the softening water inventory based on 100 parts by weight.

As bottom material involved in the method for the present invention, it also may include pH adjusting agent.In some cases, in order to adapt to not Same demand, for example, under the conditions of same reaction temperature, when the pH of reaction mixture is lower than 3, persulfuric acid salt form decomposition of initiator Speed sharply increases, and the violent gel easy to form of polymerization reaction, this just needs to add pH adjusting agent to adjust reaction mixture PH carries out stable polymerization reaction.As pH adjusting agent, any inorganic base and organic base and its aqueous solution can be used, preferably Sodium hydrate aqueous solution, ammonia spirit.The concentration of sodium hydrate aqueous solution is usually 5-10 weight %.The additive amount of pH adjusting agent It depends on the needs.For example, for the sodium hydrate aqueous solution of 5 weight % concentration, its additive amount in bottom material is usually not More than 0.5 part, the softening water inventory based on 100 parts by weight.

Modified butadiene-styrene latex of the invention is obtained by emulsion polymerization in order to realize, it is also necessary to provide comprising styrene, soft Change the monomer emulsion of water and residual emulsifier.The monomer emulsion provides and carries out pre-emulsified effect to monomer.The monomer It also may include initiator in emulsion.It, usually can be in monomer cream such as when emulsion polymerization uses redox type initiator Changing includes partial oxidation agent component in liquid, and rest part is included in bottom material.In order to provide the monomer emulsion, usually by benzene It is the monomer of liquid under the room temperature such as ethylene, (emulsifier needed for i.e. entire styrene-butadiene emulsion polymerization subtracts for softened water and residual emulsifier Remove part emulsifier used in bottom material) uniformly mixing, form aqueous emulsion.

In the present invention, the dosage of styrene is usually 20-75 parts, and preferably 40-50 parts, based on the soft of 100 parts by weight Change water inventory.

As monomer emulsion involved in the method for the present invention, it also may include esters of unsaturated carboxylic acids as comonomer. Esters of unsaturated carboxylic acids can make polymer emulsion have preferable weatherability, preferable adhesion strength, the transparency and pollution resistance. As esters of unsaturated carboxylic acids comonomer, the C of (methyl) acrylic acid can be used₁-C₈The hydroxyl of Arrcostab or (methyl) acrylic acid C₁-C₈Or mixtures thereof Arrcostab, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl-prop Olefin(e) acid hydroxyl ethyl ester and its any mixture.The dosage of esters of unsaturated carboxylic acids is typically not greater than 10 parts, preferably 0-6 parts, is based on 100 The softening water inventory of parts by weight.

As monomer emulsion involved in the method for the present invention, it also may include unsaturated carboxylic acid as comonomer.No Saturated carboxylic acid can make polymer emulsion mechanical stability with higher, freeze-thaw stability and good application property.As Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and its any mixing can be used in unsaturated carboxylic acid comonomer Object.The dosage of unsaturated carboxylic acid is typically not greater than 5 parts, and preferably 0-4 parts, the softening water inventory based on 100 parts by weight.

As monomer emulsion involved in the method for the present invention, it also may include cross-linking monomer.The cross-linking monomer is usually Organic compound containing two or more ethylenical unsaturated double bonds.As cross-linking monomer, can be used divinylbenzene, Bis- (methyl) acrylic acid glycol esters, diallyl maleate and its any mixture.The dosage of cross-linking monomer is typically not greater than 4 Part, preferably 0-3 parts, the softening water inventory based on 100 parts by weight.

As monomer emulsion involved in the method for the present invention, it also may include molecular weight regulator.The molecular-weight adjusting Agent is any molecular weight regulator for being suitable for synthesizing styrene-butadiene latex.Molecular weight regulator can be substantially reduced molecular weight, to drop The viscosity of low styrene-butadiene latex improves the workability of styrene-butadiene latex.Molecular weight regulator can also be controlled by adjusting its dosage Molecular weight.As molecular weight regulator, lauryl mercaptan, mercaptopropionic acid butyl ester, thiuram-disulfide, two thio can be used Isocyanates etc..Molecular weight regulator is preferably lauryl mercaptan.Molecular regulation agent dosage is usually 0-2 parts, preferably 0.1-0.5 parts, the softening water inventory based on 100 parts by weight.

As monomer emulsion involved in the method for the present invention, it also may include pH adjusting agent.It, can be with as pH adjusting agent Use any inorganic base and organic base and its aqueous solution, preferably sodium hydrate aqueous solution.The concentration of sodium hydrate aqueous solution is usual For 5-10 weight %.The additive amount of pH adjusting agent depends on the needs.For example, for the sodium hydrate aqueous solution of 5 weight % concentration For, its additive amount in monomer emulsion is typically not greater than 0.5 part, the softening water inventory based on 100 parts by weight.

As monomer emulsion involved in the method for the present invention, it also may include initiator.Particularly, it is gone back when using oxidation When substance system initiated polymerization, partial oxidation agent component can be added in monomer emulsion.In the case, add in bottom material The weight ratio for the oxidant constituents added in the oxidant constituents and monomer emulsion added is usually 2:7-4:1, preferably 1:2-3: 2。

In order to implement emulsion polymerization of the invention, by a part of monomer emulsion and bottom material under an inert atmosphere in reactor In be uniformly mixed, after gained mixture is warming up to 60-75 DEG C, by the remaining monomer emulsion, butadiene and the initiation Agent aqueous solution is continuously added to simultaneously respectively, and temperature remains 60-95 DEG C during charging, charging finish further polymerize to get To modified butadiene-styrene latex.

According to the present invention, emulsion polymerization needs to carry out under an inert atmosphere.Here inert atmosphere refers to being not involved in fourth The atmosphere of the chemical reaction of benzene emulsion polymerization.Advantageously, carrying out in a nitrogen atmosphere.It is reacted for this purpose, usually being purged with nitrogen Device simultaneously pours nitrogen.A part of monomer emulsion and bottom material just heat up after mixing in the reactor under an inert atmosphere, temperature After degree is increased to 60-75 DEG C, start slowly to divide the remaining monomer emulsion, butadiene and the initiator solution It is not added continuously in reactor not simultaneously.Monomer emulsion total amount is usually accounted for the part monomer emulsion that bottom material first mixes 5-30%, preferably 10-15%.In the methods of the invention, the dosage of butadiene is usually 25-70 parts, and preferably 35-60 parts, base In the softening water inventory of 100 parts by weight.Here " being continuously added to simultaneously respectively " refers to remaining monomer emulsion, fourth two Alkene and initiator solution these three materials are added separately in reaction kettle, and respectively charging is continuous, and these three materials Not in accordance with sequencing but substantially sequentially it is added in reactor in no particular order.Three kinds of materials respectively need slowly Addition.Addition can be carried out by metering pump.The starting that these three materials respectively feed is substantially while carrying out, and feeds and continue Time may be the same or different, preferably identical.Typically, it is small to be respectively no more than 8 for the feed time of these three materials When, addition in preferably 3-6 hours finishes.During adding aforementioned three kinds of materials, polymerization reaction is had, so that reaction Temperature increases.Usually requiring to control the temperature during charging is 60-95 DEG C, preferably 70-90 DEG C.After charging finishes, each list Body not yet fully reacting, it is also necessary to further polymerization, to obtain modified butadiene-styrene latex.Temperature during the polymerization is generally also protected Hold is 60-95 DEG C, preferably 70-95 DEG C.The time further polymerizeing is usually 0.5-3 hours, preferably 1-2 hours.Reactor Type is not particularly limited, and generallys use reaction kettle.

In order to promote the quality of modified butadiene-styrene latex, it is also necessary to after the modified butadiene-styrene latex for directly obtaining polymerization carries out Reason.For this purpose, the modified butadiene-styrene latex degassing for usually directly obtaining polymerization removes residual monomer, pH and filtering are adjusted in cooling.Degassing It is carried out usually in degassing tower, vacuumizes removing residual monomer；Sometimes also need to be passed through steam by the way that residual monomer is stripped off. Adjusting pH is in order to adapt to downstream application, according to downstream application it needs to be determined that needing to be tuned into great pH.Typically, using pH The pH of styrene-butadiene latex is adjusted to 7.0-9.0 by regulator.Filtering is the micro gel in order to filter out polymerization process generation.

In one embodiment of the invention, the dosage of each material in parts by weight is as follows:

Total soft water: 100 parts；

Butadiene: 25-70 parts；

Styrene: 20-75 parts；With

Emulsifier: 0.5-5 parts.

In a preferred embodiment of the invention, the dosage of each material in parts by weight is as follows:

Total soft water: 100 parts；

Butadiene: 35-60 parts；

Styrene: 40-50 parts；With

Emulsifier: 0.6-4 parts.

Here " total soft water " refers to that emulsion polymerization obtains all softened waters used in styrene-butadiene latex, including in bottom material Softened water, the softened water in monomer emulsion, included in the softened water in initiator solution and its all raw material Softened water.

Pre-emulsification semi-continuous seed emulsion polymerization method through the invention prepares styrene-butadiene latex, has at low cost, work Skill is simple, is easy to the advantages that large-scale production.By the method for the invention, the nano oxygen in the aqueous dispersions of inorganic nanometer oxide Compound is not necessarily to can be used to the present invention through surface chemical modification, after emulsion polymerization, these nano-oxide particles uniform subdivisions It dissipates in styrene-butadiene latex particle, effectively plays antibacterial and mouldproof effect.

According to the second aspect of the invention, provide what the method that one kind prepares modified butadiene-styrene latex through the invention obtained Modified butadiene-styrene latex.The latex not only itself has excellent antimildew and antibacterial performance, but also is produced again by it as adhesive The products such as rawhide leather, cardboard itself also have excellent antimildew and antibacterial performance while with excellent adhesion strength.

In modified butadiene-styrene latex of the invention, the average grain diameter of emulsion particle is usually 50-500 nanometers, preferably 80-300 Nanometer.The latex solid content of modified butadiene-styrene latex of the present invention is usually 30-60 weight %, preferably 45-55 weight %.

Modified butadiene-styrene latex of the invention is a kind of novel styrene-butadiene latex, not only has excellent adhesiveness, but also Also there is excellent antimildew and antibacterial performance.Therefore, according to the third aspect of the present invention, provide and prepare by the method for the invention Purposes of the modified butadiene-styrene latex as adhesive.Modified butadiene-styrene latex of the invention can be used as adhesive, especially as life Produce the adhesive of regenerative leather and cardboard.The modified butadiene-styrene latex has high bond strength as adhesive, and assigns and giving birth to The product of production is with excellent antimildew and antibacterial performance.

The last one aspect according to the present invention, provides and uses the modified butadiene-styrene latex of the present invention to produce as adhesive Product.Modified butadiene-styrene latex of the invention not only has high bond strength, and also assigns product produced and prevented with excellent Mould anti-microbial property, therefore particularly suitable for production regenerative leather and cardboard, so as to prevent leather " burning skin " and cardboard " certainly Combustion " phenomenon.Therefore, not only there is high bond strength as the product that adhesive produces using modified butadiene-styrene latex of the present invention, and And also there is excellent antimildew and antibacterial performance.There are many products for using modified butadiene-styrene latex of the present invention to produce as adhesive, Especially regenerative leather and cardboard.

Embodiment

Technical solution of the present invention will be further explained by embodiment below.These embodiments are merely to illustrate this It invents and is not construed as limitation of the invention.

The number addressed in embodiment unless otherwise instructed, refers both to parts by weight；The percentage addressed in embodiment for example without It illustrates, refers both to percentage by weight.Particular technique or condition are not specified in embodiment, according to the art text It offers described routine techniques or condition carries out.

Embodiment 1

Polymeric kettle is vacuumized, 3 parts of nano zine oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 80nm, admittedly contain Amount 30%, Nanjing Tian Hang new material Co., Ltd), 62.4 parts of softened waters, 0.1 part of 5% sodium hydrate aqueous solution, 0.1 part of second two Amine tetraacethyl disodium, 0.5 part of sodium bicarbonate, 0.2 part of different phenylpropyl alcohol hydrogen peroxide, 0.3 part of sodium peroxydisulfate, 1.2 parts of dodecyl sulphur Sour sodium and 0.8 part of nonylphenol polyoxyethylene ether (TX-9, Jiangsu Hai'an petrochemical plant), as bottom material after being dispersed with stirring uniformly. By 50 parts of styrene, 5 parts of n-butyl acrylates, 0.8 part of acrylic acid, 0.5 part of n-dodecyl mercaptan, 2 parts of divinylbenzenes, 1 Part lauryl sodium sulfate, 0.5 part of nonylphenol polyoxyethylene ether (TX-9, Jiangsu Hai'an petrochemical plant), 15 parts of softened waters, 0.5 part of different phenylpropyl alcohol hydrogen peroxide and 0.4 part of 5% sodium hydrate aqueous solution mix, and are then dispersed into surely with high pressure homogenizer Fixed monomer emulsion.1 part of sodium hydrogensulfite, which is dissolved, with 20 parts of softened waters obtains initiator solution.Prepare 35 parts of butadiene.

10% above-mentioned monomer emulsion is added in the polymeric kettle added with above-mentioned bottom material, after being uniformly mixed 60 DEG C are warming up to, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene and initiator is separated by metering pump Aqueous solution, three kinds of respective time for adding of stream are 4.5 hours, and the temperature during dropwise addition in polymeric kettle is controlled at 70 ± 1 DEG C. After all materials are all added dropwise, insulation reaction 1.5 hours at 75 ± 1 DEG C.Then gained latex is transferred to degassing Tower vacuumizes removing residual monomer, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtains styrene-butadiene latex production Product.The data of the latex products are shown in Table 2, and wherein partial size is surveyed using Zetasizer Nano ZS90 (Malvern company, Britain) Amount.

Embodiment 2

Polymeric kettle is vacuumized, 3 parts of nano zine oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 30nm, admittedly contain Amount 30%, Hangzhou intelligence titanium purify Science and Technology Ltd.) and 3 parts of titanium dioxide water-dispersion liquids (average grain diameter 80nm, solid contents 30%, Nanjing Tian Hang new material Co., Ltd), 70 parts of softened waters, 0.02 part of 5% sodium hydrate aqueous solution, 0.1 part of ethylenediamine tetraacetic Acetic acid disodium, 0.5 part of ammonium hydrogen carbonate, 0.5 part of sodium peroxydisulfate, 1.5 parts of neopelexes and 0.2 part of isomery C₁₃Fat Alcohol polyoxyethylene ether (TO12, BASF), as bottom material after being dispersed with stirring uniformly.By 48 parts of styrene, 0.1 part of tertiary dodecyl Mercaptan, 5 parts of n-butyl acrylates, 2 parts of divinylbenzenes, 0.2 part of neopelex, 0.5 part of isomery C₁₃Poly alkyl alcohol Ethylene oxide ether (TO12, BASF), 15.73 parts of softened waters and 0.08 part of 5% sodium hydroxide are uniformly mixed, then with high-pressure homogeneous Machine is dispersed into stable monomer emulsion.1.5 parts of sodium peroxydisulfates, which are dissolved, with 10 parts of softened waters obtains initiator solution.It is quasi- Standby 40 parts of butadiene.

5% above-mentioned monomer emulsion is added in the polymeric kettle added with above-mentioned bottom material, after being uniformly mixed 60 DEG C are warming up to, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene and initiator is separated by metering pump Aqueous solution, three kinds of respective time for adding of stream are 5 hours, and the temperature during dropwise addition in polymeric kettle is controlled at 80 ± 1 DEG C.When After all materials are all added dropwise, insulation reaction 1 hour at 85 ± 1 DEG C.Then gained latex degassing tower is transferred to take out Residual monomer is removed in vacuum, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtain styrene-butadiene latex product.It should The data of latex products are shown in Table 2, and wherein partial size is measured using Zetasizer Nano ZS90 (Malvern company, Britain).

Embodiment 3

Polymeric kettle is vacuumized, 10 parts of nano titanium dioxide water-dispersion liquids of investment after nitrogen displacement (average grain diameter 15nm, Gu Content 15%, Hangzhou intelligence titanium purify Science and Technology Ltd.), 60 parts of softened waters, 0.01 part of 5% sodium hydrate aqueous solution, 0.5 part of second Edetate disodium, 0.1 part of sodium bicarbonate, 1 part of ammonium persulfate, 1 part of lauryl sodium sulfate and 0.3 part of fatty alcohol polyoxy second Alkene ether (BCH9, Sol dimension), as bottom material after being dispersed with stirring uniformly.By 75 parts of styrene, 0.12 part of tert-dodecylmercaotan, 5 Part hydroxy-ethyl acrylate, 1.2 parts of methacrylic acids, 2 parts of double acrylic acid glycol esters, 1 part of lauryl sodium sulfate, 1 part of fat Alcohol polyoxyethylene ether (BCH9, Sol dimension), 21 parts of softened waters and 0.04 part of 5% sodium hydrate aqueous solution are uniformly mixed, and are then used High pressure homogenizer is dispersed into stable monomer emulsion.The initiation that 1.5 parts of sodium peroxydisulfates obtain is dissolved with 10.45 parts of softened waters Agent aqueous solution.Prepare 55 parts of butadiene.

10% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred It is warming up to 70 DEG C after even, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene is separated by metering pump and is drawn Agent aqueous solution is sent out, three kinds of respective time for adding of stream are 6 hours, and the reaction temperature during dropwise addition in polymeric kettle is controlled 80 ±1℃.After all materials are all added dropwise, insulation reaction 2 hours at 85 ± 1 DEG C.Then gained latex is transferred to Degassing tower vacuumizes removing residual monomer, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtains styrene-butadiene latex Product.The data of the latex products are shown in Table 2, and wherein partial size is surveyed using Zetasizer Nano ZS90 (Malvern company, Britain) Amount.

Embodiment 4

Polymeric kettle is vacuumized, 6 parts of nano-aluminium oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 30nm, Solid content 20%, Xuancheng Jingrui New Material Co., Ltd.) and 4 parts of titanium dioxide water-dispersion liquids (average grain diameter 30nm, solid contents 30%, Hangzhou intelligence titanium purify Science and Technology Ltd.), 67 parts of softened waters, 0.01 part of 5% sodium hydrate aqueous solution, 0.1 part of ethylenediamine Tetraacethyl disodium, 0.5 part of sodium bicarbonate, 0.5 part of sodium peroxydisulfate, 1.3 parts of isomery tridecanols ether sodium sulfate (BES20, Baths Husband) and 0.5 part of octyl phenol polyoxyethylene ether (TX-10, Jiangsu Hai'an petrochemical plant), as bottom material after being dispersed with stirring uniformly. By 40 parts of styrene, 0.2 part of tert-dodecylmercaotan, 8 parts of n-butyl acrylates, 2 parts of divinylbenzenes, 4 parts of itaconic acids, 1 part Isomery tridecanol ether sodium sulfate (BES20, BASF), 1 part of octyl phenol polyoxyethylene ether (TX-10, Jiangsu Hai'an petrochemical industry Factory), 15.35 parts of softened waters and 0.04 part of 5% sodium hydrate aqueous solution be uniformly mixed, be then dispersed into high pressure homogenizer Stable monomer emulsion.1.5 parts of sodium peroxydisulfates, which are dissolved, with 10 parts of softened waters obtains initiator solution.Prepare 32 parts of fourths two Alkene.

8% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred It is warming up to 60 DEG C after even, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene is separated by metering pump and is drawn Agent aqueous solution is sent out, three kinds of respective time for adding of stream are 4.5 hours, and the reaction temperature control during dropwise addition in polymeric kettle exists 80±1℃.After all materials are all added dropwise, insulation reaction 1 hour at 85 ± 1 DEG C.Then gained latex is shifted Removing residual monomer is vacuumized to degassing tower, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtain butadiene-styrene rubber Milk product.The data of the latex products are shown in Table 2, and wherein partial size uses Zetasizer Nano ZS90 (Malvern company, Britain) Measurement.

Embodiment 5

Polymeric kettle is vacuumized, 16.67 parts of nano zine oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 40nm, Solid content 30%, Xuancheng Jingrui New Material Co., Ltd.), 63 parts of softened waters, 0.02 part of 5% sodium hydrate aqueous solution, 0.1 part of second Edetate disodium, 0.5 part of sodium bicarbonate, 0.5 part of sodium peroxydisulfate, 1.2 parts of C₁₂-C₁₄Fatty alcohol-ether sodium sulfate (FES993, BASF) and 0.3 part of modified fatty alcohol polyethenoxy ether (A1080, BASF), as bottom material after being dispersed with stirring uniformly.By 52 Part styrene, 0.1 part of tert-dodecylmercaotan, 6 parts of methyl methacrylates, 2.5 parts of double acrylic acid glycol esters, 1 part of propylene Acid, 0.5 part of maleic acid, 1.5 parts of C₁₂-C₁₄Fatty alcohol-ether sodium sulfate (FES993, BASF), 0.5 part of modified fatty alcohol polyoxy second Alkene ether (A1080, BASF), 15.27 parts of softened waters and 0.04 part of 5% sodium hydrate aqueous solution are uniformly mixed, and then use high pressure Homogenizer is dispersed into stable monomer emulsion.It is water-soluble that initiator is obtained with 10 parts of softened waters 1.5 parts of sodium peroxydisulfates of dissolution Liquid.Prepare 46 parts of butadiene.

10% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred It is warming up to 60 DEG C after even, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene is separated by metering pump and is drawn Agent aqueous solution is sent out, three kinds of respective time for adding of stream are 4.5 hours, and the reaction temperature control during dropwise addition in polymeric kettle exists 80±1℃.After all materials are all added dropwise, insulation reaction 1 hour at 85 ± 1 DEG C.Then gained latex is shifted Removing residual monomer is vacuumized to degassing tower, with filtering after 5% sodium hydrate aqueous solution tune pH after cooling, obtains styrene-butadiene latex production Product.The data of the latex products are shown in Table 2, and wherein partial size is surveyed using Zetasizer Nano ZS90 (Malvern company, Britain) Amount.

Embodiment 6

Polymeric kettle is vacuumized, 3 parts of nano ceric oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 90nm, Gu Content 30%, Nanjing Tian Hang new material Co., Ltd), 65 parts of softened waters, 0.01 part of 5% sodium hydrate aqueous solution, 0.2 part of second two Amine tetraacethyl disodium, 0.3 part of sodium bicarbonate, 0.2 part of sodium peroxydisulfate, 0.2 part of C₁₂-C₁₄Fatty alcohol-ether sodium sulfate (FES77, Bath Husband) and 0.1 part of PO-EO block polymer (PE6100, BASF), as bottom material after being dispersed with stirring uniformly.By 30 parts of styrene, 0.1 part of tert-dodecylmercaotan, 1.2 parts of methacrylic acids, 0.5 part of itaconic acid, 10 parts of methyl methacrylates, 0.2 part of C₁₂- C₁₄Fatty alcohol-ether sodium sulfate (FES77, BASF), 22.78 parts of softened waters and 0.11 part of 5% sodium hydrate aqueous solution mixing are equal It is even, stable monomer emulsion is then dispersed into high pressure homogenizer.1.5 parts of sodium peroxydisulfates are dissolved with 10 parts of softened waters to obtain Initiator solution.Prepare 58 parts of butadiene.

10% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred It is warming up to 75 DEG C after even, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene is separated by metering pump and is drawn Agent aqueous solution is sent out, three kinds of respective time for adding of stream are 5.5 hours, and the reaction temperature control during dropwise addition in polymeric kettle exists 85±1℃.After all materials are all added dropwise, insulation reaction 2 hours at 95 ± 1 DEG C.Then gained latex is transferred to Degassing tower vacuumizes removing residual monomer, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtains styrene-butadiene latex Product.The data of latex products are shown in Table 2, and wherein partial size is surveyed using Zetasizer Nano ZS90 (Malvern company, Britain) Amount.

Embodiment 7

Polymeric kettle is vacuumized, 5 parts of nano ceric oxide aqueous dispersions of investment after nitrogen displacement (average grain diameter 40nm, Gu Content 20%, Hangzhou Wanjing New Material Co., Ltd.), 3 parts of Nano zinc dioxide impact-resistant aqueous dispersions (average grain diameter 30nm, solid contents 30%, Xuancheng Jingrui New Material Co., Ltd.), 62.08 parts of softened waters, 0.02 part of 5% sodium hydrate aqueous solution, 0.37 part of second two Amine tetraacethyl disodium, 0.4 part of sodium bicarbonate, 0.8 part of sodium peroxydisulfate, 1.0 parts of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates (2A1, Tao Shi Chemistry) and 0.2 part of primary alconol polyethers (SA-9, DOW Chemical), as bottom material after being dispersed with stirring uniformly.By 40 parts of styrene, 0.2 part Tert-dodecylmercaotan, 5 parts of hydroxy-ethyl acrylates, 1.5 parts of acrylic acid, 2 parts of divinylbenzenes, 2.0 parts of dodecyl diphenyl oxides Sodium disulfonate (2A1, DOW Chemical), 0.5 part of primary alconol polyethers (SA-9, DOW Chemical), 20 parts of softened waters and 0.1 part of 5% hydrogen-oxygen Change sodium water solution to be uniformly mixed, stable monomer emulsion is then dispersed into high pressure homogenizer.With 11.7 parts of softened waters Dissolve the initiator solution that 1.7 parts of sodium peroxydisulfates obtain.Prepare 50 parts of butadiene.

12% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred It is warming up to 60 DEG C after even, then starts simultaneously at and continuously dropwise addition residual monomer emulsion, butadiene is separated by metering pump and is drawn Agent aqueous solution is sent out, three kinds of respective time for adding of stream are 5 hours, and the reaction temperature during dropwise addition in polymeric kettle is controlled 85 ±1℃.After all materials are all added dropwise, insulation reaction 1.5 hours at 90 ± 1 DEG C.Then gained latex is shifted Removing residual monomer is vacuumized to degassing tower, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtain butadiene-styrene rubber Milk product.The data of the latex products are shown in Table 2, and wherein partial size uses Zetasizer Nano ZS90 (Malvern company, Britain) Measurement.

Embodiment 8

Polymeric kettle is vacuumized, 10 parts of nano titanium dioxide water-dispersion liquids of investment after nitrogen displacement (average grain diameter 15nm, Gu Content 20%, Xuancheng Jingrui New Material Co., Ltd.), 4 parts of nano silicon dioxide dispersions (average grain diameter 50nm, solid contents 30%,Shenzhen Jing Cai Chemical Co., Ltd.), 63 parts of softened waters, 0.02 part of 5% sodium hydrate aqueous solution, 0.1 part of ethylenediamine tetrem Acid disodium, 0.5 part of sodium bicarbonate, 0.8 part of sodium peroxydisulfate, 1 part of fatty alcohol-ether sodium sulfate (LH12, Sol dimension) and 0.3 part of primary alconol Polyethers (EH-9, DOW Chemical), as bottom material after being dispersed with stirring uniformly.By 40 parts of styrene, 0.1 part of tert-dodecylmercaotan, 3 Part divinylbenzene, 1 part of itaconic acid, 1.5 parts of maleic acids, 1 part of fatty alcohol-ether sodium sulfate (LH12, Sol dimension), 1 part of primary alconol polyethers (EH-9, DOW Chemical), 15.88 parts of softened waters and 0.3 part of 5% sodium hydrate aqueous solution are uniformly mixed, then with high-pressure homogeneous Machine is dispersed into stable monomer emulsion.1.5 parts of sodium peroxydisulfates, which are dissolved, with 10 parts of softened waters obtains initiator solution.It is quasi- Standby 55 parts of butadiene.

5% above-mentioned monomer emulsion is added in the polymerization reaction kettle added with above-mentioned bottom material, is stirred When being warming up to 60 DEG C after even, then start simultaneously at by metering pump separate continuously be added dropwise residual monomer emulsion, butadiene and Initiator solution, three kinds of respective time for adding of stream are 5 hours, and the reaction temperature control during dropwise addition in polymeric kettle exists 85±1℃.After all materials are all added dropwise, insulation reaction 2 hours at 90 ± 1 DEG C.Then gained latex is shifted Removing residual monomer is vacuumized to degassing tower, is cooled to room temperature and is filtered with after 5% sodium hydrate aqueous solution tune pH, obtain butadiene-styrene rubber Milk product.The data of the latex products are shown in Table 2, and wherein partial size uses international precision instrument Zetasizer Nano ZS90 (Malvern company, Britain) measurement.

Comparative example 1

Embodiment 2 is repeated, but does not use any Zinc oxide water dispersion liquid and titanium dioxide water-dispersion liquid.Gained butadiene-styrene rubber The data of milk product are shown in Table 3, and wherein partial size is measured using Zetasizer Nano ZS90 (Malvern company, Britain).

Comparative example 2

Embodiment 4 is repeated, but does not use any aluminum oxide aqueous dispersions and titanium dioxide water-dispersion liquid.Gained fourth The data of benzene latex products are shown in Table 3, and wherein partial size is measured using Zetasizer Nano ZS90 (Malvern company, Britain).

Comparative example 3

Embodiment 5 is repeated, but does not use any Zinc oxide water dispersion liquid.The data of gained styrene-butadiene latex product are shown in Table 3, Wherein partial size is measured using Zetasizer Nano ZS90 (Malvern company, Britain).

Comparative example 4

Embodiment 2 is repeated, but is dissipated in the course of the polymerization process without using any Zinc oxide water dispersion liquid and aqueous titanium dioxide Liquid, but Zinc oxide water dispersion liquid described in embodiment 2 and titanium dioxide water-dispersion liquid addition are finally filtered into resulting glue In cream.The data of gained styrene-butadiene latex product are shown in Table 3, and wherein partial size uses Zetasizer Nano ZS90 (Britain Malvern Company) measurement.

Comparative example 5

Embodiment 4 is repeated, but does not use any aluminum oxide aqueous dispersions and titanium dioxide water in the course of the polymerization process Dispersion liquid, but last filtering gained is added in Zinc oxide water dispersion liquid described in embodiment 2 and titanium dioxide water-dispersion liquid Latex in.The data of gained styrene-butadiene latex product are shown in Table 3, and wherein partial size uses Zetasizer Nano ZS90 (Britain Malvern company) measurement.

Comparative example 6

Embodiment 5 is repeated, but does not use any Zinc oxide water dispersion liquid in the course of the polymerization process, but will be in embodiment 5 The Zinc oxide water dispersion liquid addition is finally filtered in resulting latex.The data of gained styrene-butadiene latex product are shown in Table 3, wherein Partial size is measured using Zetasizer Nano ZS90 (Malvern company, Britain).

Performance test

According to standard listed by table 1, the properties of latex obtained by embodiment and comparative example are tested, test result is shown in Table 2 With table 3.

The standard of the test institute's reference of table 1

Project	Standard used
		Total solid content %	The measurement of SH/T 1154-1999 synthetic rubber latex total solid content
Viscosity mPa.s	The measurement of SH/T 1152-1999 (2005) synthetic latex viscosity
		PH value	The measurement of SH/T 1150-1999 synthetic rubber latex pH
Mechanical stability %	Measurement of the SH/T 1151-1999 synthetic latex to mechanical stability
		Chemical stability %	The measurement of SH/T1608-1995 styrene-butadiene latex calcium ion stability
Lotion germ contamination grade	The inspection of ISO 9252-1989 synthetic latex microorganism
		Leather mildew-proof grade	QB/T4199-2011 Leather mildew-proof performance test methods
Leather pin hole tearing strength	GBT 17928-1999 leather pin hole tearing strength measuring method
		Cardboard interlaminar strength	TEXON TP03:2002

Regenerated leather used is provided by Qingyuan City Yin Jun leather Co., Ltd in test, and the regenerated leather is close with a thickness of 1.60mm Degree is 0.53g/cm³, base weight 920g/m²；Cardboard used is provided by industry fiber Science and Technology Ltd., Dongguan City Xinhua, the cardboard With a thickness of 1.52mm, density 0.53g/cm³, base weight 810g/m²。

Modified butadiene-styrene latex obtained by 2 embodiment of table and properties of product data

Latex obtained by 3 comparative example of table and properties of product data

Claims

Aqueous dispersions, part initiator and the portion of inorganic nanometer oxide comprising softened water, with antibacterial and antimildew function are provided The bottom material for dividing emulsifier, when using redox initiation system, the initiator for including in the bottom material is Redox Initiator body All or part of oxidant constituents in system；

There is provided include styrene, softened water and residual emulsifier monomer emulsion, when using redox initiation system and When the Oxidant section of the initiation system is added in bottom material, also comprising in redox initiation system in the monomer emulsion Remainder oxidant constituents；

Initiator solution of the remaining initiator in softened water, initiator water when using redox initiation system are provided The initiator that solution includes is the reducing agent component in redox initiation system；

A part of monomer emulsion is uniformly mixed in the reactor under an inert atmosphere with the bottom material, gained is mixed It is after object is warming up to 60-75 DEG C, the remaining monomer emulsion, butadiene and the initiator solution is continuous simultaneously respectively It is added, temperature remains 60-95 DEG C during charging, and charging, which finishes, further to be polymerize to get modified butadiene-styrene latex is arrived.

2. the method according to claim 1, wherein when using redox initiation system and causing the Oxidant section of system It also include the remainder oxidant constituents in redox initiation system when being added in bottom material, in the monomer emulsion, The weight ratio for the oxidant constituents added in the oxidant constituents and monomer emulsion added in bottom material at this time is 2:7-4:1.

3. the method according to claim 1, wherein when using redox initiation system and causing the Oxidant section of system It also include the remainder oxidant constituents in redox initiation system when being added in bottom material, in the monomer emulsion, The weight ratio for the oxidant constituents added in the oxidant constituents and monomer emulsion added in bottom material at this time is 1:2-3:2.

4. the method according to claim 1, wherein the aqueous dispersions of the inorganic nanometer oxide with antibacterial and antimildew function include Nano granular of zinc oxide, titanium dioxide nanoparticle and/or nano ceric oxide particle；Inorganic with antibacterial and antimildew function receives The aqueous dispersions of rice oxide also include the inorganic nanometer oxide without antibacterial and antimildew function；And/or inorganic nano oxidation The average grain diameter of composition granule is less than 100nm.

5. method according to claim 4, wherein the inorganic nanometer oxide for not having antibacterial and antimildew function is nanometer titanium dioxide Silicon particle and/or nano-aluminium oxide particle.

6. method according to claim 4, wherein the average grain diameter of inorganic nanometer oxide particle is 20-90nm.

7. method as claimed in one of claims 1-6, wherein the dosage of each material in parts by weight is as follows:

Total soft water: 100 parts；

Inorganic nanometer oxide in the aqueous dispersions of inorganic nanometer oxide with antibacterial and antimildew function: 0.5-8 parts, and If there is the inorganic nanometer oxide without antibacterial and antimildew function in aqueous dispersions, amount is aoxidized no more than inorganic nano 50 weight % of object total amount；

Butadiene: 25-70 parts；

Styrene: 20-75 parts；With

Emulsifier: 0.5-5 parts.

8. method as claimed in one of claims 1-6, wherein the dosage of each material in parts by weight is as follows: total soft water: 100 Part；

Inorganic nanometer oxide in the aqueous dispersions of inorganic nanometer oxide with antibacterial and antimildew function: 0.8-5 parts, and If there is the inorganic nanometer oxide without antibacterial and antimildew function in aqueous dispersions, amount is aoxidized no more than inorganic nano 50 weight % of object total amount；

Butadiene: 35-60 parts；

Styrene: 40-50 parts；With

Emulsifier: 0.6-4 parts.

9. method as claimed in one of claims 1-6, wherein the emulsifier is anion emulsifier, nonionic emulsifier Or the compound emulsifying agent of anion emulsifier and nonionic emulsifier.

10. method according to claim 9, wherein anion emulsifier is one of to be selected from the group or a variety of: C₁₀-C₁₈Alkyl Sulfate type emulsifier, C₈-C₁₈Fatty alcohol ether sulphate type emulsifier, C₁₀-C₁₈Alkyl benzene sulphonate salt form emulsifier, C₈-C₁₈Rouge Fat alcohol ether benzene sulfonate type emulsifier, C₁₀-C₁₈Alkyl sulfonic acid salt form emulsifier, C₈-C₁₈Fatty alcohol ether sulfonate type emulsifier, And/or nonionic emulsifier is one of to be selected from the group or a variety of: Polyoxyethylene Ether, PO-EO block polymer type, poly- Ethylene oxide (20) sorbitan fatty acid ester, sorbitan fatty acid ester.

11. method according to claim 9, wherein anion emulsifier is one of to be selected from the group or a variety of: dodecyl Sodium sulphate, neopelex, fatty alcohol-ether sodium sulfate and disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, and/or, nonionic Emulsion Agent is one of to be selected from the group or a variety of: octyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, isomery decyl alcohol polyoxy second Alkene ether, modified fatty alcohol polyethenoxy ether, fatty alcohol polyoxyethylene ether, PO-EO block polymer, primary alconol polyethers, Tween-60 And/or Arlacel-80.

12. method according to claim 11, wherein fatty alcohol-ether sodium sulfate is C₁₂-C₁₄Fatty alcohol-ether sodium sulfate.

13. method according to claim 11, wherein fatty alcohol-ether sodium sulfate is isomery tridecanol ether sodium sulfate.

14. method as claimed in one of claims 1-6 wherein also includes chelating agent, pH buffer and/or pH tune in bottom material Save agent.

15. method according to claim 14, wherein chelating agent is one of to be selected from the group or a variety of: ethylenediamine tetra-acetic acid, Disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, and/or, pH buffer is one of to be selected from the group or a variety of: carbonic acid Hydrogen salt, carbonate and phosphate, and/or, pH adjusting agent is sodium hydrate aqueous solution and/or ammonia spirit.

16. method according to claim 15, wherein chelating agent is disodium ethylene diamine tetraacetate, and/or, the bicarbonate, Carbonate and phosphate are their own alkali metal salt and ammonium salt.

17. method according to claim 15, wherein the bicarbonate, carbonate and phosphate be their own sodium salt and Sylvite.

18. method according to claim 15, wherein the bicarbonate is sodium bicarbonate and ammonium hydrogen carbonate.

19. method according to claim 12, wherein the dosage of chelating agent is 0.05-1 parts, the softened water based on 100 parts by weight； And/or the dosage of pH buffer is 0.1-2 parts, the softened water based on 100 parts by weight.

20. method according to claim 19, wherein the dosage of chelating agent is 0.1-0.5 parts, the softening based on 100 parts by weight Water；And/or the dosage of pH buffer is 0.2-1 parts, the softened water based on 100 parts by weight.

21. method as claimed in one of claims 1-6 wherein also includes esters of unsaturated carboxylic acids, insatiable hunger in monomer emulsion With carboxylic acid, cross-linking monomer and/or molecular weight regulator.

22. method according to claim 21, wherein esters of unsaturated carboxylic acids is the C of (methyl) acrylic acid₁-C₈Arrcostab or (first Base) acrylic acid hydroxyl C₁-C₈Or mixtures thereof Arrcostab, and/or, unsaturated carboxylic acid is one of to be selected from the group or a variety of: third Olefin(e) acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid, and/or, cross-linking monomer is one of to be selected from the group or a variety of: Divinylbenzene, bis- (methyl) acrylic acid glycol esters and diallyl maleate, and/or, molecular weight regulator is under One of group is a variety of: lauryl mercaptan, mercaptopropionic acid butyl ester, thiuram-disulfide and two isothiocyanic acid esters.

23. method according to claim 22, wherein esters of unsaturated carboxylic acids is methyl acrylate, ethyl acrylate, acrylic acid fourth Ester, 2-ethylhexyl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, methacrylic acid second Ester, butyl methacrylate, hydroxyethyl methacrylate and its any mixture, and/or, molecular weight regulator is dodecyl Mercaptan.

24. method according to claim 22, wherein the softening water inventory based on 100 parts by weight, the dosage of esters of unsaturated carboxylic acids No more than 10 parts；And/or the dosage of unsaturated carboxylic acid is no more than 5 parts；And/or the dosage of cross-linking monomer is no more than 4 parts；With/ Or, the dosage of molecular weight regulator is 0-2 parts.

25. method according to claim 24, wherein the softening water inventory based on 100 parts by weight, the dosage of esters of unsaturated carboxylic acids It is 0-6 parts；And/or the dosage of unsaturated carboxylic acid is 0-4 parts；And/or the dosage of cross-linking monomer is 0-3 parts；And/or molecule The dosage for measuring regulator is 0.1-0.5 parts.

26. method as claimed in one of claims 1-6, the wherein emulsifier in bottom material and the emulsifier in monomer emulsion Weight ratio be 1:9-8:2；And/or the initiator in the initiator and initiator solution in bottom material and monomer emulsion Weight ratio be 1:9-7:3.

27. method according to claim 26, the wherein weight ratio of the emulsifier in bottom material and the emulsifier in monomer emulsion Example is 4:6-7:3；And/or the weight ratio of the initiator in the initiator and initiator solution in bottom material and monomer emulsion Example is 3:7-5:5.

28. method as claimed in one of claims 1-6, wherein initiator is one of to be selected from the group or a variety of: peroxide Compound type initiator and redox type initiator.

29. method according to claim 28, wherein initiator and initiation when using Peroxide type initiator, in bottom material Initiator in agent aqueous solution is identical or different.

30. method as claimed in one of claims 1-6, wherein latex solid content is 30-60 weight %；And/or in latex Emulsion particle average grain diameter be 50-500 nanometers.

31. method according to claim 30, wherein latex solid content is 45-55 weight %；And/or the emulsion particle in latex Average grain diameter be 80-300 nanometers.

32. the modified butadiene-styrene latex obtained by the method as required by any one of claim 1-31.

33. use of the modified butadiene-styrene latex obtained by the method as required by any one of claim 1-31 as adhesive On the way.

34. according to the purposes of claim 33, wherein the modified butadiene-styrene latex is as the viscous of production regenerative leather and/or cardboard Mixture.

35. using the modified butadiene-styrene latex obtained by the method as required by any one of claim 1-31 as adhesive The product of production.

36. being regenerative leather and/or cardboard according to the product of claim 35.