CN102241794B - Preparation method of reversible agglomeration and re-dispersion latex based on amidine compound - Google Patents
Preparation method of reversible agglomeration and re-dispersion latex based on amidine compound Download PDFInfo
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Abstract
The invention discloses a preparation method of a reversible agglomeration and re-dispersion latex based on an amidine compound. In the preparation method, an amidine-containing compound is used as a copolymerization monomer or a reactive emulsifier, a chain transfer agent, an initiator and other additives to be applied in the emulsion polymerization of radically polymerizable monomers to prepare a stable polymer latex, wherein the amidine group is firmly bonded on the surfaces of latex particles by virtue of covalent bonds. The agglomeration of the latex particles of the latex is realized by heating and introducing nitrogen gas or adding a small amount of base solution, and the agglomerated latex particles can be dispersed by introducing carbon dioxide gas to obtain the stable latex. The agglomeration and re-dispersion process is reversible and easy to control.
Description
Technical field
The present invention relates to the preparation method of a kind of reversible coagulation and redispersible latex; Relate in particular to a kind of amidino compounds that will contain as auxiliary agents such as comonomer or reactive emulsifier, chain-transfer agent, initiators, the method for the polymer latex through emulsion polymerization prepared reversible coagulation and redispersion.
Background technology
Synthetic latex is the important component part of polymeric articles, is widely used in industrial circles such as paper, textiles, coating, tackiness agent, sealer, and annual global latex turnout number is in ten million ton.Along with the development of modern science with technology, latex has also obtained application gradually in frontiers such as biomedicine, advanced material, information, has a extensive future.Synthetic latex is in water, to be dispersed into product that the polyreaction of emulsion obtain through tensio-active agent (emulsifying agent) effect through monomer; Wherein water accounts for the 45-60% of latex volume; Even a small amount of highly filled latex; Also moisture about 26-40%, the transportation that the existence of big water gaging increases latex undoubtedly and storage cost, prolongation latex time of drying.Synthetic latex stable extremely important, it directly has influence on the preparation and the use of latex, influences the cohesion of latex and redispersible simultaneously.Patent CN1217733 disclose a kind of in the aqueous solution polymer powders redispersible, this powder in makeup or pharmaceutical prepn or the application in the plant protection preparation and a kind of method that is prepared in polymer powders redispersible in the aqueous solution; This polymer powder contains the multipolymer of free acid radical or base, regulates the redispersion that the pH value realizes latex through before drying, adding buffer reagent.Patent CN1325921 discloses a kind of redispersible synthetic resin powder for preparing the surface adsorption polyvinyl alcohol resin; This powder has fabulous redispersibility, resistance to blocking, film forming properties and water-repellancy, can easily be distributed to the admixture that forms emulsion and also can be used as cement and mortar in the water.Patent CN101173021 discloses a kind of acrylic acid series nucleocapsid polymer emulsion and redispersable latex powder and preparation method thereof, and this redispersable latex powder is by acrylic acid series nucleocapsid polymer emulsion, protective colloid, anti-caking agent, and the spray method through emulsion prepares; Its solid content high (near 100%), the difficulty that can reduce conveying, stores can be used the papery packing; Reduce packing cost, and stability in storage is good, the shelf lives is long; Not can because of water freeze or volatilize go bad; Can in water, dissolve rapidly, homodisperse forms the latax with former matrix polymer emulsion same performance again.Patent CN101168585 discloses a kind of preparation method of hydrophobicity redispersable latex powder; Be by 100 parts of raw emulsions; 4～10 parts of Z 150PH; 3～15 parts of compositions of anti-caking agent can use in building concrete and mortar, can obviously improve workability, water tolerance, the weathering resistance of building concrete, mortar.
Recently, Liu and Jessop etc. has delivered the research report that is entitled as " changeable tensio-active agent " on the Science periodical, and they find through simple, eco-friendly trigger condition, can reversible regulation and control suc as formula 1
The surfactivity of hexadecyl that shows and dodecyl amidine: amidine generates supercarbonate with carbon dioxide reaction in water, have surfactivity; Use nitrogen, argon gas or air to remove carbonic acid gas, amidine loses surfactivity.
The activity (right side) of formula 1. " changeable " amidine class tensio-active agent and inactivation (left side) state:
They use the dodecyl amidine is that tensio-active agent has carried out vinylbenzene water microsuspension, prepares weight average particle diameter and be 17 microns PS fine suspension, and the logical argon gas of fine suspension condenses.But the polymer particle of the report cohesion stable fine suspension of redispersible formation whether; And the particle diameter of microsuspension synthetic polymer particle arrives the micron order scope in submicron; Be different from the latex particle size of letex polymerization synthetic tens, directly the chain alkyl amidine be used for letex polymerization and still have any problem to the hundreds of nanometer.
Summary of the invention
The objective of the invention is to deficiency, a kind of method for preparing reversible coagulation and redispersible latex based on amidine compound is provided to prior art.
The objective of the invention is to realize through following technical scheme:
A kind of method for preparing reversible coagulation and redispersible latex may further comprise the steps:
(1) configuration of monomer emulsion: to contain amidino compounds water-soluble with a certain amount of; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification, the amount that contains amidino compounds is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 55% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion system of step (1), and initiator amount is 0.1 ~ 2% of an emulsion total mass, and heating begins reaction, after reaction for some time, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously; The polymer latex Ruzhong that perhaps obtains toward step (2) adds small amount of alkali solution and reaches 9 ~ 10 to pH, just can realize the cohesion of latex particle, to condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
A kind of method for preparing reversible coagulation and redispersible latex may further comprise the steps:
(1) configuration of monomer emulsion: contain amidino compounds and tensio-active agent is water-soluble with a certain amount of; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification; The amount that contains amidino compounds is 0.1 ~ 5% of a monomer emulsion total mass, and dosage of surfactant is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 55% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion system of step (1), and initiator amount is 0.1 ~ 2% of an emulsion total mass, and heating begins reaction, after reaction for some time, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously; The polymer latex Ruzhong that perhaps obtains toward step (2) adds small amount of alkali solution and reaches 9 ~ 10 to pH, just can realize the cohesion of latex particle, to condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
A kind of method for preparing reversible coagulation and redispersible latex may further comprise the steps:
(1) configuration of monomer emulsion: a certain amount of tensio-active agent is water-soluble; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification, dosage of surfactant is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 55% of a monomer emulsion total mass;
(2) letex polymerization: the initiator that will contain amidino groups joins in the described monomer emulsion system of step (1), and initiator amount is 0.1 ~ 2% of an emulsion total mass, and heating begins reaction, after reaction for some time, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously; The polymer latex Ruzhong that perhaps obtains toward step (2) adds small amount of alkali solution and reaches 9 ~ 10 to pH, just can realize the cohesion of latex particle, to condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
The invention has the beneficial effects as follows: the inventive method contains amidino compounds as auxiliary agents such as comonomer or reactive emulsifier, chain-transfer agent, initiators through use; Use it for the letex polymerization of vinylbenzene or vinyl acetate or (methyl) acrylic ester monomer; Prepare stable polymer latex, make amidine group through the covalent linkage form firm be combined in the latex particle surface.This latex can be realized the cohesion of latex particle through heating logical nitrogen or adding small amount of alkali solution, and the latex particle of cohesion can realize that redispersion be stable latex through logical dioxide gas.The process of this cohesion-redispersion is reversible, and control easily.Therefore, utilize the present invention can prepare the polymer latex of reversible coagulation and redispersion very easily.
Embodiment
Conventional surfactants in the letex polymerization normally is enriched in the surface of polymer particle by physical adsorption; When latex cohesion takes place or receives high-shear, freeze-thaw cycle to do the time spent; Particle surface emulsifying agent layer can be affected; Desorb takes place and come off, thus the stability of influence cohesion post polymerization thing particle restorability again.Therefore,, make surface active groups, can satisfy the requirement that realizes latex reversible coagulation and redispersion not because of the cohesion of latex breaks away from particle surface if can tensio-active agent stably be combined in the surface of polymer particle.
For this reason; The present invention proposes to use through design and contains amidino compounds as auxiliary agents such as comonomer or reactive emulsifier, chain-transfer agent, initiators; Use it for the letex polymerization of vinylbenzene or vinyl acetate or (methyl) acrylic ester monomer; Prepare stable polymer latex, make amidine group through the covalent linkage form firm be combined in the latex particle surface.Like this, the synthetic polymer latex can be realized the cohesion of latex particle through heating logical nitrogen or adding small amount of alkali solution, and the latex particle of cohesion can realize that redispersion be stable latex through logical dioxide gas.The process of this cohesion-redispersion is reversible, and control easily.
The present invention prepares the polymer latex of reversible coagulation and redispersion through following three kinds of methods.
Wherein, method one may further comprise the steps:
(1) configuration of monomer emulsion: with a certain amount of contain amidino compounds water-soluble after; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification; Obtain monomer emulsion, the amount that contains amidino compounds is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 40% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion of step (1); Initiator amount is 0.1 ~ 0.5% of a monomer emulsion quality; Heating begins reaction; Polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9 ~ 10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
Method two may further comprise the steps:
(1) configuration of monomer emulsion: with a certain amount of contain amidino compounds and tensio-active agent water-soluble after; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification; The amount that contains amidino compounds is 0.1 ~ 5% of a monomer emulsion total mass, and dosage of surfactant is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 40% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion system of step (1); Initiator amount is 0.1 ~ 0.5% of an emulsion total mass; Heating begins reaction; Polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9 ~ 10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
Method three comprises following steps:
(1) configuration of monomer emulsion: a certain amount of tensio-active agent is water-soluble; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification, dosage of surfactant is 0.1 ~ 5% of a monomer emulsion total mass, and monomer mass is 10 ~ 40% of a monomer emulsion total mass;
(2) letex polymerization: the initiator that will contain amidino groups joins in the described monomer emulsion system of step (1); Initiator amount is 0.1 ~ 0.5% of an emulsion total mass; Heating begins reaction; Polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9 ~ 10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
More than three kinds of methods contain amidino compounds as auxiliary agents such as comonomer or reactive emulsifier, chain-transfer agent, initiators through use; Use it for monomeric letex polymerizations such as vinylbenzene, vinyl carboxylates, esters of acrylic acid, methyl acrylic ester, divinyl, isoprene, chloroprene,
-vinyl toluene, vinylchlorid, vinylidene chloride, vinyl cyanide, vinylformic acid, methylacrylic acid, maleic anhydride, alkyl vinyl ether; Prepare stable polymer latex, make amidine group through the covalent linkage form firm be combined in the latex particle surface.In the said method one, not extra adding emulsifying agent contains amidino compounds and can be used as comonomer or chain-transfer agent or reactive emulsifier, and polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours; In the said method two, a certain amount of emulsifying agent of extra adding contains amidino compounds and can be used as comonomer or chain-transfer agent or reactive emulsifier, and polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours; In the said method three, a certain amount of emulsifying agent of extra adding contains the initiator initiated polymerization of amidino compounds as letex polymerization, and polymerization temperature is controlled between 40 ~ 80 ℃, and the reaction times was controlled at 4 ~ 12 hours.The polymer latex that three kinds of methods prepare all can be through heating logical nitrogen or add the cohesion that small amount of alkali solution realized latex particle, and the latex particle of cohesion can realize that redispersion be stable latex through logical dioxide gas.The process of this cohesion-redispersion is reversible, and control easily.Therefore, utilize the present invention can prepare the polymer latex of reversible coagulation and redispersion very easily.
Step (1) neutralization of said method one and method two contains amidino compounds and comprises and contain the amidino groups comonomer, contain amidino groups polymerizable type tensio-active agent, contain amidino groups chain-transfer agent etc.Its concrete structure formula is shown in table 1-3.
The amidino compounds that contains in the step of said method three (2) is the initiator as letex polymerization, and its concrete structure formula is as shown in table 4.
Said method one; Monomer in the step of method two and method three (1) is a vinylbenzene; Vinyl carboxylates; Esters of acrylic acid; Methyl acrylic ester; Divinyl; Isoprene; Chloroprene;
-vinyl toluene; Vinylchlorid; Vinylidene chloride; Vinyl cyanide; Vinylformic acid; Methylacrylic acid; Maleic anhydride; Alkyl vinyl ether etc.
Tensio-active agent comprises cationic emulsifier, nonionic emulsifier etc. in the step of said method two and method three (1); Described cationic emulsifier has kiber alkyl amine salt, alkyl secondary amine salt, alkyl quaternary ammonium salts, ether structure quaternary ammonium salt, amide structure quaternary ammonium salt, heterocycle structure quaternary ammonium salt, alkyl biguanide hydrochloride etc.; Described nonionic emulsifier has polyoxyethylene carboxylic ester's class, polyol carboxylate's class, polyoxyethylene polyols carboxylic acid esters Voranol EP 2001, polyoxyethylene alkylaryl ether etc.
Initiator in said method one and the method two step (2) comprises chemical initiator, photochemical initiators etc.; Described chemical initiator has azo-initiator; Comprise 4, said photochemical initiators such as 4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate, azo di-isopropyl tetrahydroglyoxaline are 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone etc.
Alkaline solution in the step (3) of said method one, method two and method three is sodium hydroxide solution, potassium hydroxide solution, aqua calcis, ammoniacal liquor, sodium carbonate solution etc.
The solid content 10 ~ 55% of the reversible coagulation that finally obtains and the polymer latex of redispersion.
Further specify the present invention program and result through specific embodiment below, but can not think that the present invention only limits among these embodiment.In an embodiment, remove specified otherwise, all marks and percentage ratio all are weight ratios.
Embodiment 1
(1) in the 50ml there-necked flask, adds 0.125 part and contain amidino compounds M-B2 (n=1) as comonomer, 19 parts of deionized waters, mechanical stirring;
(2) 5 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.094 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in 1 part of deionized water and add initiated polymerization in the monomer emulsion;
(4) reacted 8 hours stopped reaction down at 70 ℃;
(5) polymer latex that obtains is regulated pH to 9 ~ 10 with a small amount of 0.1M aqueous sodium hydroxide solution, and its latex particle is condensed, and logical dioxide gas and the ultrasonic latex particle that makes disperse to obtain stable polymer latex again.
The transformation efficiency of the final styrene monomer of polymerization system is 94.3%, and the transformation efficiency that comonomer contains amidino compounds M-B2 (n=1) is 100%.Adopt gel permeation chromatography (GPC) to measure the molecular weight and the heterogeneity index of polymkeric substance, its weight-average molecular weight is 85kD, and MWD is 11.5.Employing scattering of light laser particle analyzer is measured the particle diameter of latex particle, and the equal particle diameter of latex particle Z before the cohesion is 128.7nm, and the equal particle diameter of latex particle Z that redispersion obtains after three cohesions is respectively 138.8nm, 151.3nm, 147.4nm.Explain that the polymer latex for preparing with said method one has good reversible coagulation and redispersion ability.
Embodiment 2
(1) in the 50ml there-necked flask, adding 0. 25 parts contains amidino compounds S-A5 (n=8 is m=0) as response type surfactant active, 19 parts of deionized waters, mechanical stirring;
(2) 5 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.094 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in 1 part of deionized water and add initiated polymerization in the monomer emulsion;
(4) reacted 5 hours stopped reaction down at 65 ℃;
(5) polymer latex that obtains descended logical nitrogen 0.5 hour at 70 ℃, and its latex particle is condensed, and logical dioxide gas and the ultrasonic latex particle that makes disperse to obtain stable polymer latex again.
The transformation efficiency of the final styrene monomer of polymerization system is 97.6%.Adopt gel permeation chromatography (GPC) to measure the molecular weight and the heterogeneity index of polymkeric substance, its weight-average molecular weight is 512kD, and MWD is 2.7.Employing scattering of light laser particle analyzer is measured the particle diameter of latex particle, and the equal particle diameter of latex particle Z before the cohesion is 102.6nm, and the equal particle diameter of latex particle Z that redispersion obtains after three cohesions is respectively 155.4nm, 160.3nm, 163.7nm.Explain that the polymer latex for preparing with said method one has good reversible coagulation and redispersion ability.
Embodiment 3
(1) in the 50ml there-necked flask, adding 0.125 part, to contain amidino compounds M-B2 (n=1) be tensio-active agent, 19 parts of deionized waters as comonomer, 0.125 part of dodecyl amine hydrochlorate, mechanical stirring;
(2) 5 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.047 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in 1 part of deionized water and add initiated polymerization in the monomer emulsion;
(4) reacted 8 hours stopped reaction down at 70 ℃;
(5) polymer latex that obtains can make its latex particle condense with a small amount of 0.1M aqueous sodium hydroxide solution, and logical dioxide gas and the ultrasonic latex particle that makes disperse to obtain stable polymer latex again.
The transformation efficiency of the final styrene monomer of polymerization system is 99.9%, and the transformation efficiency that comonomer contains amidino compounds M-B2 (n=1) is 100%.Employing scattering of light laser particle analyzer is measured the particle diameter of latex particle, and the equal particle diameter of latex particle Z before the cohesion is 77.2nm, and the equal particle diameter of latex particle Z that redispersion obtains after three cohesions is respectively 87.6nm, 90.0nm, 89.3nm.Explain that the polymer latex for preparing with said method two has good reversible coagulation and redispersion ability.
Embodiment 4
(1) in the 50ml there-necked flask, adding 0.075 part of dodecyl amine hydrochlorate is tensio-active agent, 20 parts of deionized waters, mechanical stirring;
(2) 4 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.125 part and contain amidino compounds, after the logical dioxide gas of adding 1mL deionized water dissolves to it fully, be added to initiated polymerization in the monomer emulsion as initiator In4;
(4) reacted 8 hours stopped reaction down at 70 ℃;
(5) polymer latex that obtains is regulated pH to 9 ~ 10 with the 0.1M aqueous sodium hydroxide solution, and its latex particle is condensed, and logical dioxide gas and the ultrasonic latex particle that makes disperse to obtain stable polymer latex again.
The transformation efficiency of the final styrene monomer of polymerization system is 90.4 %.Employing scattering of light laser particle analyzer is measured the particle diameter of latex particle, and the equal particle diameter of latex particle Z before the cohesion is 82.0nm, and the equal particle diameter of latex particle Z that redispersion obtains after three cohesions is respectively 103.2nm, 110.3nm, 108.4nm.Explain that the polymer latex for preparing with said method three has good reversible coagulation and redispersion ability.
Embodiment 5
(1) in the 50ml there-necked flask, adding 0.125 part, to contain amidino compounds M-B2 (n=1) be tensio-active agent, 19 parts of deionized waters as comonomer, 0.125 part of dodecyl amine hydrochlorate, mechanical stirring;
(2) 12 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.094 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in 1 part of deionized water and add initiated polymerization in the monomer emulsion;
(4) reacted 8 hours stopped reaction down at 70 ℃;
(5) polymer latex that obtains can make its latex particle condense with a small amount of 0.1M aqueous sodium hydroxide solution, and logical dioxide gas and the ultrasonic latex particle that makes disperse to obtain stable polymer latex again.
The equal particle diameter of latex particle Z that redispersion obtains after three cohesions is more or less the same with the preceding equal particle diameter of latex particle Z of cohesion, explains that the polymer latex for preparing with said method two has good reversible coagulation and redispersion ability.
Comparative Examples 1
(1) in the 50ml there-necked flask, adding 0.125 part of dodecyl amine hydrochlorate is tensio-active agent, 20 parts of deionized waters, mechanical stirring;
(2) 5 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.047 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in the less water and add initiated polymerization in the monomer emulsion;
(4) reacted 8 hours stopped reaction down at 70 ℃;
The transformation efficiency of the final styrene monomer of polymerization system is 92.8%.Adopt gel permeation chromatography (GPC) to measure the molecular weight and the heterogeneity index of polymkeric substance, its weight-average molecular weight is 349kD, and MWD is 7.4.Adopt the scattering of light laser particle analyzer to measure the particle diameter of latex particle, the equal particle diameter of its Z is 74.4 nm.The polymer latex that obtains is regulated pH to 9 ~ 10 with the 0.1M aqueous sodium hydroxide solution, and its latex particle is condensed, but logical dioxide gas and the ultrasonic latex particle that can't make disperse to obtain stable polymer latex again.Explain that the polymer latex that this method prepares can't realize reversible coagulation and redispersion.
Comparative Examples 2
(1) in the 50ml there-necked flask, adding 0.125 part of dodecyl amine hydrochlorate is tensio-active agent, 20 parts of deionized waters, mechanical stirring;
(2) 5 parts of monomer styrenes are added in the solution of step (1), letting nitrogen in and deoxidizing led to dioxide gas after 15 minutes;
(3) take by weighing 0.094 part of azo di-isopropyl imidazoline salt hydrochlorate (V-50), be dissolved in the less water and add initiated polymerization in the monomer emulsion;
(4) reacted 8 hours stopped reaction down at 70 ℃;
The transformation efficiency of the final styrene monomer of polymerization system is 96.7%.Adopt gel permeation chromatography (GPC) to measure the molecular weight and the heterogeneity index of polymkeric substance, its weight-average molecular weight is 184kD, and MWD is 7.1.Adopt the scattering of light laser particle analyzer to measure the particle diameter of latex particle, the equal particle diameter of its Z is 73.5 nm.The polymer latex that obtains is regulated pH to 9 ~ 10 with the 0.1M aqueous sodium hydroxide solution, and its latex particle is condensed, but logical dioxide gas and the ultrasonic latex particle that can't make disperse to obtain stable polymer latex again.Explain that the polymer latex that this method prepares can't realize reversible coagulation and redispersion.
Comprehensive the foregoing description and Comparative Examples are visible; The inventive method contains amidino compounds as auxiliary agents such as comonomer or reactive emulsifier, chain-transfer agent, initiators through use; Use it for the letex polymerization of free radical polymerizable monomer; Prepare stable polymer latex, make amidine group through the covalent linkage form firm be combined in the latex particle surface.This latex can be realized the cohesion of latex particle through heating logical nitrogen or adding small amount of alkali solution, and the latex particle of cohesion can realize that redispersion be stable latex through logical dioxide gas.The process of this cohesion-redispersion is reversible, and control easily.Therefore, utilize the present invention can prepare the polymer latex of reversible coagulation and redispersion very easily.
The foregoing description is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
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Table 1. contains the chemical structural formula of amidino compounds as comonomer
Table 2. contains the chemical structural formula of amidino compounds as polymerizable type tensio-active agent
Table 3. contains the chemical structural formula of amidino compounds as chain-transfer agent
Table 4. contains the chemical structural formula of amidino compounds as initiator
Claims (8)
1. a method for preparing reversible coagulation and redispersible latex is characterized in that, this method may further comprise the steps:
(1) configuration of monomer emulsion: with a certain amount of contain amidino compounds water-soluble after; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification; Obtain monomer emulsion, the amount that contains amidino compounds is 0.1～5% of a monomer emulsion total mass, and monomer mass is 10～40% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion of step (1); Initiator amount is 0.1～0.5% of a monomer emulsion quality; Heating begins reaction; Polymerization temperature is controlled between 40～80 ℃, and the reaction times was controlled at 4～12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9～10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
2. a method for preparing reversible coagulation and redispersible latex is characterized in that, this method may further comprise the steps:
(1) configuration of monomer emulsion: with a certain amount of contain amidino compounds and tensio-active agent water-soluble after; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification; The amount that contains amidino compounds is 0.1～5% of a monomer emulsion total mass, and dosage of surfactant is 0.1～5% of a monomer emulsion total mass, and monomer mass is 10～40% of a monomer emulsion total mass;
(2) letex polymerization: initiator is joined in the described monomer emulsion system of step (1); Initiator amount is 0.1～0.5% of an emulsion total mass; Heating begins reaction; Polymerization temperature is controlled between 40～80 ℃, and the reaction times was controlled at 4～12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9～10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
3. a method for preparing reversible coagulation and redispersible latex is characterized in that, this method may further comprise the steps:
(1) configuration of monomer emulsion: a certain amount of tensio-active agent is water-soluble; Disposable or add a certain amount of monomer gradually; Fully stir preparatory emulsification, dosage of surfactant is 0.1～5% of a monomer emulsion total mass, and monomer mass is 10～40% of a monomer emulsion total mass;
(2) letex polymerization: the initiator that will contain amidino groups joins in the described monomer emulsion system of step (1); Initiator amount is 0.1～0.5% of an emulsion total mass; Heating begins reaction; Polymerization temperature is controlled between 40～80 ℃, and the reaction times was controlled at 4～12 hours, just can obtain the polymer latex of high conversion;
(3) reversible coagulation of polymer latex and redispersion: logical nitrogen, argon gas or air toward the polymer latex Ruzhong that step (2) obtains, heating simultaneously realizes the cohesion of latex particle; Perhaps add small amount of alkali solution and reach 9～10, the cohesion of realization latex particle to pH toward the polymer latex Ruzhong that step (2) obtains; To condensed latex in logical dioxide gas, can realize that just redispersion is stable latex.
4. according to claim 1 or the said method for preparing reversible coagulation and redispersible latex of claim 2; It is characterized in that; In the said step (1), contain amidino compounds for containing the amidino groups comonomer, contain amidino groups polymerizable type tensio-active agent or containing the amidino groups chain-transfer agent.
5. according to the said method for preparing reversible coagulation and redispersible latex of claim 1, claim 2 or claim 3; It is characterized in that the monomer in the said step (1) is vinylbenzene, vinyl carboxylates, esters of acrylic acid, methyl acrylic ester, divinyl, isoprene, chloroprene, alpha-methyl styrene, vinylchlorid, vinylidene chloride, vinyl cyanide, vinylformic acid, methylacrylic acid, maleic anhydride or alkyl vinyl ether.
6. according to claim 2 or the said method for preparing reversible coagulation and redispersible latex of claim 3, it is characterized in that in the said step (1), said tensio-active agent comprises cationic emulsifier, nonionic emulsifier and amphoteric emulsifier; Described cationic emulsifier is kiber alkyl amine salt, alkyl secondary amine salt, alkyl quaternary ammonium salts, ether structure quaternary ammonium salt, amide structure quaternary ammonium salt, heterocycle structure quaternary ammonium salt or alkyl biguanide hydrochloride; Described nonionic emulsifier is polyoxyethylene carboxylic ester's class, polyol carboxylate's class, polyoxyethylene polyols carboxylic acid esters Voranol EP 2001 or polyoxyethylene alkylaryl ether; Described amphoteric emulsifier is carboxylic-acid, sulfuric acid ester, phosphoric acid ester or sulfonic acid class.
7. according to claim 1 or the said method for preparing reversible coagulation and redispersible latex of claim 2, it is characterized in that the initiator in the said step (2) comprises chemical initiator and photochemical initiators; Described chemical initiator is 4,4 '-azo two (4-cyanopentanoic acid), azo diisobutyl amidine hydrochlorides, azo di-isopropyl imidazoline salt hydrochlorate or azo di-isopropyl tetrahydroglyoxaline; Said photochemical initiators is 2-hydroxyl-1-[4-(hydroxyl) phenyl]-2-methyl isophthalic acid-acetone.
8. according to the said method for preparing reversible coagulation and redispersible latex of claim 1, claim 2 or claim 3; It is characterized in that; In the said step (3), said alkaline solution is sodium hydroxide solution, potassium hydroxide solution, aqua calcis, ammoniacal liquor or sodium carbonate solution.
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