CN103626933A - Polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion and preparation method and application thereof - Google Patents
Polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of high molecule synthesis. In order to solve the problems that the content of nano SiO2 in an acrylate polymer emulsion system is lower and the modifying process on the surface of SiO2 is tedious and the like, the invention provides a polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion which consists of 20-60 parts of a polysilsesquioxane emulsion, 15-35 parts of alkyl methacrylate, 15-35 parts of alkyl acrylate, 1-5 parts of hydroxyl alkyl acrylate, 0.1-1 part of an initiator, 40-80 parts of water, 30-60 parts of a silica sol and 5-15 parts of a cosolvent. The emulsion has good appearance and storage stability. The film is high in transparency, the hardness reaches 6H, the adhesive force is level 1, and the content of silicon based on SiO2 reaches over 25%. The high silicon content polysilsesquioxane-polyacrylate-nano SiO2 composite emulsion integrates advantages of organic and inorganic materials, and the film has excellent performances such as ageing resistance, heat resistance, scratch resistance, wear resistance and high hardness. The emulsion has a wide application prospect in the fields of coatings and adhesives.
Description
Technical field
The present invention relates to Polymer Synthesizing field, relate in particular to a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion and preparation method thereof and application.
Technical background
Water-borne coatings is with water to replace organic solvent, safe, nontoxic when producing and using, and can meet energy-saving and emission-reduction, circulation and Sustainable development demand, and exploitation high-performance aqueous coating has become the emphasis that coatings industry is first developed.Solvent based coating is become to water-borne coatings, and after assurance film forming, hardness of film height and scoring resistance are excellent, are the difficult problems that coating Water-borne modification process must overcome.Water-and acrylate emulsion is as a kind of environmentally friendly product, there is good gloss retention, excellent film-forming properties and the feature such as environment friendly and pollution-free, be widely used in the multiple fields such as coating and tackiness agent, but acrylate resin molecule mostly is linear structure, at aspects such as hardness, scratch resistant and resistant to chemical media, there is wretched insufficiency.
Along with the continuous growth of people to emulsion film technical requirements, exploitation have high rigidity and good heat resistance can emulsion become a focus of development.Wherein, development organic inorganic hybridization modification technology, introduces polymer emulsion by the polysilsesquioxane that contains inorganic structure and inorganic nano-particle, is an important solution route.Si-O bond energy large (450kJ/mol) in polysilsesquioxane molecular structure, much larger than C-C bond energy (345kJ/mol) and C-O bond energy (351kJ/mol), simultaneously its molecular structure feature makes it have good resistant of high or low temperature, weathering resistance, mechanical property that ventilation property is fire-retardant and excellent, has been subject to scientific research personnel's extensive concern.But its film-forming properties and sticking power are poor, bad to adhesion.
Chinese patent CN102977253 A discloses a kind of organosilicon-modified acrylate hybridisation emulsion and preparation method thereof and application, take acrylate monomer as raw material, by acrylate monomer, react with the polyfunctionality silsesquioxane of carbon-carbon double bonds, make silsesquioxane group be combined and prepare organosilicon-modified acrylate hybridisation emulsion with the form of covalent linkage with acrylic ester polymer, improved high-and low-temperature resistance and the water resistance of acrylic ester polymer, but the SiO that films
2inorganic content is lower, and hardness of film is not enough.
Chinese patent 101948561A discloses a kind of organic/inorganic silicon hybrid resin for coating and preparation method thereof.Adopt sol-gel method to prepare nanometer SiO
2colloidal sol, and with organo-siloxane to nanometer SiO
2carry out surface modification and make it have reactivity, then prepare hybridization coating resin with acrylate monomer polymerization, film there is good mechanical property, resistance to elevated temperatures and good snappiness.But this method need to adopt organo-siloxane to nanometer SiO
2carry out surface modification, process is loaded down with trivial details, SiO in resin
2content is lower, and hardness of film is inadequate, is 2H to the maximum.
Summary of the invention
For solving nanometer SiO
2in acrylate polymer emulsion system, content is on the low side and need to be to SiO
2the problems such as modifying surface process is loaded down with trivial details, the invention provides a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation method of composite emulsion, emulsion has good outward appearance and stability in storage.The transparency of filming is high, and hardness reaches 6H, and 1 grade of sticking power, with SiO
2meter silicone content reaches more than 25%.This high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion set the advantage of organic-inorganic material, the performances such as having excellent ageing-resistant, heat-resisting, scrape resistant, wear resistance and high rigidity of filming, is with a wide range of applications at coating and sizing agent field.
Another object of the present invention is to provide a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation method of composite emulsion.
The present invention is achieved by the following technical solutions: a kind of polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion, described polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion is made by following component, and the mass parts of each component is:
Polysilsesquioxane emulsion 20-60 part,
Alkyl methacrylate 15-35 part,
Alkyl acrylate 15-35 part,
Vinylformic acid hydroxyalkyl acrylate 1-5 part,
Initiator 0.1-1 part,
Water 40-80 part,
Silicon sol 30-60 part,
Cosolvent 5-15 part;
Wherein, polysilsesquioxane emulsion is made by following component, and the mass parts of each component is:
Emulsifying agent 0.5-3 part,
Alkaline catalysts 1-3 part,
Silane coupling agent 10-30 part
Water 100-200 part.
Described emulsifying agent is anionic emulsifier and nonionic emulsifier compound, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), sodium lauryl sulphate (SDS); Described nonionic emulsifying agent is the mixture of one or more arbitrary proportions in polyoxyethylene octylphenol ether OP-10, polyoxyethylene octylphenol ether OP-15, polyoxyethylene octylphenol ether OP-30, polyoxyethylene nonylphenol ether NP-10, polyoxyethylene nonylphenol ether NP-15 or polyoxyethylene nonylphenol ether NP-30; As preferably, the mass ratio of nonionic emulsifier and anionic emulsifier is 1-2:1.
Described alkaline catalysts is selected from a kind of in ammoniacal liquor, sodium hydroxide, potassium hydroxide; As preferably, the mass concentration of ammoniacal liquor is 20% ~ 28%.
Described silane coupling agent is selected from the silane coupling agent containing alkene unsaturated group, is selected from a kind of in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three butoxy silanes, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl three butoxy silanes;
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer;
Described vinylformic acid hydroxyalkyl acrylate is the mixture of one or more arbitrary proportions of 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl;
Described initiator is selected from persulfuric acid salt system, is selected from Potassium Persulphate, Sodium Persulfate, ammonium persulphate a kind of;
Described water is deionized water;
Described silicon sol is alkaline silica sol, and particle diameter is 5-30nm, with SiO
2meter, the mass content of silicon is 30-40%; Silicon sol particle diameter is 5-30nm, and particle is too large, can affect the film forming of composite emulsion, so generally select particle diameter little, 5-30nm is than better suited, and what between silica sol particle and acrylic ester emulsion, can merge during film forming like this is quite a lot of.Alkaline silica sol is conducive to composite emulsion later stage collosol and gel film forming.
Described cosolvent is the mixture of one or more arbitrary proportions in methyl alcohol, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol or ethylene glycol.
Above-mentioned a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation method of composite emulsion, described preparation method is following steps:
(1) preparation of polysilsesquioxane emulsion: emulsifying agent, alkaline catalysts and water are added in reactor, be warming up to 40-60 ℃ and stir 15-30 minute, silane coupling agent was added slowly and added in 0.5-2 hour, keep stirring reaction 12-24 hour, obtain polysilsesquioxane emulsion;
(2) polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation method of composite emulsion is:
A, alkyl methacrylate and alkyl acrylate are mixed and made into monomer I, 10%-20% and the vinylformic acid hydroxyalkyl acrylate of getting mix monomer I mass parts are mixed and made into monomer II; As preferably, mix monomer I multipolymer second-order transition temperature is-20-20 ℃;
B, polysilsesquioxane emulsion 20-60 part (mass parts) and the 70%-85% of quality part, the 60%-80% of initiator mass parts prepared by step (1) add in reactor, stir and be warming up to 75-80 ℃ after 10-20 minute, then monomer I is slowly added in reactor, within 2-4 hour, drip off, dropwise rear insulation 15-30 minute;
C, remaining initiator is dissolved in remaining water,, within 1-2 hour, being added drop-wise to continuously the product that step b obtains, dropwising rear reaction 0.5-1 hour, then be warming up to 80-85 ℃ of insulation 1-2 hour with monomer II, then be cooled to 40-50 ℃, filter discharging and obtain emulsion; The joining day that limits material is for maintaining thermal equilibrium and the certain speed of reaction of reaction mass in reactor, and different weight of material can keep by the reactor in corresponding size the speed of response of material.
D, by cosolvent in the emulsion that slowly adds step c to obtain for 0.5-1 hour, keep stirring after 15-30 minute, silicon sol was slowly added at 1-2 hour, stir and obtain polysilsesquioxane-polyacrylic ester-nanometer SiO after 1-6 hour
2composite emulsion.Composite emulsion outward appearance is the milky emulsion of blueing light.
As preferably, in whole preparation process, maintain whipped state.
The present invention adopts containing alkene unsaturated group silane coupling agent as presoma, by sol-gel method, prepare polysilsesquioxane emulsion, and take this polysilsesquioxane and obtain polysilsesquioxane-Polyacrylate Nano-Particles as core and acrylate monomer carry out in-situ polymerization, finally add silicon sol and cosolvent to obtain high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
The present invention utilizes the polysilsesquioxane modified acrylate emulsion containing two key functional groups that bond energy is higher, can bring into play both advantages, improves the high-and low-temperature resistance performance of acrylic ester polymer.In addition, by adding inorganic nano-particle can imitate the film performance that improves emulsion, development and the application of the compound emulsion of organic-inorganic have greatly been promoted.Inorganic nano material is as SiO
2there is the distinct advantages such as excellent wear resistance, high rigidity, scratch resistance, ageing-resistant, ultraviolet-resistent property, its is introduced and in organic polymer emulsion, can improve the hardness of filming, scratch resistant, the performance such as weather-proof.By nanometer SiO
2evenly spread in acrylate resin, the hardness that can overcome acrylate resin is low, and the shortcoming such as wear no resistance improves tensile strength and shock strength and resistance toheat, reaches the object of improving unmodified resin material property.By acrylate-nanometer SiO
2when composite emulsion is used as coating, film and have excellent mechanical property, base material is had to good sticking power, the water tolerance of filming, solvent resistance, the more general emulsion of heat-resisting and resistance to flame retardant resistance all improve a lot.
High silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO of the present invention
2the application of composite emulsion on coating and sizing agent field.A kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO that the present invention makes
2composite emulsion, has good outward appearance, and solid content is 30-40%.Film with SiO
2meter, the mass content of silicon is 25-30%.Emulsion film hardness reaches 6H, adhesion 1 grade.This high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion set the advantage of organic-inorganic material, the performances such as having excellent ageing-resistant, heat-resisting, scrape resistant, wear resistance and high rigidity of filming, is with a wide range of applications at coating and sizing agent field.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention's employing is presoma containing the silane coupling agent of alkene unsaturated group, by sol-gel method, prepare the polysilsesquioxane inorganic particulate containing two key groups, and as core directly and acrylate monomer carry out in-situ polymerization and prepare polysilsesquioxane-polyacrylate dispersion, avoided preparing SiO by sol-gel method
2need be after surface modification could with the complicated processes of acrylate monomer polymerization.
(2) in composite emulsion, introduced inorganic nano SiO
2, the simultaneously existence of polysilsesquioxane in emulsion, has improved the content of emulsion film silicon, has also further improved the hardness of filming.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, raw materials used all commercially available in embodiment, wherein commercial silicon sol is alkalescence.Particle diameter is 5-30nm, with SiO
2meter, the mass content of silicon is 30-40%.It should be noted that, embodiment does not form limiting the scope of the invention.
Embodiment 1
(1) preparation of polysilsesquioxane emulsion: in mass fraction, the ammoniacal liquor and the 100 parts of water that by 0.3 part of polyoxyethylene octylphenol ether OP-10,0.2 part of dodecyl diphenyl oxide disodium sulfonate (DSB), 1 part of mass concentration, are 28% add in reactor, being warming up to 40 ℃ stirs 15 minutes, 10 parts of γ-methacryloxypropyl trimethoxy silane were added slowly and added in 0.5 hour, keep stirring reaction 12 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 15 parts of methyl methacrylates and 15 parts of butyl acrylates are mixed and made into monomer I, 10% and 1 part of 2-Hydroxy ethyl acrylate getting mix monomer I is mixed and made into monomer II;
60% of 70%, 0.1 part of initiator potassium persulfate in b, 20 parts of polysilsesquioxane emulsions prepared by step (1) and 40 parts of water adds in reactor, stir and be warming up to 75 ℃ after 10 minutes, then monomer I is slowly added in reactor, within 2 hours, drip off, dropwise rear insulation 15 minutes;
C, remaining initiator is dissolved in remaining water,, within 1 hour, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 0.5 hour, then be warming up to 80 ℃ of insulations 1 hour with monomer II, be then cooled to 40 ℃, filter discharging and obtain emulsion.
D, by 5 parts of Virahols in the emulsion that slowly adds step c to obtain for 0.5 hour, keep stirring after 15 minutes, 30 parts of silicon sol were slowly added at 1 hour, stir and after 1 hour, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 33.6%.Emulsion film is with SiO
2meter, the mass content of silicon is 26.2%, emulsion film hardness reaches 6H, adhesion 1 grade.
Embodiment 2
(1) preparation of polysilsesquioxane emulsion: in mass fraction, 0.5 part of polyoxyethylene octylphenol ether OP-15,0.5 part of Sodium dodecylbenzene sulfonate (LAS), 1.5 parts of sodium hydroxide and 120 parts of water are added in reactor, being warming up to 45 ℃ stirs 20 minutes, 15 parts of vinyltriethoxysilanes were added slowly and added in 1 hour, keep stirring reaction 16 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 15 parts of β-dimethyl-aminoethylmethacrylates, 10 parts of propyl methacrylates and 20 parts of methyl acrylates are mixed and made into monomer I, 15% and 2 part of vinylformic acid-3-hydroxy propyl ester getting mix monomer I is mixed and made into monomer II;
65% of 75%, 0.3 part of initiator Sodium Persulfate in b, 30 parts of polysilsesquioxane emulsions prepared by step (1) and 50 parts of water adds in reactor, stir and be warming up to 77 ℃ after 15 minutes, then monomer I is slowly added in reactor, within 2.5 hours, drip off, dropwise rear insulation 20 minutes;
C, remaining initiator is dissolved in remaining water,, within 1.5 hours, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 45 minutes, then be warming up to 82 ℃ of insulations 1.5 hours with monomer II, be then cooled to 45 ℃, filter discharging and obtain emulsion.
D, by 4 parts of methyl alcohol, 4 parts of isopropylcarbinols in the emulsion that slowly adds step c to obtain for 0.5 hour, keep stirring after 20 minutes, 40 parts of silicon sol were slowly added at 1.5 hours, stir and after 2 hours, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 36.0%.Emulsion film is with SiO
2meter, the mass content of silicon is 25.4%, emulsion film hardness reaches 6H, adhesion 1 grade.
Embodiment 3
(1) preparation of polysilsesquioxane emulsion: in mass fraction, 1 part of polyoxyethylene octylphenol ether OP-30,0.5 part of sodium lauryl sulphate (SDS), 2 parts of potassium hydroxide and 140 parts of water are added in reactor, being warming up to 50 ℃ stirs 25 minutes, 20 parts of γ-methacryloxypropyl triethoxyl silanes were added slowly and added in 1.5 hours, keep stirring reaction 18 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 10 parts of methyl methacrylates, 15 parts of butyl methacrylate and 15 parts of ethyl propenoates, 10 parts of propyl acrylates are mixed and made into monomer I, 20% and 3 part of vinylformic acid-4-hydroxyl butyl ester getting mix monomer I is mixed and made into monomer II;
70% of 80%, 0.5 part of initiator ammonium persulfate in b, 35 parts of polysilsesquioxane emulsions prepared by step (1) and 60 parts of water adds in reactor, stir and be warming up to 78 ℃ after 20 minutes, then monomer I is slowly added in reactor, within 3 hours, drip off, dropwise rear insulation 30 minutes;
C, remaining initiator is dissolved in remaining water,, within 2 hours, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 1 hour, then be warming up to 83 ℃ of insulations 2 hours with monomer II, be then cooled to 50 ℃, filter discharging and obtain emulsion.
D, by 5 parts of ethanol, 5 parts of ethylene glycol in the emulsion that slowly adds step c to obtain for 1 hour, keep stirring after 30 minutes, 50 parts of silicon sol were slowly added at 2 hours, stir and after 3 hours, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 34.8%.Emulsion film is with SiO
2meter, the mass content of silicon is 26.8%, emulsion film hardness reaches 6H, adhesion 1 grade.
Embodiment 4
(1) preparation of polysilsesquioxane emulsion: in mass fraction, the ammoniacal liquor and the 160 parts of water that by 1.2 parts of polyoxyethylene nonylphenol ether NP-10,0.8 part of sodium lauryl sulphate (SDS), 2.5 parts of mass concentrations, are 20% add in reactor, being warming up to 55 ℃ stirs 30 minutes, 25 parts of vinyltrimethoxy silanes were added slowly and added in 2 hours, keep stirring reaction 20 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 25 parts of propyl methacrylates and 15 ethyl propenoates, 15 parts of butyl acrylates are mixed and made into monomer I, 10% and 3.5 part of vinylformic acid-5-hydroxyl pentyl ester getting mix monomer I is mixed and made into monomer II;
75% of 75%, 0.6 part of initiator potassium persulfate in b, 40 parts of polysilsesquioxane emulsions prepared by step (1) and 65 parts of water adds in reactor, stir and be warming up to 76 ℃ after 15 minutes, then monomer I is slowly added in reactor, within 3.5 hours, drip off, dropwise rear insulation 30 minutes;
C, remaining initiator is dissolved in remaining water,, within 1.5 hours, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 0.5 hour, then be warming up to 81 ℃ of insulations 1.5 hours with monomer II, be then cooled to 45 ℃, filter discharging and obtain emulsion.
D, by 7 parts of methyl alcohol, 3 parts of ethanol in the emulsion that slowly adds step c to obtain for 0.5 hour, keep stirring after 20 minutes, 55 parts of silicon sol were slowly added at 1.5 hours, stir and after 4 hours, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 35.3%.Emulsion film is with SiO
2meter, the mass content of silicon is 27.5%, emulsion film hardness reaches 6H, adhesion 1 grade.
Embodiment 5
(1) preparation of polysilsesquioxane emulsion: in mass fraction, 1.5 parts of polyoxyethylene nonylphenol ether NP-15,1.0 parts of Sodium dodecylbenzene sulfonatees (LAS), 3 parts of potassium hydroxide and 180 parts of water are added in reactor, being warming up to 60 ℃ stirs 20 minutes, 25 parts of γ-methacryloxypropyl three butoxy silanes were added slowly and added in 1.5 hours, keep stirring reaction 24 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 15 parts of methacrylic acid pentyl esters prepared by step (1), 15 parts of N-Hexyl methacrylates and 10 parts of vinylformic acid pentyl esters, 10 parts of Isooctyl acrylate monomers are mixed and made into monomer I, and 15% and 4 part of own ester of vinylformic acid-6-hydroxyl getting mix monomer I is mixed and made into monomer II;
B, by 80% of 80%, 0.8 part of initiator Sodium Persulfate in 50 parts of polysilsesquioxane emulsions and 70 parts of water, add in reactor, stir and be warming up to 80 ℃ after 20 minutes, then monomer I is slowly added in reactor, within 4 hours, drip off, dropwise rear insulation 30 minutes;
C, remaining initiator is dissolved in remaining water,, within 2 hours, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 1 hour, then be warming up to 85 ℃ of insulations 2 hours with monomer II, be then cooled to 50 ℃, filter discharging and obtain emulsion.
D, by 6 parts of ethanol, 6 parts of Virahols in the emulsion that slowly adds step c to obtain for 1 hour, keep stirring after 30 minutes, 55 parts of silicon sol were slowly added at 1.5 hours, stir and after 5 hours, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 31.1%.Emulsion film is with SiO
2meter, the mass content of silicon is 28.0%, emulsion film hardness reaches 6H, adhesion 1 grade.
Embodiment 6
(1) preparation of polysilsesquioxane emulsion: in mass fraction, 2 parts of polyoxyethylene nonylphenol ether NP-30,1.0 parts of dodecyl diphenyl oxide disodium sulfonates (DSB), 3 parts of sodium hydroxide and 200 parts of water are added in reactor, being warming up to 60 ℃ stirs 20 minutes, 30 parts of vinyl three butoxy silanes were added slowly and added in 2 hours, keep stirring reaction 24 hours, obtain polysilsesquioxane emulsion;
(2) high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation of composite emulsion:
A, 20 parts of Isooctyl methacrylates, 15 parts of methacrylic acid pentyl esters and 15 parts of ethyl propenoates, 20 parts of Ethyl acrylate are mixed and made into monomer I, get 20% and 2 part of 2-Hydroxy ethyl acrylate of mix monomer I, 3 parts of vinylformic acid-3-hydroxy propyl esters are mixed and made into monomer II;
80% of 85%, 1 part of initiator ammonium persulfate in b, 60 parts of polysilsesquioxane emulsions prepared by step (1) and 80 parts of water adds in reactor, stir and be warming up to 79 ℃ after 20 minutes, then monomer I is slowly added in reactor, within 4 hours, drip off, dropwise rear insulation 30 minutes;
C, remaining initiator is dissolved in remaining water,, within 2 hours, being added drop-wise to continuously the emulsion that step b obtains, dropwising rear reaction 1 hour, then be warming up to 84 ℃ of insulations 2 hours with monomer II, be then cooled to 45 ℃, filter discharging and obtain emulsion.
D, by 10 parts of methyl alcohol, 5 parts of trimethyl carbinols in the emulsion that slowly adds step c to obtain for 1 hour, keep stirring after 30 minutes, 60 parts of silicon sol were slowly added at 2 hours, stir and after 6 hours, obtain stable high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion.
Composite emulsion outward appearance is the milky white liquid that is blue, emulsion solid content 34.1%.Emulsion film is with SiO
2meter, the mass content of silicon is 25.5%, emulsion film hardness reaches 6H, adhesion 1 grade.
Claims (7)
1. polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion, is characterized in that, described polysilsesquioxane-polyacrylic ester-nanometer SiO
2composite emulsion is made by following component, and the mass parts of each component is:
Polysilsesquioxane emulsion 20-60 part,
Alkyl methacrylate 15-35 part,
Alkyl acrylate 15-35 part,
Vinylformic acid hydroxyalkyl acrylate 1-5 part,
Initiator 0.1-1 part,
Water 40-80 part,
Silicon sol 30-60 part,
Cosolvent 5-15 part;
Wherein, polysilsesquioxane emulsion is made by following component, and the mass parts of each component is:
Emulsifying agent 0.5-3 part,
Alkaline catalysts 1-3 part,
Silane coupling agent 10-30 part
Water 100-200 part.
2. a kind of polysilsesquioxane-polyacrylic ester-nanometer SiO according to claim 1
2composite emulsion, is characterized in that,
Described emulsifying agent is anionic emulsifier and nonionic emulsifier compound, and wherein anionic emulsifier is selected from the mixture of one or more arbitrary proportions in dodecyl diphenyl oxide disodium sulfonate (DSB), Sodium dodecylbenzene sulfonate (LAS), sodium lauryl sulphate (SDS); Described nonionic emulsifying agent is the mixture of one or more arbitrary proportions in polyoxyethylene octylphenol ether OP-10, polyoxyethylene octylphenol ether OP-15, polyoxyethylene octylphenol ether OP-30, polyoxyethylene nonylphenol ether NP-10, polyoxyethylene nonylphenol ether NP-15 or polyoxyethylene nonylphenol ether NP-30;
Described alkaline catalysts is selected from a kind of in ammoniacal liquor, sodium hydroxide, potassium hydroxide;
Described silane coupling agent is selected from the silane coupling agent containing alkene unsaturated group, is selected from a kind of in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three butoxy silanes, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl three butoxy silanes;
Described alkyl methacrylate is selected from the mixture of one or more arbitrary proportions in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, Isooctyl methacrylate;
Described alkyl acrylate is selected from the mixture of one or more arbitrary proportions in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, Isooctyl acrylate monomer;
Described vinylformic acid hydroxyalkyl acrylate is the mixture of one or more arbitrary proportions of 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl;
Described initiator is selected from persulfuric acid salt system, is selected from Potassium Persulphate, Sodium Persulfate, ammonium persulphate a kind of;
Described water is deionized water;
Described silicon sol is alkaline silica sol, and particle diameter is 5-30nm, with SiO
2meter, the mass content of silicon is 30-40%;
Described cosolvent is the mixture of one or more arbitrary proportions in methyl alcohol, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol or ethylene glycol.
3. a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO according to claim 2
2the preparation method of composite emulsion, is characterized in that, the mass ratio of nonionic emulsifier and anionic emulsifier is 1-2:1.
4. a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO according to claim 2
2the preparation method of composite emulsion, is characterized in that, the mass concentration of ammoniacal liquor is 20% ~ 28%.
5. one kind according to the polysilsesquioxane-polyacrylic ester-nanometer SiO described in claim 1 to 4 any one
2the preparation method of composite emulsion, is characterized in that, described preparation method is following steps:
(1) preparation of polysilsesquioxane emulsion: emulsifying agent, alkaline catalysts and water are added in reactor, be warming up to 40-60 ℃ and stir 15-30 minute, silane coupling agent was added slowly and added in 0.5-2 hour, keep stirring reaction 12-24 hour, obtain polysilsesquioxane emulsion;
(2) polysilsesquioxane-polyacrylic ester-nanometer SiO
2the preparation method of composite emulsion is:
A, alkyl methacrylate and alkyl acrylate are mixed and made into monomer I, 10%-20% and the vinylformic acid hydroxyalkyl acrylate of getting mix monomer I mass parts are mixed and made into monomer II;
B, polysilsesquioxane emulsion prepared by step (1) add in reactor with the 70%-85% of quality part, the 60%-80% of initiator mass parts, stir and be warming up to 75-80 ℃ after 10-20 minute, then monomer I is slowly added in reactor, within 2-4 hour, drip off, dropwise rear insulation 15-30 minute;
C, remaining initiator is dissolved in remaining water,, within 1-2 hour, being added drop-wise to continuously the product that step b obtains, dropwising rear reaction 0.5-1 hour, then be warming up to 80-85 ℃ of insulation 1-2 hour with monomer II, then be cooled to 40-50 ℃, filter discharging and obtain emulsion;
D, by cosolvent in the emulsion that slowly adds step c to obtain for 0.5-1 hour, keep stirring after 15-30 minute, silicon sol was slowly added at 1-2 hour, stir and obtain polysilsesquioxane-polyacrylic ester-nanometer SiO after 1-6 hour
2composite emulsion.
6. a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO according to claim 5
2the preparation method of composite emulsion, is characterized in that, mix monomer I multipolymer second-order transition temperature is-20-20 ℃.
7. a kind of high silicon content polysilsesquioxane-polyacrylic ester-nanometer SiO as claimed in claim 1
2the application of composite emulsion on coating and sizing agent field.
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