CN102199259B - Nano modified chlorinated polyether resin with core-shell structure and preparation method thereof - Google Patents
Nano modified chlorinated polyether resin with core-shell structure and preparation method thereof Download PDFInfo
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- CN102199259B CN102199259B CN 201110086740 CN201110086740A CN102199259B CN 102199259 B CN102199259 B CN 102199259B CN 201110086740 CN201110086740 CN 201110086740 CN 201110086740 A CN201110086740 A CN 201110086740A CN 102199259 B CN102199259 B CN 102199259B
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Abstract
The invention discloses a nano modified chlorinated polyether resin with a core-shell structure and a preparation method thereof. In the nano modified chlorinated polyether resin, a chlorinated polyether resin is used as a polymer substrate, and nano particles modified by a coupling agent are evenly distributed in the polymer substrate. The preparation method comprises the following steps: firstly, carrying out surface modification on the nano particles by utilizing the coupling agent; then adding vinyl chloride and vinyl isobutyl ether monomers and coating the nano particles through a water-phase micro-suspension polymerization method, so as to obtain the nano modified chlorinated polyether resin with the core-shell structure. According to the invention, environment pollution dose not occur, the operation is safe and simple, the product has the advantages of high yield, high purity and stable quality and property, and the preparation method is suitable for industrial production.
Description
One, technical field
The present invention relates to a kind of nano composite material and preparation method thereof, specifically a kind of nano modification chlorinated polyether resin and preparation method thereof with nucleocapsid structure.
Two, background technology
Inorganic nano-particle can significantly improve polymer properties, and therefore, nanoparticle-polymkeric substance compounding technology has obtained developing widely and using.Chlorinated polyether resin is a kind of chlorine-containing polymer that is formed by 75% vinylchlorid and 25% vinyl isobutyl ether copolymerization; Its production technique environmentally safe; Antiseptic property is very excellent, therefore chlorinated polyether resin has been widely used in the surface anticorrosive coating of member abroad, to replace general chlorinated rubber.Nanoparticle is because the singularity of its surface and structure; Can produce special effectses such as UVA, bacterinertness; If nanoparticle and chlorinated polyether resin are prepared into nanoparticle-chlorinated polyether resin matrix material, then can significantly improve performances such as the mechanical property of chlorinated polyether resin, anti-liquid medium and weathering resistance.
In recent years, comparatively rare about the research of nano modification chlorinated polyether resin.Xu Xiaoying (Xu Xiaoying, to refined, Li Yan etc. nano-TiO
2The preliminary study [J] of slurry modification chlorinated polyether resin corrosion protection coating. material protection, 2004,37 (8): 24-26) and to refined (to refined, Zhang Shengtao, Li Yan etc. rutile type nano TiO
2The research [J] of slurry modification chlorinated polyether resin corrosion protection coating. electrochemistry; 2005; 11 (4): 393-397) wait human nano titania slurry modification chlorinated polyether resin; Its method of modifying be earlier with rutile type nano titanic oxide in organic solvent high speed decentralized system form slurry, disperse with sand milling dispersion machine high-speed stirring with chlorinated polyether resin solution again, thereby the realization nano titanium oxide is to the modification of chlorinated polyether resin.The advantage of this method is that preparation technology is simple, and is easy to operate, and the corrosion resistance nature of chlorinated polyether resin corrosion protection coating has obtained raising to a certain degree; Its shortcoming is: the simple physics blend is difficult to nano titanium oxide is evenly dispersed in the chlorinated polyether resin matrix, and the performance of the performance of nano titanium oxide is suppressed, thereby has limited the application of this nano modification chlorinated polyether resin in high-tech sector.
Three, summary of the invention
The present invention aims to provide a kind of nano modification chlorinated polyether resin with nucleocapsid structure and preparation method thereof.The technical issues that need to address are that nano particle is dispersed in the resin matrix uniformly.
Thinking of the present invention is before polyreaction, to add the nanoparticle after the surface-treated in the reaction system; Make monomer at the nanoparticle surface polymerization reaction take place; Formation has the nano particle-polymer composites of nucleocapsid structure, thereby realizes that nanoparticle combines with polymkeric substance with the form of chemical bond.The method of utilizing polymerization to coat is carried out nano modification to chlorinated polyether resin, can farthest solve the agglomeration traits of nanoparticle, realizes nanoparticle good dispersion in polymkeric substance.
Technical solution problem of the present invention adopts following technical scheme:
A kind of characteristics with nano modification chlorinated polyether resin of nucleocapsid structure of the present invention are: be polymeric matrix with the chlorinated polyether resin, in said polymeric matrix, be uniformly distributed with coupling agent modified nano particle; The mass ratio of said nano particle and chlorinated polyether resin is 1-2: 100;
Said nano particle is silicon-dioxide, titanium oxide or lime carbonate; The particle diameter of said nano particle is 50-150nm.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure are: at first with coupling agent nano particle is carried out surface-treated; Add vinylchlorid and vinyl isobutyl ether monomer then; Through water microsuspension method nano particle is coated, obtain having the nano modification chlorinated polyether resin of nucleocapsid structure.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure also are: said coupling agent is a silane coupling agent.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure also are: said silane coupling agent is γ-methacryloxypropyl trimethoxy silane.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure also are to operate according to the following steps:
A, surface-treated
In coupling agent, add organic solvent and deionized water; Adjust pH is 8.5-9.0; Stirring at room added nano particle after 30 minutes, and in 45-50 ℃ of ultra-sonic dispersion 1.5-2 hour, the constant stirring of holding temperature was 3-10 hour behind the ultra-sonic dispersion; Then 80 ℃ down dry 6-8 hour powder, obtain modified nanoparticles after, the drying also centrifugal with the said powder of organic solvent washing;
The mass ratio of said nano particle and said coupling agent is 1: 1-3;
The mass ratio of said nano particle and described deionized water is 1: 1-2.5;
Said organic solvent is absolute ethyl alcohol, Virahol or N, dinethylformamide;
B, coating
The modified nanoparticles that step a is obtained adds in the deionized water, and ultra-sonic dispersion 1.5-2 hour, the quality of said deionized water was 100-150 a times of said modified nanoparticles quality; Add vinylchlorid, vinyl isobutyl ether, initiator, dispersion agent, emulsifying agent and buffer reagent then; In 70-85 ℃ of stirring reaction 7-10 hour; Reaction finishes after-filtration; And, promptly got nano modification chlorinated polyether resin in 10 hours with nucleocapsid structure 35-45 ℃ of following vacuum-drying with deionized water wash 2-3 time;
The mass ratio of said modified nanoparticles, vinylchlorid and vinyl isobutyl ether is 1-2: 60-75: 25-40;
Said initiator is peroxide initiator or azo-initiator, and add-on is the 0.75-1% of vinylchlorid and vinyl isobutyl ether total mass;
Said dispersion agent is Z 150PH or hydroxypropylcellulose, and add-on is the 0.075-0.4% of vinylchlorid and vinyl isobutyl ether total mass;
Said emulsifying agent is an anionic emulsifier, and add-on is the 0.075-0.2% of vinylchlorid and vinyl isobutyl ether total mass;
Said buffer reagent is water soluble carbonate, supercarbonate, phosphoric acid salt or hydrophosphate, and add-on is the 2-4.5% of vinylchlorid and vinyl isobutyl ether total mass.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure also are: said peroxide initiator is dilauroyl peroxide, Lucidol or the Lucidol tert-butyl ester; Said azo-initiator is Diisopropyl azodicarboxylate or ABVN.
Preparing method's the characteristics that the present invention has the nano modification chlorinated polyether resin of nucleocapsid structure also are: said anionic emulsifier is sodium lauryl sulphate, sodium laurylsulfonate, X 2073, StNa or sodium dibutyl naphthalene sulfonate.
Compared with present technology, beneficial effect of the present invention is embodied in:
1, the present invention has realized the chemically bonded of chlorinated polyether resin and nano particle, and nano particle is evenly dispersed in the resin.
2, the adding of nano particle among the present invention has improved monomeric transformation efficiency effectively, and the yield of product obviously improves, and has shortened the reaction times, makes this method be applicable to industrial production more.
3, through the chlorinated polyether resin of nano modification, on mechanical property and antiseptic property, compare with unmodified chlorinated polyether resin, have significantly and improve.
4, method used in the present invention, the surface modification technology of nano particle and the synthesis technique of resin all do not contain environment and the deleterious solvent of personnel health, whole process flow safety, environmental protection.
5, the nano-silicon dioxide modified chlorinated polyether resin with nucleocapsid structure that the present invention prepares can be widely used in a lot of fields such as coating, printing ink and sizing agent, particularly has very high using value in this material protection field of protective system.
Four, description of drawings
Fig. 1 is the nanometer SiO of embodiment 1 preparation
2The transmission electron microscope photo of modification chlorinated polyether resin.
Fig. 2 is the nano-TiO of embodiment 4 preparations
2The transmission electron microscope photo of modification chlorinated polyether resin.
Five, embodiment
Embodiment 1:
The nanometer SiO that has nucleocapsid structure in the present embodiment
2The modification chlorinated polyether resin prepares by following method:
A, surface-treated
In there-necked flask, add 4g γ-methacryloxypropyl trimethoxy silane, 200g absolute ethyl alcohol and 6.3g deionized water, use ammoniacal liquor to regulate the pH value and be 8.5-9.0, stir adding 4g nanometer SiO after 30 minutes under the room temperature
2(particle diameter 50nm) places ultrasonic pond with there-necked flask, is warming up to 45 ℃; Ultra-sonic dispersion 2 hours, holding temperature is constant, continues to stir 8 hours; Then reaction solution was got powder down in dry 6 hours at 80 ℃; With absolute ethanol washing powder and centrifugal, dry, repeated washing, centrifugal, dry three times, obtain modified Nano SiO
2
B, coating
The modified Nano SiO that step a is obtained
2Add in the 400g deionized water, ultra-sonic dispersion 1.5 hours is then with nanometer SiO
2Aqueous dispersions place autoclave; Add 120g vinylchlorid, 80g vinyl isobutyl ether, 1.5g dilauroyl peroxide, 0.5g hydroxypropylcellulose, 0.15g X 2073 and 4g sodium hydrogencarbonate again; Under agitation slowly be warming up to 70-75 ℃ of polymerase 17 hour; Reaction finishes after-filtration, and with deionized water wash 3 times, promptly gets the nanometer SiO that the milky white granules shape has nucleocapsid structure in 10 hours 45 ℃ of following vacuum-dryings
2The modification chlorinated polyether resin.
The nanometer SiO of present embodiment preparation
2The transmission electron microscope photo of modification chlorinated polyether resin is seen Fig. 1.Can find out that by Fig. 1 the nano modification chlorinated polyether resin of preparing is nucleocapsid structure, promptly nano silicon is nuclear, coated with uniform chlorinated polyether resin.The polymer beads particle diameter is 80-100nm, and the nano silicon particle diameter of coating is 50nm.
Embodiment 2:
The nanometer CaCO that has nucleocapsid structure in the present embodiment
3The modification chlorinated polyether resin prepares by following method:
A, surface-treated
In there-necked flask, add 6g γ-methacryloxypropyl trimethoxy silane, 200g Virahol and 8.5g deionized water, use ammoniacal liquor to regulate the pH value and be 8.5-9.0, stir adding 4g nanometer CaCO after 30 minutes under the room temperature
3(particle diameter 50nm) places ultrasonic pond with there-necked flask, is warming up to 45 ℃; Ultra-sonic dispersion 2 hours, holding temperature is constant, continues to stir 10 hours; Then with reaction solution dry powders that get under 80 ℃; With washed with isopropyl alcohol powder and centrifugal, dry, repeated washing, centrifugal, dry three times, obtain modified Nano CaCO
3
B, coating
The modified Nano CaCO that step a is obtained
3Add in the 450g deionized water, ultra-sonic dispersion 2 hours is then with nanometer CaCO
3Aqueous dispersions place autoclave; Add 120g vinylchlorid, 80g vinyl isobutyl ether, 1.5g Lucidol, 0.15g Z 150PH, 0.2g sodium laurylsulfonate and 4.5g sodium hydrogen phosphate again; Under agitation slowly be warming up to 70-75 ℃ of polymerase 17 hour; Reaction finishes after-filtration, and with deionized water wash 3 times, promptly gets the nanometer CaCO that the milky white granules shape has nucleocapsid structure in 10 hours 45 ℃ of following vacuum-dryings
3The modification chlorinated polyether resin.
Embodiment 3:
The nanometer SiO that has nucleocapsid structure in the present embodiment
2The modification chlorinated polyether resin prepares by following method:
A, surface-treated
In there-necked flask, add 12g γ-methacryloxypropyl trimethoxy silane, 200gN, dinethylformamide and 4g deionized water use ammoniacal liquor to regulate the pH value and are 8.5-9.0, stir under the room temperature to add 4g nanometer SiO after 30 minutes
2(particle diameter 100nm) places ultrasonic pond with there-necked flask, is warming up to 45 ℃; Ultra-sonic dispersion 1.5 hours, holding temperature is constant, continues to stir 10 hours; With reaction solution dry powders that get under 80 ℃, use N then, dinethylformamide washing powder is also centrifugal, dry; Repeated washing, centrifugal, dry three times obtain modified Nano SiO
2
B, coating
The modified Nano SiO that step a is obtained
2Add in the 500g deionized water, ultra-sonic dispersion 1.5 hours is then with nanometer SiO
2Aqueous dispersions place autoclave; Add 140g vinylchlorid, 60g vinyl isobutyl ether, 2g Diisopropyl azodicarboxylate, 0.5g hydroxypropylcellulose, 0.2g sodium lauryl sulphate and 6g sodium hydrogencarbonate again; Under agitation slowly be warming up to 80-85 ℃ of polymerase 17 hour; Reaction finishes after-filtration, and with deionized water wash 3 times, promptly gets the nanometer SiO that the milky white granules shape has nucleocapsid structure in 10 hours 40 ℃ of following vacuum-dryings
2The modification chlorinated polyether resin.
Embodiment 4:
The nano-TiO that has nucleocapsid structure in the present embodiment
2The modification chlorinated polyether resin prepares by following method:
A, surface-treated
In there-necked flask, add 8g γ-methacryloxypropyl trimethoxy silane, 200g absolute ethyl alcohol and 10g deionized water, use ammoniacal liquor to regulate the pH value and be 8.5-9.0, stir adding 4g nano-TiO after 30 minutes under the room temperature
2(particle diameter 150nm) places ultrasonic pond with there-necked flask, is warming up to 45 ℃; Ultra-sonic dispersion 1.5 hours, holding temperature is constant, continues to stir 9 hours; Then with reaction solution dry powders that get under 80 ℃; With absolute ethanol washing powder and centrifugal, dry, repeated washing, centrifugal, dry three times, obtain modified Nano TiO
2
B, coating
The modified Nano TiO that step a is obtained
2Add in the 600g deionized water, ultra-sonic dispersion 2 hours is then with nano-TiO
2Aqueous dispersions place autoclave; Add 150g vinylchlorid, 50g vinyl isobutyl ether, 1.8g ABVN, 0.8g hydroxypropylcellulose, 0.4g StNa and 9g sodium hydrogencarbonate again; Under agitation slowly be warming up to 80-85 ℃ of polymerization 10 hours; Reaction finishes after-filtration, and with deionized water wash 3 times, promptly gets the nano-TiO that the milky white granules shape has nucleocapsid structure in 10 hours 35 ℃ of following vacuum-dryings
2The modification chlorinated polyether resin.
The nano-TiO of present embodiment preparation
2The transmission electron microscope photo of modification chlorinated polyether resin is seen Fig. 2.Can find out that by Fig. 2 the nano modification chlorinated polyether resin of preparing is nucleocapsid structure, promptly nano titanium oxide is nuclear, coated with uniform chlorinated polyether resin.The polymer beads particle diameter is 220-250nm, and the nano titanium oxide particle diameter of coating is 150nm.
Claims (4)
1. preparation method with nano modification chlorinated polyether resin of nucleocapsid structure; It is characterized in that: at first nano particle is carried out surface-treated with coupling agent; Add vinylchlorid and vinyl isobutyl ether monomer then; Through water microsuspension method nano particle is coated, obtain having the nano modification chlorinated polyether resin of nucleocapsid structure; Said coupling agent is a silane coupling agent;
The mass ratio of said nano particle and chlorinated polyether resin is 1-2:100;
Said nano particle is silicon-dioxide, titanium oxide or lime carbonate; The particle diameter of said nano particle is 50-150nm;
Specifically operation according to the following steps:
A, surface-treated
In coupling agent, add organic solvent and deionized water; Adjust pH is 8.5-9.0; Stirring at room added nano particle after 30 minutes, and in 45-50 ℃ of ultra-sonic dispersion 1.5-2 hour, the constant stirring of holding temperature was 3-10 hour behind the ultra-sonic dispersion; Then 80 ℃ down dry 6-8 hour powder, obtain modified nanoparticles after, the drying also centrifugal with the said powder of organic solvent washing;
The mass ratio of said nano particle and said coupling agent is 1:1-3;
The mass ratio of said nano particle and described deionized water is 1:1-2.5;
Said organic solvent is absolute ethyl alcohol, Virahol or N, dinethylformamide;
B, coating
The modified nanoparticles that step a is obtained adds in the deionized water, and ultra-sonic dispersion 1.5-2 hour, the quality of said deionized water was 100-150 a times of said modified nanoparticles quality; Add vinylchlorid, vinyl isobutyl ether, initiator, dispersion agent, emulsifying agent and buffer reagent then; In 70-85 ℃ of stirring reaction 7-10 hour; Reaction finishes after-filtration; And, promptly got nano modification chlorinated polyether resin in 10 hours with nucleocapsid structure 35-45 ℃ of following vacuum-drying with deionized water wash 2-3 time;
Said initiator is peroxide initiator or azo-initiator, and add-on is the 0.75-1% of vinylchlorid and vinyl isobutyl ether total mass;
Said dispersion agent is Z 150PH or hydroxypropylcellulose, and add-on is the 0.075-0.4% of vinylchlorid and vinyl isobutyl ether total mass;
Said emulsifying agent is an anionic emulsifier, and add-on is the 0.075-0.2% of vinylchlorid and vinyl isobutyl ether total mass;
Said buffer reagent is water soluble carbonate, supercarbonate, phosphoric acid salt or hydrophosphate, and add-on is the 2-4.5% of vinylchlorid and vinyl isobutyl ether total mass.
2. preparation method according to claim 1 is characterized in that: said peroxide initiator is dilauroyl peroxide, Lucidol or the Lucidol tert-butyl ester; Said azo-initiator is Diisopropyl azodicarboxylate or ABVN.
3. preparation method according to claim 1 is characterized in that: said silane coupling agent is γ-methacryloxypropyl trimethoxy silane.
4. preparation method according to claim 1 is characterized in that: said anionic emulsifier is sodium lauryl sulphate, sodium laurylsulfonate, X 2073, StNa or sodium dibutyl naphthalene sulfonate.
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| CN104177866A (en) * | 2014-08-28 | 2014-12-03 | 确成硅化学股份有限公司 | Modification method of white carbon black |
| CN108976667B (en) * | 2018-08-09 | 2020-11-17 | 南昌航空大学 | Preparation method, product and application of super-hydrophobic material |
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| CN1566202A (en) * | 2003-06-30 | 2005-01-19 | 中国科学院化学研究所 | Peel-off polyvinyl chloride-organic montmorillonite composite nano-material and preparation process thereof |
| CN101381436A (en) * | 2008-10-10 | 2009-03-11 | 合肥工业大学 | Nucleocapsid type sericite-compound material and preparation method thereof |
| CN101851308A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof |
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| CN1566202A (en) * | 2003-06-30 | 2005-01-19 | 中国科学院化学研究所 | Peel-off polyvinyl chloride-organic montmorillonite composite nano-material and preparation process thereof |
| CN101381436A (en) * | 2008-10-10 | 2009-03-11 | 合肥工业大学 | Nucleocapsid type sericite-compound material and preparation method thereof |
| CN101851308A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof |
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