CN104262530B - Unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion and preparation method thereof - Google Patents
Unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of unmodified Ludox/polystyrene acrylate nano core-shell emulsion and preparation method thereof.With commercial available alkaline Ludox, styrene, acrylic ester monomer as primary raw material, it is not necessary to nanoparticle is carried out loaded down with trivial details surface modification, under reactive emulsifier effect, seed monomer is at Nano-meter SiO_22In situ Polymerization, then carries out shell monomer polymerization, forms high Ludox/polystyrene acrylate nano core-shell polymer emulsion so that it is have the multifrequency natures such as particle diameter is little, silicone content is high, clad ratio is high, stability.The method production technology is simple, and quickly, the composite emulsion obtained has obvious nano core-shell composite construction in synthesis, and with nano silicon as core, arylate polyester is as shell；Having the performances such as good resistance to water, stain resistance, thermostability, acid and alkali-resistance, and environmental protection, difficult combustion, the transparency is good.Can be widely applied to the multiple coating fields such as top-grade building coating, electronic package material, boats and ships anticorrosive paint.
Description
Technical field
The invention belongs to environment-protection nano nucleocapsid water-based emulsion field, particularly relate to a kind of unmodified Ludox/polystyrene-propylene
Acid esters nano core-shell emulsion and preparation method thereof.
Background technology
About the nano-material modified and existing many researchs of styrene-acrylic emulsion preparation, but, having of nano-material modified styrene-acrylic emulsion
Efficacious prescriptions method is the most less.It is that the method by physical blending prepares complex emulsions in early days, prepares coating as film forming binder, such as: " receive
Rice interior wall coating " (application number 200810147407.1 publication date 2009-01-07), " a kind of nanometer silica sol modified exterior wall painting
Material and preparation method thereof " (application number 201310331019.X publication date 2013-10-23), " a kind of antifouling imitative porcelain four-in-one
Coating " (application number 201310460051.8 publication date 2014-02-05), " a kind of Ludox Thief zone multifunctional transparent cover
Paint " (application number 201310688008.7 publication date 2014-04-16).This method technique is simple, but SiO2Particle can not
Forming effective interaction with polymer latex particles, the bin stability of blending emulsion is poor, and the improvement to emulsion property is imitated
Fruit is the best, is primarily due to nano-particle and can not get dispersed in styrene-acrylic emulsion matrix.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of production technology is simple, not the changing of high-performance and low-cost, high clad ratio
Property Ludox/Polystyrene-acrylate nano core-shell emulsion and preparation method thereof.
For solve above-mentioned technical problem, the present invention by the following technical solutions: unmodified Ludox/Polystyrene-acrylate
Nano core-shell emulsion, unmodified Ludox/Polystyrene-acrylate nano-core-shell structure with nanometer silicon dioxide particle is
Core, copolymer in cinnamic acrylic ester are shell；The solid content of emulsion is 30～60%, in terms of silicon dioxide, in emulsion
SiO2Mass content be 10～25%.
Above-mentioned unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion, mainly by commercial available alkaline Ludox, benzene second
Alkene and acrylic ester monomer are made.
The preparation method of above-mentioned unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion, molten with commercial available alkaline silicon
Glue, styrene and acrylic ester monomer are primary raw material, under reactive emulsifier effect, make styrene and acrylate
Class monomer is at the SiO of non-modified2Particle surface generation in-situ polymerization, obtains with SiO2For the seed emulsion of core, then planting
Sub-emulsion breast grain surface carries out cinnamic acrylic ester shell polymerization, to obtain final product.
The preparation method of above-mentioned unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion, comprises the following steps:
<1>preparation of Ludox/cinnamic acrylic ester seed emulsion
With commercial available alkaline Ludox, styrene and acrylic ester monomer as primary raw material, under reactive emulsifier effect,
Make styrene and acrylic ester monomer at the SiO of non-modified2Particle surface generation in-situ polymerization, obtains seed emulsion；
<2>synthesis of unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion
In seed emulsion, add non-reacted emulsifying agent, sodium carbonate, initiator, start at the uniform velocity to drip Styrene And Chloroalkyl Acrylates
Esters mix monomer carries out shell polymerization, obtains unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion.
Commercial available alkaline Ludox, in terms of silicon dioxide, the weight content of silicon is 30～50%, and mean diameter is 10～30nm,
PH value is 9～10；
Acrylic ester monomer be methyl methacrylate, n-butyl acrylate, methacrylic acid, ethyl methacrylate,
Two or more in acrylic acid；
Reactive emulsifier is allyloxy Nonylphenoxy propanol polyoxyethylene ether, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyl
One or two in epoxide fatty alcohol oxygen vinyl Ether ammonium sulfate, allyloxy Nonylphenoxy propanol polyoxyethylene ether ammonium sulfate
Kind；
Non-reacted emulsifying agent is anionic or nonionic emulsifier, anionic emulsifier be sodium lauryl sulphate,
One or both in dodecyl sodium sulfate, dodecylbenzene sodium sulfonate；
Initiator is Ammonium persulfate..
The preparation method of above-mentioned unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion, is carried out by following operation:
<1>seeded emulsion polymerization: the four-hole boiling flask that will be equipped with agitator, reflux condensing tube, thermometer and titration funnel is placed in
In thermostat water bath, with 300～400r/min constant speed stirrings, at N2Under protection, count by weight, add 100～140
Part deionized water, 3～5 parts of reactive emulsifiers, add the commercial available alkaline Ludox of 150～300 parts, dispersion after 10 minutes
Uniformly；It is gradually heating to 75 DEG C, and keeps constant temperature, add 0.20～0.50 part of initiator, start to titrate 8～20 parts of benzene
Ethylene-acrylic acid esters mix monomer, drips off for 10～30 minutes, and is incubated 1 hour, obtains seed emulsion；
<2>shell monomer polymerization: 3～5 parts of non-reacted emulsifying agents of addition in seed emulsion, 0.8～2.0 part of sodium carbonate,
0.4～0.8 part of initiator, starts at the uniform velocity 100～150 parts of cinnamic acrylic ester class mix monomers of dropping, and 2.5～3 is little
Time drip complete；It is warming up to 80 DEG C, after insulation 1h, is cooled to room temperature, adjust pH value to 8～8.5, filter discharging,
Obtain the unmodified Ludox of shallow white blueing/Polystyrene-acrylate nano core-shell emulsion.
Non-reacted emulsifying agent is dissolved in 10 parts of distilled water and makes solution and add, and sodium carbonate is dissolved in 10 parts of distilled water and makes solution and add
Entering, initiator is dissolved in 10 parts of distilled water and makes solution addition.
The problem existed for current environment-protection nano nucleocapsid water-based emulsion and preparation thereof, it is molten that inventor establishes a kind of unmodified silicon
The preparation method of glue/Polystyrene-acrylate nano core-shell emulsion, it may be assumed that with commercial available alkaline Ludox, styrene and propylene
Esters of gallic acid monomer is primary raw material, it is not necessary to nanoparticle is carried out loaded down with trivial details surface modification treatment, in reactive emulsifier effect
Under, based on multiple mechanisms such as interface medium, Electrostatic Absorption, use special seeding polymerization technique, make styrene and acrylic acid
Esters monomer is at the SiO of non-modified2Particle surface generation in-situ polymerization, obtains with SiO2For the seed emulsion of core, then exist
Seed emulsion breast grain surface carries out cinnamic acrylic ester shell polymerization, obtains with nanometer silicon dioxide particle as core, benzene second
Alkene-acrylate copolymer is the composite polymer particle of shell, synthesizes the unmodified Ludox/polystyrene-the third of excellent performance
Olefin(e) acid ester nano core-shell emulsion.
The method production technology of the present invention is simple, synthesis is quick, and composite polymer particle has obvious nano core-shell composite construction,
Particle diameter is little and narrowly distributing (60～80nm).Synthesis unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion by
, the silicone content high features such as (account for the 40-50% of total dry film quality), nucleocapsid covering property good, good stability little in particle diameter so that it is
Film has the performances such as high transparent, resistance to water, hardness is high, adhesive force is strong, has good stain resistance, heat-resisting simultaneously
Property, the performance such as acid and alkali-resistance, and environmental protection, difficult combustion, be a kind of high-performance, low cost new environment-protection nano nucleocapsid water-based emulsion.
Therefore, to be widely used in top-grade building coating, metal protection coating, boats and ships anticorrosive paint etc. as film forming matter many for this emulsion
Plant paint field.The novel nano composite water soluble exterior coating product properties developed accordingly meets water-based exterior wall paint state
More than high-class product technology requirement in mark GB/T9755-2001, the most water-fast, resistance to acids and bases, resistance to soiling, resistance to manually
Aging is the most excellent.Due to the use of high content silicon colloidal sol, the present invention has been greatly saved petroleum resources, with low cost, both
The requirement meeting performance meets again the demand of modern environmental protection development.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of the unmodified Ludox of the present invention/Polystyrene-acrylate nano core-shell composite polymer particle.
Detailed description of the invention
Embodiment 1
<1>seeded emulsion polymerization: the four-hole boiling flask that will be equipped with agitator, reflux condensing tube, thermometer and titration funnel is placed in constant temperature
In water-bath, stir with 400r/min constant speed, at N2Under protection, count by weight, addition 100g deionized water,
3g reactive emulsifier allyloxy Nonylphenoxy propanol polyoxyethylene ether, adds the commercial available alkaline silicon of 150g after 10 minutes
Colloidal sol (in terms of silicon dioxide, the weight content of silicon is 30%, and mean diameter is 10nm, and pH value is 9), is uniformly dispersed；
It is gradually heating to 75 DEG C, and keeps constant temperature, add 0.20g Ammonium persulfate. (be dissolved in 10g distilled water and make solution addition),
Start to titrate 8g cinnamic acrylic ester class mix monomer (styrene/acrylic N-butyl/methyl methacrylate/propylene
Acid=47/49/3/1, mass ratio), within 10 minutes, drip off, and be incubated 1 hour, obtain seed emulsion；
<2>shell monomer polymerization: add the non-reacted emulsifier sodium lauryl sulfate of 3g in seed emulsion and (be dissolved in 10g distillation
Water is made solution and is added), 0.8g sodium carbonate (is dissolved in 10g distilled water and makes solution addition), and 0.4g Ammonium persulfate. (is dissolved in
10g distilled water is made solution and is added), start at the uniform velocity dropping 100g cinnamic acrylic ester class mix monomer (styrene/the third
Olefin(e) acid N-butyl/methyl methacrylate/acrylic acid=47/49/3/1, mass ratio), dropping in 2.5 hours is complete；It is warming up to
80 DEG C, after insulation 1h, be cooled to room temperature, adjust pH value to 8, filter discharging, the shallow unmodified Ludox of white blueing/
Polystyrene-acrylate nano core-shell emulsion.
After testing, this example emulsion appearance is that blueing is translucent, and mean diameter is 30nm.
Embodiment 2
<1>seeded emulsion polymerization: the four-hole boiling flask that will be equipped with agitator, reflux condensing tube, thermometer and titration funnel is placed in constant temperature
In water-bath, stir with 300r/min constant speed, at N2Under protection, count by weight, add 140g deionized water, 5g
Reactive emulsifier allyloxy hydroxypropyl azochlorosulfonate acid sodium, adds the commercial available alkaline Ludox of 300g (with titanium dioxide after 10 minutes
Silicon meter, the weight content of silicon is 50%, and mean diameter is 30nm, and pH value is 10), it is uniformly dispersed；It is gradually heating to 75 DEG C,
And keep constant temperature, add 0.50g Ammonium persulfate. (be dissolved in 10g distilled water and make solution addition), start to titrate 20g benzene second
Alkene-esters of acrylic acid mix monomer (styrene/acrylic N-butyl/ethyl methacrylate/methacrylic acid
=46/47/4/3, mass ratio), within 20 minutes, drip off, and be incubated 1 hour, obtain seed emulsion；
<2>shell monomer polymerization: add 6g non-reacted emulsifying agent dodecylbenzene sodium sulfonate in seed emulsion and (be dissolved in 10g to steam
Distilled water is made solution and is added), 2.5g sodium carbonate (is dissolved in 10g distilled water and makes solution addition), and 0.8g Ammonium persulfate. is (molten
Make solution in 10g distilled water to add), beginning at the uniform velocity dropping 150g cinnamic acrylic ester class mix monomer (styrene/
N-butyl acrylate/ethyl methacrylate/methacrylic acid=46/47/4/3, mass ratio), dropping in 3 hours is complete；Heat up
To 80 DEG C, after insulation 1h, be cooled to room temperature, adjust pH value to 8, filter discharging, the shallow unmodified Ludox of white blueing
/ Polystyrene-acrylate nano core-shell emulsion.
Embodiment 3
<1>seeded emulsion polymerization: the four-hole boiling flask that will be equipped with agitator, reflux condensing tube, thermometer and titration funnel is placed in constant temperature
In water-bath, stir with 300r/min constant speed, at N2Under protection, count by weight, addition 120g deionized water,
4g reactive emulsifier allyloxy fatty alcohol oxygen vinyl Ether ammonium sulfate, adds the commercial available alkaline Ludox of 250g after 10 minutes
(in terms of silicon dioxide, the weight content of silicon is 40%, and mean diameter is 20nm, and pH value is 9), is uniformly dispersed；Gradually
It is warming up to 75 DEG C, and keeps constant temperature, add 0.30g Ammonium persulfate. (be dissolved in 10g distilled water and make solution addition), start
Titration 15g cinnamic acrylic ester class mix monomer (styrene/acrylic N-butyl/acrylic acid=48/48/4, mass ratio),
Within 20 minutes, drip off, and be incubated 1 hour, obtain seed emulsion；
<2>shell monomer polymerization: add 4g non-reacted emulsifying agent dodecyl sodium sulfate and detergent alkylate sulphur in seed emulsion
The mixture (mass ratio 1:1 is dissolved in 10g distilled water and makes solution addition) of acid sodium, 1.3g sodium carbonate (is dissolved in 10g to steam
Distilled water is made solution and is added), 0.6g Ammonium persulfate. (is dissolved in 10g distilled water and makes solution addition), starts at the uniform velocity to drip 130g
Cinnamic acrylic ester class mix monomer (styrene/acrylic N-butyl/acrylic acid=48/48/4, mass ratio), 2.5 is little
Time drip complete；Be warming up to 80 DEG C, after insulation 1h, be cooled to room temperature, adjust pH value to 8, filter discharging, shallow in vain
The unmodified Ludox of blueing/Polystyrene-acrylate nano core-shell emulsion.
After testing, this example emulsion appearance is that blueing is translucent, and mean diameter is 65nm.
Embodiment 4
Substantially the same manner as Example 1, only in the seeded emulsion polymerization of step<1>, reactive emulsifier changes allyloxy nonyl into
Phenoxypropanol polyoxyethylene ether ammonium sulfate.
Embodiment 5
Substantially the same manner as Example 1, only in the shell monomer polymerization of step<2>, non-reacted emulsifying agent changes detergent alkylate into
Sodium sulfonate.
Embodiment 6
Substantially the same manner as Example 1, only in the shell monomer polymerization of step<2>, non-reacted emulsifying agent changes dodecyl sulfur into
Acid sodium and the mixture (mass ratio 1:1) of dodecyl sodium sulfate.
Ludox unmodified to embodiment 1-6 gained/Polystyrene-acrylate nano core-shell product emulsion carries out key property
Detection, result such as table 1 and Fig. 1.
Table 1 emulsion key property index
Fig. 1 shows, the particle size analysis in complex emulsions of the present invention is 60～80nm, is (interior with nanometer silicon dioxide particle as core
Layer depth black), polymer (outer layer is light grey) is the clad structure of shell, and dispersibility is splendid.
Claims (5)
1. unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion, it is characterised in that: described unmodified silicon is molten
Glue/Polystyrene-acrylate nano-core-shell structure with nanometer silicon dioxide particle as core, cinnamic acrylic ester copolymerization
Thing is shell；The solid content of described emulsion is 30～60%, in terms of silicon dioxide, and SiO in emulsion2Mass content be
10～25%；This emulsion, with alkaline silica sol, styrene and acrylic ester monomer as raw material, is made at reactive emulsifier
Under with, make styrene and acrylic ester monomer at the SiO of non-modified2Particle surface generation in-situ polymerization, obtain with
SiO2For the seed emulsion of core, then carry out cinnamic acrylic ester shell polymerization on seed emulsion breast grain surface, to obtain final product.
2. the preparation method of unmodified Ludox described in claim 1/Polystyrene-acrylate nano core-shell emulsion, its feature
It is: with alkaline silica sol, styrene and acrylic ester monomer as raw material, under reactive emulsifier effect, makes
Styrene and acrylic ester monomer are at the SiO of non-modified2Particle surface generation in-situ polymerization, obtains with SiO2For core
Seed emulsion, then carry out cinnamic acrylic ester shell polymerization on seed emulsion breast grain surface, to obtain final product.
The preparation method of unmodified Ludox the most according to claim 2/Polystyrene-acrylate nano core-shell emulsion,
It is characterized in that comprising the following steps:
<1>preparation of Ludox/cinnamic acrylic ester seed emulsion
With alkaline silica sol, styrene and acrylic ester monomer as raw material, under reactive emulsifier effect, make styrene
With acrylic ester monomer at the SiO of non-modified2Particle surface generation in-situ polymerization, obtains seed emulsion；
<2>synthesis of unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion
In seed emulsion, add non-reacted emulsifying agent, sodium carbonate, initiator, start at the uniform velocity to drip Styrene And Chloroalkyl Acrylates
Esters mix monomer carries out shell polymerization, obtains unmodified Ludox/Polystyrene-acrylate nano core-shell emulsion.
The preparation method of unmodified Ludox the most according to claim 3/Polystyrene-acrylate nano core-shell emulsion,
It is characterized in that:
Described alkaline silica sol, in terms of silicon dioxide, the weight content of silicon is 30～50%, and mean diameter is 10～30nm, pH
Value is 9～10；
Described acrylic ester monomer be methyl methacrylate, n-butyl acrylate, methacrylic acid, ethyl methacrylate,
Two or more in acrylic acid；
Described reactive emulsifier is allyloxy Nonylphenoxy propanol polyoxyethylene ether, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyl
One or two in epoxide fatty alcohol oxygen vinyl Ether ammonium sulfate, allyloxy Nonylphenoxy propanol polyoxyethylene ether ammonium sulfate
Kind；
Described non-reacted emulsifying agent is anionic or nonionic emulsifier, anionic emulsifier be sodium lauryl sulphate,
One or both in dodecyl sodium sulfate, dodecylbenzene sodium sulfonate；
Described initiator is Ammonium persulfate..
The preparation method of unmodified Ludox the most according to claim 4/Polystyrene-acrylate nano core-shell emulsion,
It is characterized in that carrying out by following operation:
<1>four-hole boiling flask that will be equipped with agitator, reflux condensing tube, thermometer and titration funnel is placed in thermostat water bath, with 300～
400r/min constant speed stirs, at N2Under protection, count by weight, add 100～140 parts of deionized waters, 3～5 parts
Reactive emulsifier, adds the alkaline silica sol of 150～300 parts, is uniformly dispersed after 10 minutes；It is gradually heating to 75 DEG C,
And keep constant temperature, add 0.20～0.50 part of initiator, start to titrate 8～20 parts of cinnamic acrylic ester class mix monomers,
Within 10～30 minutes, drip off, and be incubated 1 hour, obtain seed emulsion；
<2>in seed emulsion, 3～5 parts of non-reacted emulsifying agents are added, 0.8～2.0 part of sodium carbonate, 0.4～0.8 part of initiator,
Starting at the uniform velocity 100～150 parts of cinnamic acrylic ester class mix monomers of dropping, dropping in 2.5～3 hours is complete；It is warming up to
80 DEG C, after insulation 1h, be cooled to room temperature, adjust pH value to 8～8.5, filter discharging, the shallow unmodified silicon of white blueing is molten
Glue/Polystyrene-acrylate nano core-shell emulsion.
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| CN105418850A (en) * | 2015-11-30 | 2016-03-23 | 何晨旭 | Nano-scale core-shell type wax-acrylic polymer emulsion for coating and preparation method of nano-scale core-shell type wax-acrylic polymer emulsion |
| CN107266939A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN107266715B (en) * | 2016-04-08 | 2019-06-07 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN106892629B (en) * | 2017-01-21 | 2019-10-25 | 浙江益森科技股份有限公司 | A kind of preparation method of the high bonding force environmental protection type polymer spraying and decorating mortar of assembled architecture |
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| CN108587424A (en) * | 2018-05-29 | 2018-09-28 | 芜湖市元奎新材料科技有限公司 | Water-proof heat-insulating paint |
| CN109369920B (en) * | 2018-08-30 | 2021-04-30 | 上海理工大学 | Preparation of polystyrene-SiO 2 core-shell nano composite particles with concave structures |
| CN110845678A (en) * | 2019-11-28 | 2020-02-28 | 佛山市新量子环保材料有限公司 | Fluorine modified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method and application thereof |
| CN113527563B (en) * | 2021-07-23 | 2022-11-01 | 武汉工程大学 | Ethanol dilution resistant modified styrene-acrylic emulsion and preparation method and application thereof |
| CN113410468B (en) * | 2021-08-19 | 2021-11-23 | 江苏卓高新材料科技有限公司 | Negative electrode binder and preparation method thereof, preparation method of negative electrode sheet and lithium ion battery |
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