CN102430372B - Preparation method of strawberry-shaped organic-inorganic nanometer composite microsphere - Google Patents
Preparation method of strawberry-shaped organic-inorganic nanometer composite microsphere Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title abstract description 11
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- 239000004816 latex Substances 0.000 claims abstract description 81
- 229920000126 latex Polymers 0.000 claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 81
- 229920001577 copolymer Polymers 0.000 claims abstract description 55
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 48
- 239000000084 colloidal system Substances 0.000 claims abstract description 36
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- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims description 81
- 239000002114 nanocomposite Substances 0.000 claims description 60
- 241000220223 Fragaria Species 0.000 claims description 59
- 235000016623 Fragaria vesca Nutrition 0.000 claims description 59
- 235000011363 Fragaria x ananassa Nutrition 0.000 claims description 59
- 239000000839 emulsion Substances 0.000 claims description 49
- 239000008187 granular material Substances 0.000 claims description 46
- 235000012239 silicon dioxide Nutrition 0.000 claims description 34
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims description 29
- 229920005604 random copolymer Polymers 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 230000009477 glass transition Effects 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 7
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- 230000001105 regulatory effect Effects 0.000 claims description 6
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
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- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
The invention discloses a preparation method of a strawberry-shaped organic-inorganic nanometer composite microsphere. The preparation method comprises the following steps: 1, adding a silica colloid to a styrene acrylate copolymer latex drop by drop under stirring, and adding an acid drop by drop to adjust the pH value of the obtained material to 4.5-5.7 to form a blending system; 2, heating the blending system to 60-100DEG C under stirring, and continuously stirring for 0.5-3.0h under the shearing effect to obtain an organic-inorganic nanometer composite latex system; 3, cooling the organic-inorganic nanometer composite latex system, and adding an alkali drop by drop to adjust the pH value of the latex system to 10-12 to obtain the firmly-combined stably-dispersed strawberry-shaped organic-inorganic nanometer composite microsphere with the surface embedded with small silica particles. The preparation method has the advantages of wide resource and easy availableness of raw materials, simple preparation technology, good latex particle controllability, and wide adjustable range of the particle size of the composite microsphere. The strawberry-shaped organic-inorganic nanometer composite microsphere prepared with the method, which has the advantages of high composite degree, good structure firmness and stable placement, can be applied to the fields of coatings, rubbers, plastics, the biology and the like.
Description
Technical field
The present invention relates to field of nanocomposite materials, be specifically related to a kind of preparation method of strawberry shape organic-inorganic nano composite microsphere.
Background technology
Organic-inorganic nano composite microsphere is widely used in fields such as coating, rubber, plastics, biology.Organic-inorganic nano composite microsphere preparation method commonly used at present mainly contains situ aggregation method and physics composite algorithm two big classes.
Situ aggregation method is mainly by active forces such as organic and inorganic two alternate Electrostatic Absorption, soda acid complexing, chemical bondings, thickly combines at the in-situ polymerization on inorganic particle surface and with both are tighter by monomer.For example publication number is the preparation method that the Chinese patent application of CN 1587291A discloses a kind of strawberry organic-inorganic nano composite microsphere, utilize alkaline auxiliary monomer to be adsorbed on the acid silicon dioxide surface, in water-based system, carry out polymerization of vinyl monomer again, make strawberry organic-inorganic nano composite microsphere.Publication number is the preparation method that the Chinese patent application of CN 1631926A discloses a kind of strawberry organic-inorganic nano composite microsphere, utilize the electropositive vinyl monomer to be adsorbed on the elecrtonegativity silica surface, in water-based system, carry out polymerization of vinyl monomer again, can make strawberry organic-inorganic nano composite microsphere equally.The complex microsphere that makes by above-mentioned in-situ polymerization has the combined efficiency height, in conjunction with advantages such as fastness are good.But owing to latex phase and complex microsphere in the preparation process form synchronously, the degree of association is big each other, thereby the control of the morphosis of complex microsphere is vulnerable to bigger restriction; In addition, the in-situ polymerization system is complicated, and reaction condition is relatively harsher, also must compare particular compound by some usually, and these compounds or toxic, or relatively more expensive.
The physics composite algorithm is mainly used physisorption, thus between organic and inorganic compound degree with relative relatively poor in conjunction with fastness.Wherein, pik woods emulsification effect (Pickering emulsification effect) is a kind of typical effect mechanism of using always, and this effect refers to that granule itself has all the time and be adsorbed onto large particle surface automatically, thus effectively reduce whole system total surface can trend.But Pickering emulsification effect is still a kind of physics compound action with dynamic adsorption equilibrium feature in essence, therefore absorption stability under its poised state is all relevant with factors such as wetting of particulates, amphipathic property, shape, surface electrical behavior and particle size ratio, concentration ratios with adsorption capacity, very easily is subjected to Effect of Environmental such as system acid-base value, salinity, decentralized photo concentration and the suction behavior takes place to take off on a large scale.This limitation makes conventional Pickering method can not make organic and inorganic complex microsphere stable, firm, efficient combination.
Summary of the invention
The invention provides the preparation method of the strawberry shape organic-inorganic nano composite microsphere that a kind of technology is simple, easy to implement, compound firmly, structural controllability is strong.
A kind of preparation method of strawberry shape organic-inorganic nano composite microsphere may further comprise the steps:
(1) in the phenylpropyl alcohol copolymer latex, drips silicon dioxide colloid under the stirring, drip acid for adjusting pH to 4.5～5.7 again, form co-mixing system;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 60～100 ℃, continues to stir 0.5～3.0h under shear action, obtains organic-inorganic nano compounded latex system;
(3) the organic-inorganic nano compounded latex system cooling that step (2) is obtained, the cooling back drips alkali regulation system pH to 10～12, obtains the strawberry shape organic-inorganic nano composite microsphere.
The present invention utilizes the Pickering emulsification effect between bulky grain and granule, will hang down electronegative inorganic sol granule (being silica dioxide granule) earlier and be adsorbed onto the big micelle of polymer (being the emulsion particle in the phenylpropyl alcohol copolymer latex) surface efficiently and stably; By improving the co-mixing system temperature, impel the big micelle of polymer top layer softening again, inlay the top layer that enters the big micelle of polymer with the form of half embedding thereby will have certain oil loving inorganic sol granule; At last by cooling (generally can be cooled to room temperature) to the glass transition temperature of big micelle polymer (as a little more than, be equal to or less than the glass transition temperature of big micelle polymer), freeze or suppress the molecular motion ability of big micelle polymer segment, thereby solidify the morphosis of above-mentioned strawberry shape complex microsphere, the elecrtonegativity of inlaying silica particles by raising improves the dispersion stabilization of whole complex microsphere in aqueous phase system simultaneously.
In order to obtain better invention effect, the present invention is carried out further preferred:
In the step (1), described phenylpropyl alcohol copolymer latex is by styrene (hard monomer) and the copolymer latex of butyl acrylate (soft monomer) by the conventional emulsion polymerization preparation.The phenylpropyl alcohol copolymer latex can directly be buied from the market according to the needs of its glass transition temperature and particle size.
Glass transition temperature (the T of polystyrene
g) be about 100 ℃, the T of butyl polyacrylate
gBe about-54 ℃, the T of phenylpropyl alcohol random copolymerization polymer (being the phenylpropyl alcohol random copolymer)
gCan realize by the ratio that changes the soft or hard monomer, and can pass through FOX formula (Jin Riguang, Hua Youqing edit " Polymer Physics " third edition P142, Chemical Industry Press) estimation.T when the phenylpropyl alcohol random copolymer
gWhen low, compound degree can be better between organic and inorganic, but the structural strength of corresponding complex microsphere can be relatively poor, otherwise the compound degree of person can be relatively poor.Therefore take all factors into consideration compound degree between organic/inorganic and the structural strength of complex microsphere, the glass transition temperature of phenylpropyl alcohol random copolymer is 10～50 ℃ in the described phenylpropyl alcohol copolymer latex, and more preferably 25～35 ℃.Under higher shear heat blending temperature (60～100 ℃), glass transition temperature is that the macromolecular chain segment of 10～50 ℃ phenylpropyl alcohol random copolymer has stronger molecular motion ability, can be mounted in the emulsion particle top layer being adsorbed on the form of its surperficial silica dioxide granule with half embedding by the softening of emulsion particle top layer.And be cooled to about the glass transition temperature of big micelle polymer as after 5～35 ℃, glass transition temperature is that the molecular motion ability of 10～50 ℃ phenylpropyl alcohol random copolymer segment significantly weakens, even the molecular motion ability of segment can be freezed fully, thereby, can make above-mentioned silica dioxide granule be embedded in half being fixed of embedding form in the emulsion particle top layer, also can make resulting strawberry shape organic-inorganic nano composite microsphere have preferably structural strength, dimensional stability, bin stability and external stressed strong resistivity simultaneously.The average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 100～400nm, particle diameter profile exponent Span value (Span=(D
90-D
10)/D
50, D wherein
90, D
10And D
50Represent to be equivalent to by the mass accumulation that the little side of particle diameter begins 90%, 10% and 50% o'clock corresponding particle size of gross weight respectively) smaller or equal to 1.The particle diameter regulation and control of emulsion particle can realize by emulsification system, monomer consumption and the adding mode that changes in the emulsion polymerisation.
Silicon dioxide colloid can pass through conventional
Method (detailed process can be with reference to following document:
W, Fink A, Bohn E.Controlled growth of monodisperse silica spheres in the micron size range.J Colloid Interface Sci, 1968,26 (1): 62-69) make.Good by the silica dioxide granule in the silicon dioxide colloid of this method preparation stably dispersing, wetability in aqueous phase system, do not need can be directly used among the present invention through any modification.
The residual organic group that has part not remove of the silica particles of method preparation, these organic groups can give silica particles certain lipophile.These characteristics of silicon dioxide colloid are conducive to all realize that cryogenic absorption and the high temperature on the emulsion particle surface of silica dioxide granule in the phenylpropyl alcohol copolymer latex inlays.
The average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 10～40nm, and particle diameter profile exponent Span value is smaller or equal to 1.Average grain diameter is 10～20nm more preferably, this is for the Pickering absorption that realizes the emulsion particle in silica dioxide granule and the phenylpropyl alcohol copolymer latex better and inlays, and the size ratio that generally needs emulsion particle in the control phenylpropyl alcohol copolymer latex and silica dioxide granule is at one more than the order of magnitude.
Hydrochloric acid is selected in described acid for use, specifically can select the watery hydrochloric acid as mass percentage concentration 10%.Regulate pH value to 4.5～5.7 by dripping hydrochloric acid.This be because silica equipotential point in the scope of pH=3～4, under selected system pH=4.5～5.7 environment, the zeta current potential of dioxide/silica gel surface is in the low scope of 5～20mv.Therefore, on the one hand, silicon dioxide colloid has certain dispersion stabilization under selected acid or alkali environment, be unlikely to take place the behavior of reuniting on a large scale, easily is adsorbed onto the emulsion particle surface in the phenylpropyl alcohol copolymer latex simultaneously again; On the other hand, the electrostatic repulsion between silica dioxide granule a little less than, be unlikely to influence the fine and close absorption of individual layer on the emulsion particle surface of silica dioxide granule in the phenylpropyl alcohol copolymer latex.Further by the assessment of the compound degree of organic/inorganic and system stability, preferred system pH value is 5.0～5.2.
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1: 5～100.When greater than this weight ratio scope, a large amount of not free silicon dioxide particles of absorption can appear at continuous aqueous phase, and namely the compound degree of silica is lower; When less than this scope, the covering of the emulsion particle surface silica dioxide particle in the phenylpropyl alcohol copolymer latex is complete inadequately, and there is the large-area exposed region that is not adsorbed with silica dioxide granule in the emulsion particle surface.
In the step (2), co-mixing system is warming up to 60～100 ℃, in the time of also can correspondingly being warming up to 60～100 ℃ owing to the phenylpropyl alcohol random copolymer, approaches even reach the flow temperature (T of phenylpropyl alcohol random copolymer easily
f), thereby the segment of phenylpropyl alcohol random copolymer even whole macromolecular chain all can have stronger molecular motion ability.In addition, particularly under the plasticization of the microdialysis water on emulsion particle top layer and adsorbed water, the softening viscosity flow of the easier generation of phenylpropyl alcohol random copolymer on the shallow top layer of emulsion particle and amoeboid movement.Thereby, corresponding emulsion particle top layer has stronger adhesive capacity and interior inclusive, and then a large amount of silica dioxide granules of surface attachment can be mounted to the oarse-grained top layer of emulsion particle with the form of half embedding, thereby the Stability Analysis of Structures that finally is easy to get, compound firm strawberry shape organic-inorganic nano composite microsphere.
Co-mixing system stirs 0.5～3.0h down at 60～100 ℃, is in order to realize homogenizing of co-mixing system better on the one hand, is collision, adhesion chance in order to increase silica dioxide granule and emulsion particle on the other hand.Thereby promote inorganic sol granule (silica dioxide granule) in evenly fully the adsorbing and inlay of organic bulky grain (emulsion particle in the phenylpropyl alcohol copolymer latex) top layer, and promote phenylpropyl alcohol random copolymer macromolecular chain in the emulsion particle top layer in the entanglement of silica dioxide granule rough surface and adhere to.
In the step (3), the condition of described cooling is: 2～10min is cooled to 5～35 ℃.The organic-inorganic nano compounded latex is quickly cooled to 5～35 ℃, purpose is the molecular motion ability of quick freezing phenylpropyl alcohol random copolymer polymer segment, thereby latex bulky grain (emulsion particle) is to half embedding state of inorganic sol granule (silica dioxide granule) when coming mutually to maintain high temperature better by solidifying emulsion particle, and the form of inlaying of this half embedding can greatly improve between organic and inorganic compound degree and in conjunction with fastness.
Described alkali is selected ammoniacal liquor for use, specifically can select the weak aqua ammonia as mass percentage concentration 5%, regulate organic-inorganic nano compounded latex system pH to 10～12 by dropping ammonia, so that the silica dioxide granule that inlay on the emulsion particle surface has higher surperficial elecrtonegativity, thereby can make whole complex microsphere in aqueous phase system, have better dispersion stabilization, be beneficial to finally obtain the strawberry shape organic-inorganic nano composite microsphere colloid of stably dispersing.Simultaneously this also is fully to take off suction for what impel the non-embedding type physical absorption silica dioxide granule in strawberry shape organic-inorganic nano composite microsphere surface.
In the whole process of preparation, remain to stir and shear.In step (1) and step (3), stir to shear just in order to suppress and to avoid particle deposition and reunion in the system, thereby shear rate is not had strict requirement; In step (2), stir to shear and be not only in order to suppress deposition and to reunite, the more important thing is collision, adhesion chance in order to increase silica dioxide granule and emulsion particle simultaneously, thereby promote inorganic sol granule (silica dioxide granule) evenly fully adsorbing and inlay on organic bulky grain (emulsion particle in the phenylpropyl alcohol copolymer latex) top layer, therefore, shear rate there is certain requirement.Be the representative reactions device with S212B-2 type double-layer glass reaction kettle, preferably shear rate is 200～600 rev/mins (rpm).Under this shear strength, silica dioxide granule can evenly be adsorbed onto the emulsion particle surface rapidly, and is entered the emulsion particle top layer by half embedding effectively under the condition of high temperature; In addition, again can be by stirring the peptizaiton in shearing field, avoid sticking between emulsion particle that Yin Gaowen causes and and sedimentation, thereby finally obtain the strawberry shape organic and inorganic complex microsphere of uniform and stable dispersion.
The preparation method of described strawberry shape organic-inorganic nano composite microsphere, further preferred, may further comprise the steps:
(1) in the phenylpropyl alcohol copolymer latex, drips silicon dioxide colloid under the stirring, drip acid for adjusting pH to 5.0～5.2 again, form co-mixing system;
The glass transition temperature of the phenylpropyl alcohol random copolymer in the described phenylpropyl alcohol copolymer latex is 25～35 ℃;
The average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 200～300nm, and particle diameter profile exponent Span value is smaller or equal to 1;
The average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 10～20nm, and particle diameter profile exponent Span value is smaller or equal to 1;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1: 30～50;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 90～95 ℃, continues to stir 2.0～3.0h under the shear rate of 400～500rpm, obtains organic-inorganic nano compounded latex system;
(3) the organic-inorganic nano compounded latex system that step (2) is obtained is cooled to 20～25 ℃ at 2～5min, and the cooling back drips alkali and regulates pH to 10～12, obtains the strawberry shape organic-inorganic nano composite microsphere.
Silica dioxide granule is embedded in the emulsion particle top layer securely with half embedding form, forms the strawberry shape organic and inorganic complex microsphere of uniform and stable dispersion.SiO not only
2Compound degree is very high, and SiO on the single complex microsphere
2Particle also very high by the embedding degree.Further preferably make the compound degree of strawberry shape organic-inorganic nano composite microsphere higher, structural strength is better and stable composition is better, makes preferably that further the present invention has produced the technique effect of highly significant.
The preparation method of described strawberry shape organic-inorganic nano composite microsphere, further preferred, may further comprise the steps:
(1) drip silicon dioxide colloid under the stirring in the phenylpropyl alcohol copolymer latex, dripping hydrochloric acid is regulated pH to 5.0 again, forms co-mixing system;
The glass transition temperature of the phenylpropyl alcohol random copolymer in the described phenylpropyl alcohol copolymer latex is 30 ℃;
The average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 200nm, and particle diameter profile exponent Span value equals 0.8;
The average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 15nm, and particle diameter profile exponent Span value equals 0.8;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1: 50;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 95 ℃, continues to stir 2.0h under the shear rate of 500rpm, obtains organic-inorganic nano compounded latex system;
(3) the organic-inorganic nano compounded latex system that step (2) is obtained is cooled to 20 ℃ at 2min, and cooling back dropping ammonia is regulated pH to 11, obtains the strawberry shape organic-inorganic nano composite microsphere.
Transmission electron microscope photo and the SiO of the strawberry shape organic-inorganic nano composite microsphere by embodiment 3
2The data of compound degree can characterize: the strawberry shape organic-inorganic nano composite microsphere of the technical scheme preparation by embodiment 3 is SiO not only
2Compound degree is very high, and SiO on the single complex microsphere
2Particle also very high by the embedding degree.Further preferably make the compound degree of strawberry shape organic-inorganic nano composite microsphere higher, structural strength is better and stable composition is better, has obtained unforeseeable technique effect.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention prepares the phenylpropyl alcohol copolymer latex with conventional emulsion polymerization, with tradition
Legal system prepared silicon dioxide colloid, above-mentioned preparation method's technical maturity, with low cost.Used emulsion particle generates respectively by different courses of reaction with silica dioxide granule, thereby the parameters such as particle diameter of the particle diameter of emulsion particle, glass transition temperature, flow temperature and silica dioxide granule are easy to adjust, controllability is strong, modification scope is big;
(2) do not relate to chemical reaction and organic solvent in the preparation process of the present invention, need not particular matter, clean environment firendly has good economic benefits.Preparation process of the present invention only relates to the simple change of system temperature and pH value, thereby compare with numerous in-situ polymerization method for preparing based on mechanism such as charge effect, acid-base functions, have advantages such as technology is simple, easy to operate, controllability is good, production cost is lower, be fit to large-scale industrialization production;
(3) the present invention prepares that silica dioxide granule is embedded in the emulsion particle top layer securely with half embedding form in the gained strawberry shape organic-inorganic nano composite microsphere, and this complex form can not change along with the change of environmental factors such as system acid-base value, salinity, decentralized photo concentration.Thereby prepare complex microsphere with other physical absorption and compare, have compound degree height, structural strength is good, stable composition is good, advantage such as stably dispersing in aqueous phase system, can be widely used in fields such as coating, rubber, plastics, biology, have broad application prospects.
Description of drawings
Fig. 1 is the preparation process schematic diagram of strawberry shape organic-inorganic nano composite microsphere of the present invention;
Fig. 2 is that dripping hydrochloric acid is regulated before the pH value to 4.5 among the embodiment 3, the transmission electron microscope photo of phenylpropyl alcohol copolymer latex and silicon dioxide colloid simple blend product;
Fig. 3 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 3;
Fig. 4 is the transmission electron microscope photo (multiplication factor is higher) of single strawberry shape organic-inorganic nano composite microsphere among the embodiment 3;
Fig. 5 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 6;
Fig. 6 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 7;
Fig. 7 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 8;
Fig. 8 is the grading curve of silica dioxide granule, the emulsion particle in the phenylpropyl alcohol copolymer latex and strawberry shape organic-inorganic nano composite microsphere (being called for short complex microsphere among the figure) among the embodiment 10.
The specific embodiment
As shown in Figure 1, be the preparation process of strawberry shape organic-inorganic nano composite microsphere of the present invention:
(1) the present invention utilizes the Pickering effect between bulky grain and granule, in the phenylpropyl alcohol copolymer latex, drip silicon dioxide colloid under the stirring, both mix, the simple mixed form of phenylpropyl alcohol copolymer latex and silicon dioxide colloid is shown in a among Fig. 1, drip acid for adjusting pH to 4.5～5.7 then, form co-mixing system, make silica dioxide granule be adsorbed onto the emulsion particle surface in the phenylpropyl alcohol copolymer latex efficiently, shown in b among Fig. 1;
(2) co-mixing system that under stirring step (1) is obtained is warming up to 60～100 ℃, under shear action, continue to stir 0.5～3h, obtain organic-inorganic nano compounded latex system, make a large amount of silica dioxide granules of surface attachment be mounted to the emulsion particle top layer with the form of half embedding, shown in c among Fig. 1;
(3) the organic-inorganic nano compounded latex system that step (2) is obtained is cooled to 5～35 ℃ at 2～10min, organic-inorganic nano compounded latex system behind the fast cooling can well keep the silica of half embedding to inlay state, shown in d among Fig. 1, drip alkali again and regulate pH to 10～12, obtain the strawberry shape organic-inorganic nano composite microsphere of stably dispersing, shown in e among Fig. 1.
Embodiment 1～12
A kind of preparation method of strawberry shape organic-inorganic nano composite microsphere may further comprise the steps:
(1) be reaction unit with S212B-2 type double-layer glass reaction kettle, after dripping silicon dioxide colloid in the phenylpropyl alcohol copolymer latex under the stirring, drip mass percentage concentration again and be 10% hydrochloric acid, regulate pH value to 4.5～5.7 (i.e. pH values in the shear heat blending condition in the table 1), form co-mixing system;
The phenylpropyl alcohol copolymer latex is the copolymer latex that is prepared by conventional emulsion polymerization by styrene and butyl acrylate, and the styrene chain link in the phenylpropyl alcohol random copolymer in the phenylpropyl alcohol copolymer latex and the weight ratio of butyl acrylate chain link (being called for short the St/BA weight ratio in the table 1) are 6: 5～7: 2;
The glass transition temperature of phenylpropyl alcohol random copolymer in the phenylpropyl alcohol copolymer latex (being called for short Tg in the table 1) is 10～50 ℃;
The average grain diameter of the emulsion particle in the phenylpropyl alcohol copolymer latex is 100～400nm, and particle diameter profile exponent Span value is smaller or equal to 1;
(table 1 is called for short SiO to the average grain diameter of the silica dioxide granule in the silicon dioxide colloid
2Average grain diameter) be 10～40nm, particle diameter profile exponent Span value is smaller or equal to 1;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1: 5～100 (i.e. inorganic in the table 1/organic ratios);
(2) co-mixing system that under stirring step (1) is obtained is warming up to 60～100 ℃ (i.e. temperature in the shear heat blending condition in the table 1), under shear action, continue to stir 0.5～3.0h (i.e. time in the shear heat blending condition in the table 1), obtain organic-inorganic nano compounded latex system;
Shear action is carried out under the shear rate of 200～600rpm (i.e. rotating speed in the shear heat blending condition in the table 1);
(3) directly in S212B-2 type double-layer glass reaction kettle, lead to 0 ℃ cooling water, with the organic-inorganic nano compounded latex system cooling that step (2) obtains, the condition of cooling is: 2～10min is cooled to 5～35 ℃ (i.e. time in the complex microsphere system and temperature in the table 1).The dropping mass percentage concentration is 5% ammoniacal liquor adjusting pH to 10～12 (i.e. pH value in the complex microsphere system in the table 1) after finishing, and obtains the strawberry shape organic-inorganic nano composite microsphere, the average grain diameter of complex microsphere and SiO
2Compound degree is as shown in table 1, and the characterizing method that relates in the preparation process sees Table the characterizing method explanation after 1.
Embodiment 1～12 select respectively different concrete parameters set by step (1) to (3) carry out the preparation of strawberry shape organic-inorganic nano composite microsphere, the structural characterization of concrete parameter and strawberry shape organic-inorganic nano composite microsphere is as shown in table 1.
Table 1
Fig. 2 is that dripping hydrochloric acid is regulated before the pH value to 4.5 among the embodiment 3, the transmission electron microscope photo of phenylpropyl alcohol copolymer latex and silicon dioxide colloid simple blend product, Fig. 3 and Fig. 4 are the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere final among the embodiment 3.As shown in Figure 2, drip silicon dioxide colloid under the stirring in the phenylpropyl alcohol copolymer latex, through simply mixing, before dripping hydrochloric acid, system pH is neutral.The silica particles elecrtonegativity is stronger under this system acid-base value, thereby the emulsion particle surface absorption of silica dioxide granule in the phenylpropyl alcohol copolymer latex is less; And as shown in Figure 3 and Figure 4, under pH value 5.0 environment, the silica particles static behaviour a little less than, can be comparatively fully and be adsorbed onto the emulsion particle surface equably, and after the shear at high temperature blend is handled, the silica dioxide granule of absorption can be embedded in the emulsion particle top layer securely with the form of half embedding, forms the strawberry shape organic-inorganic nano composite microsphere of uniform and stable dispersion.
Fig. 5 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 6, Fig. 6 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 7, and Fig. 7 is the transmission electron microscope photo of strawberry shape organic-inorganic nano composite microsphere among the embodiment 8.As Fig. 3, Fig. 4, Fig. 5, Fig. 6, shown in Figure 7, and shown in the table 1, with respect to the strawberry shape organic-inorganic nano composite microsphere of embodiment 7, embodiment 8 preparations, the strawberry shape organic-inorganic nano composite microsphere of embodiment 3, embodiment 6 preparations has higher compound degree.The difference of compound degree is mainly reflected in two aspects: one side SiO from table 1
2With the compound level data of styrene-acrylic latex grain as can be seen; On the other hand, emulsion particle surface SiO from Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7
2Level of coverage, system in the free SiO of absorption not
2The number of particle also as can be seen.
Under given conditions, be that styrene chain link in the phenylpropyl alcohol random copolymer in the phenylpropyl alcohol copolymer latex and the weight ratio of butyl acrylate chain link are 2: 1, the glass transition temperature of phenylpropyl alcohol random copolymer is 30 ℃, the weight ratio of the phenylpropyl alcohol random copolymer in the silica in the silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1: 30～50, shear heat co-mixing system pH value is 5.0～5.2, the shear heat blending temperature is at 90～95 ℃, shear rate is 400～500rpm, under the conditions (actual conditions sees embodiment 3 and the embodiment 6 in the table 1 for details) such as pH value=11 in the complex microsphere system, particularly shear heat co-mixing system pH value is under 5.0～5.2 the situation in table 1, obtain compound degree height, structural strength is good, stable composition is good, the good organic-inorganic nano composite microsphere of dispersion stabilization in aqueous phase system has the technique effect of highly significant.
Under the specified conditions in embodiment 3 (actual conditions sees the embodiment 3 in the table 1 for details), as the SiO among Fig. 3 and the table 1
2The data of compound degree can characterize: the strawberry shape organic-inorganic nano composite microsphere of the technical scheme preparation by embodiment 3 is SiO not only
2Compound degree is very high, and SiO on the single complex microsphere
2Particle also very high by the embedding degree makes that the compound degree of strawberry shape organic-inorganic nano composite microsphere is higher, structural strength better and stable composition is better, obtained unforeseeable technique effect.
The characterizing method explanation that relates among the embodiment 1～12:
The particle diameter of measuring emulsion particle, silica dioxide granule and strawberry shape organic-inorganic nano composite microsphere by the laser particle analyzer LB-550 of company (Japanese Holiba) distributes, and obtains its average grain diameter value and particle diameter profile exponent Span value.
Observe the morphosis of strawberry shape organic-inorganic nano composite microsphere by transmission electron microscope (the Japanese JEOL JSM-1200EX T20 of company).
SiO
2Compound level calculating method is as follows: add NaCl in the strawberry shape organic-inorganic nano composite microsphere colloid of preparation, be fitted on the salinity of 1.0M (mol/L), impel sedimentation behind the system breakdown of emulsion.In filter process, use again with respect to the deionized water cyclic washing of 500 times of weight of filter cake total amount and remove wherein the not free SiO of absorption
2With other little molecule.Put into Muffle furnace behind the filtration cakes torrefaction, removed wherein organic component in 2 hours 700 ℃ of calcination, obtain the SiO of composite portion
2, its weight and add of SiO
2The percentage by weight of amount namely is defined as SiO
2Compound degree.Percentage is more high, means more SiO
2Granule can be embedded in the big emulsion particle of copolymerization surface with the form of half embedding.
Claims (6)
1. the preparation method of a strawberry shape organic-inorganic nano composite microsphere may further comprise the steps:
(1) in the phenylpropyl alcohol copolymer latex, drips silicon dioxide colloid under the stirring, drip acid for adjusting pH to 4.5～5.7 again, form co-mixing system;
The glass transition temperature of the phenylpropyl alcohol random copolymer in the described phenylpropyl alcohol copolymer latex is 10～50 ℃;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1:5～100;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 60～100 ℃, continues to stir 0.5～3.0h under shear action, obtains organic-inorganic nano compounded latex system;
Described shear action is carried out under 200～600 rev/mins shear rate;
(3) the organic-inorganic nano compounded latex system cooling that step (2) is obtained, the cooling back drips alkali regulation system pH to 10～12, obtains the strawberry shape organic-inorganic nano composite microsphere;
The condition of described cooling is: 2～10min is cooled to 5～35 ℃.
2. the preparation method of strawberry shape organic-inorganic nano composite microsphere according to claim 1, it is characterized in that, in the step (1), the average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 100～400nm, and particle diameter profile exponent Span value is smaller or equal to 1.
3. the preparation method of strawberry shape organic-inorganic nano composite microsphere according to claim 1, it is characterized in that, in the step (1), the average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 10～40nm, and particle diameter profile exponent Span value is smaller or equal to 1.
4. the preparation method of strawberry shape organic-inorganic nano composite microsphere according to claim 1 is characterized in that, in the step (1), described acid is hydrochloric acid;
Perhaps, in the step (3), described alkali is ammoniacal liquor.
5. the preparation method of strawberry shape organic-inorganic nano composite microsphere according to claim 1 is characterized in that, may further comprise the steps:
(1) in the phenylpropyl alcohol copolymer latex, drips silicon dioxide colloid under the stirring, drip acid for adjusting pH to 5.0～5.2 again, form co-mixing system;
The glass transition temperature of the phenylpropyl alcohol random copolymer in the described phenylpropyl alcohol copolymer latex is 25～35 ℃;
The average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 200～300nm, and particle diameter profile exponent Span value is smaller or equal to 1;
The average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 10～20nm, and particle diameter profile exponent Span value is smaller or equal to 1;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1:30～50;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 90～95 ℃, continues to stir 2.0～3.0h under 400～500 rev/mins shear rate, obtains organic-inorganic nano compounded latex system;
(3) the organic-inorganic nano compounded latex system that step (2) is obtained is cooled to 20～25 ℃ at 2～5min, and the cooling back drips alkali and regulates pH to 10～12, obtains the strawberry shape organic-inorganic nano composite microsphere.
6. the preparation method of strawberry shape organic-inorganic nano composite microsphere according to claim 5 is characterized in that, may further comprise the steps:
(1) drip silicon dioxide colloid under the stirring in the phenylpropyl alcohol copolymer latex, dripping hydrochloric acid is regulated pH to 5.0 again, forms co-mixing system;
The glass transition temperature of the phenylpropyl alcohol random copolymer in the described phenylpropyl alcohol copolymer latex is 30 ℃;
The average grain diameter of the emulsion particle in the described phenylpropyl alcohol copolymer latex is 200nm, and particle diameter profile exponent Span value equals 0.8;
The average grain diameter of the silica dioxide granule in the described silicon dioxide colloid is 15nm, and particle diameter profile exponent Span value equals 0.8;
The weight ratio of the phenylpropyl alcohol random copolymer in the silica in the described silicon dioxide colloid and the phenylpropyl alcohol copolymer latex is 1:50;
(2) co-mixing system that under the stirring step (1) is obtained is warming up to 95 ℃, continues to stir 2.0h under 500 rev/mins shear rate, obtains organic-inorganic nano compounded latex system;
(3) the organic-inorganic nano compounded latex system that step (2) is obtained is cooled to 20 ℃ at 2min, and cooling back dropping ammonia is regulated pH to 11, obtains the strawberry shape organic-inorganic nano composite microsphere.
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| CN108641024B (en) * | 2018-05-15 | 2021-03-30 | 华南理工大学 | Method for synthesizing magadiite/PMMA (polymethyl methacrylate) nano composite microspheres in Pickering emulsion by utilizing pH value regulation |
| CN109985584B (en) * | 2019-04-23 | 2021-09-21 | 河北工业大学 | Preparation method of adjustable and controllable strawberry-shaped silicon dioxide-organic hybrid composite microspheres |
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| WO1999047253A1 (en) * | 1998-03-19 | 1999-09-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
| CN1631926A (en) * | 2004-11-11 | 2005-06-29 | 复旦大学 | Process for preparing strawberry organic-inorganic nano composite microsphere |
| CN1654493A (en) * | 2005-01-11 | 2005-08-17 | 天津大学 | Method for preparing monodispersed large grain-size hollow styrene-acrylic polymer microsphere in low soap system |
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| WO1999047253A1 (en) * | 1998-03-19 | 1999-09-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
| CN1631926A (en) * | 2004-11-11 | 2005-06-29 | 复旦大学 | Process for preparing strawberry organic-inorganic nano composite microsphere |
| CN1654493A (en) * | 2005-01-11 | 2005-08-17 | 天津大学 | Method for preparing monodispersed large grain-size hollow styrene-acrylic polymer microsphere in low soap system |
| CN102008925A (en) * | 2010-12-17 | 2011-04-13 | 天津大学 | Method for preparing inorganic/organic composite microspheres |
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