CN102140217A - Preparation method and use of polyacrylate/silica solution composite material - Google Patents
Preparation method and use of polyacrylate/silica solution composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and use of a polyacrylate/silica solution composite material. In the invention, the silica solution modified polyacrylate/silica solution composite material is obtained by using cheap and readily available silica solution as inorganic nano modifier, by the pre-emulsification and seeded emulsion polymerization of monomers such as acrylic ester and by adding modified silica solution in the preparation process of a polyacrylate shell in a core-shell structure for effective combination, and the average particle size of the composite material is between 100 and 150 nanometers. When the polyacrylate/silica solution composite material is used as an impact resistant modifier for polrvinyl chloride, the polrvinyl chloride has high impact resistance and excellent mechanical properties such as tensile strength and processing performance. In addition, the use of the silica solution helps to reduce the production cost of products.
Description
Technical field
The present invention relates to the preparation method of a kind of nucleocapsid structure polyacrylic ester (ACR)/silicon sol matrix material and as the application of igelite anti-impact modifier.
Background technology
Silicon sol is that the colloidal particle of silicon-dioxide are scattered in the colloidal solution in the water, is amorphous Si O
2The stable dispersion of the colloid size of particle in water.Silicon sol has following characteristics: 1. colloidal sol is low viscous colloidal solution, good dispersity; 2. silicon sol has good cementability; 3. the silicon hydroxyl on silica sol particle surface and planar water can improve wettability; 4. silicon sol has good reactivity, and can carry out at homogeneous phase, by with the uniform mixing of organic resin, can improve its machinery, optics and electrical property.As a kind of important inorganic macromolecule material, silicon sol has been widely used in fields such as chemical industry, precision casting, weaving, papermaking, coating, food, electronics, ore dressing.
By silicon sol is carried out modification, make the silicon sol surface have oil loving organic group, will have the effect of very big promotion in the application aspect the organic polymer material to silicon sol.Organic/inorganic composite material has the characteristics of organism and inorganics concurrently, particularly characteristics inorganic, organic, nanoparticle three aspects are combined, prepare polymer based nanocomposites, can improve the over-all properties of polymkeric substance, for enhancing, toughening modifying and the functional modification of polymkeric substance provides new approach comprehensively.
Chinese invention patent ZL 200810220303.9 discloses a kind of nanometer SiO
2The preparation method of/ACR composite particles is by to 20 ~ 40nm nanometer SiO
2Carry out the coupling modification and obtain nanometer SiO
2Emulsion, it is compound to carry out grafting then in the process of preparation ACR particle shell, obtains a kind of nanometer SiO
2/ ACR composite particles is used for the performances such as tensile strength, shock strength and Vicat softening point of PVC processing can obviously improvement goods, thereby improves the use properties of goods.Chinese patent 200910046420 discloses a kind of Nano silica sol/acrylate composite emulsion and preparation method thereof, in the presence of Nano silica sol and alkyl alcohol solvent, adopt seed emulsion polymerization or situ aggregation method, with the acrylate monomer polymerization, obtain with the silica dioxide granule is nuclear, acrylate copolymer is the nanometer nucleocapsid structure composite emulsion that shell is formed, composite emulsion has higher tensile strength, tear strength and better acid and alkali-resistance, weather-proof, wear-resisting, performance such as anti-ultraviolet ageing and anti-soil can be used for coating for internal and external wall, all many-sides such as ground terrace paint and professional athletic ground finishing coat, and environmental protection, have vast market prospect.Chinese patent 200810010114 discloses a kind of modified silicasol and the application in the preparation water-borne coatings thereof, with the water silica sol is after raw material carries out modification, be applied to the preparation of coating used as base-material, the aqueous inorganic paint that makes has organic coating high-decoration, good sticking power, toughness concurrently, the high rigidity that has inorganic paint again, chemical-resistant can be widely used in substrate surface and building trades such as metal, glass, timber, plastics.
Summary of the invention
The invention discloses the preparation method and the application thereof of a kind of nucleocapsid structure polyacrylic ester (ACR)/silicon sol matrix material, by selecting suitable properties-correcting agent, silicon sol is carried out modification, make the silicon sol surface have oil loving organic group, improve the consistency of itself and organic resin; Adopting the seed emulsion semi-continuous process, is monomer with the butyl acrylate, N, N
,-methylene-bisacrylamide is as linking agent, and Potassium Persulphate is as initiator, and sodium lauryl sulphate makes seed emulsion as the emulsifying agent stabilising system; With butyl acrylate and vinylbenzene is monomer, N, N
,-methylene-bisacrylamide is as linking agent, and Potassium Persulphate is as initiator, and sodium lauryl sulphate prepares stratum nucleare as the emulsifying agent stabilising system; With methyl methacrylate and vinylbenzene is monomer, N, N
,-methylene-bisacrylamide is as linking agent, Potassium Persulphate is as initiator, adopting sodium lauryl sulphate and reactive emulsifier alkyl phenol ether ammonium sulfate is compound emulsifying agent, makes organic monomer and quantitative modified silicasol mix and obtains stabilising system, the preparation shell.React completely after breakdown of emulsion washs, promptly obtain nanometer ACR/ silicon sol composite particles after the drying.Preparation method's particular content of a kind of Polyacrylate matrix material provided by the invention comprises the steps:
(1) adopts γ-(methacryloxypropyl) propyl trimethoxy silicane, 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, two kinds in the γ-An Bingjisanyiyangjiguiwan as properties-correcting agent, at 40 ~ 60 ℃ silicon sol is carried out surface modification, in 5 ~ 8 hours reaction times, obtain modified silicasol, the properties-correcting agent consumption is 1.0%～12.0% of a silicon sol total amount, and wherein the mass ratio of two kinds of properties-correcting agent is 1:1;
(2) with distilled water be solvent, butyl acrylate is as monomer A, Potassium Persulphate is an initiator, consumption is 0.1～0.8% of a monomer A quality, sodium lauryl sulphate is as emulsifying agent, and consumption is 0.5～5.0% of a monomer A quality, also continues under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(3) be monomers B with butyl acrylate and vinylbenzene, wherein butyl acrylate and cinnamic mass ratio are 4:1, N, N
,-methylene-bisacrylamide is as linking agent, consumption is 0.02～0.1% of a monomers B quality, Potassium Persulphate is as initiator, consumption is 0.05～0.3% of a monomers B quality, and sodium lauryl sulphate is as emulsifying agent, and consumption is 0.1～1.0% of a monomers B quality, said components added in the distilled water to stir obtain pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (2), also continues to react 1 hour under the stirring, obtain examining emulsion at 75 ℃;
(4) be monomer C with methyl methacrylate and vinylbenzene, methyl methacrylate and cinnamic mass ratio are 2:1, N, N
,-methylene-bisacrylamide is as linking agent, and consumption is 0.1～0.5% of a monomer C quality, and Potassium Persulphate is as initiator, and consumption is 0.05～0.3% of a monomer C quality; Adopting sodium lauryl sulphate and reactive emulsifier alkyl phenol ether ammonium sulfate is compound emulsifying agent, the mass ratio of sodium lauryl sulphate and reactive emulsifier alkyl phenol ether ammonium sulfate is 70:30, the compound emulsifying agent consumption is 0.1～2.0% of a monomer C quality, said components and modified silicasol joined to stir in the distilled water obtain pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (3), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure Polyacrylate composite emulsion;
(5) nucleocapsid structure Polyacrylate composite emulsion obtains nucleocapsid structure Polyacrylate matrix material through breakdown of emulsion, drying.
Monomer A in the above-mentioned steps (1) (2) (3) (4): monomers B: monomer C mass ratio is 5 ~ 10:50 ~ 70:20 ~ 40, with SiO
2Meter modified silicasol consumption is 5.0～20.0% of monomer A+monomers B+monomer C total mass.
Used silicon sol is the sodium type in the above-mentioned steps (1), solid content 30 ± 1%.
Monomer A in the above-mentioned steps (2): the distilled water mass ratio is 20:80.
Monomers B in the above-mentioned steps (3): distilled water mass ratio 40:60.
Monomer C in the above-mentioned steps (4): the distilled water mass ratio is 30:70.
The particle diameter of nucleocapsid structure Polyacrylate matrix material is at 100 ~ 150nm in the above-mentioned steps (5).The present invention also provides the Polyacrylate matrix material of described preparation method's preparation to be applied to the processing of polyvinyl chloride as impact modifier.
Beneficial effect of the present invention:
The present invention selects for use silicon sol cheap and easy to get as inorganic nanometer modified dose, by monomeric pre-emulsification, seeded emulsion polymerizations such as acrylate, and the silicon sol that adds through modification in the process of nucleocapsid structure polyacrylic ester (ACR) shell preparation carries out effectively compound, obtain silica sol modified ACR/ silicon sol composite particles, median size is between 100 ~ 150nm, as polyvinyl chloride (PVC) anti-impact modifier, not only give its excellent shock resistance, have mechanical properties such as good tensile and processing characteristics simultaneously.In addition, the use of silicon sol helps reducing production cost of products.
Embodiment
Below further specify content of the present invention by specific embodiment, but be not limited to following embodiment.
Embodiment one:
(1) with composite modifier γ-(methacryloxypropyl) propyl trimethoxy silicane+3-(2,3-epoxy third oxygen) propyl trimethoxy silicane+γ-An Bingjisanyiyangjiguiwan (mass ratio of two kinds of properties-correcting agent is 1:1) adds in the silicon sol, the properties-correcting agent consumption is 3.0% of a silicon sol total amount, also reacted 6 hours under the stirring at 55 ℃, obtain modified silicasol.
(2) with distilled water be solvent, add monomer A (butyl acrylate) successively, initiator potassium persulfate is (consumption is 0.3 % of monomer A quality), emulsifier sodium lauryl sulfate (consumption be monomer A quality 3.2%), also continue under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(3) with monomers B (forming by mass ratio 4:1), linking agent N, N by butyl acrylate, vinylbenzene
,-methylene-bisacrylamide (consumption be monomers B quality 0.1%), initiator potassium persulfate (consumption is 0.18 % of monomers B quality), emulsifier sodium lauryl sulfate (consumption is 0.8 % of monomers B quality) adds successively in the distilled water to stir and obtains pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (2), also continue to react 1 hour under the stirring at 75 ℃, obtain examining emulsion;
(4) monomer C(is made up of by mass ratio 2:1 methyl methacrylate, vinylbenzene), linking agent N, N
,-methylene-bisacrylamide (consumption be monomer C quality 0.3%), initiator potassium persulfate (consumption be monomer C quality 0.15%), compound emulsifying agent is (by sodium lauryl sulphate, reactive emulsifier alkyl phenol ether ammonium sulfate is pressed mass ratio 70:30 and is formed, the compound emulsifying agent consumption be monomer C quality 1.5%) modified silicasol that obtains with step (1) joins successively to stir in the distilled water and obtains pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (3), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure polyacrylic ester (ACR)/silicon sol composite emulsion;
(5) above-mentioned ACR/ silicon sol composite emulsion obtains ACR/ silicon sol composite particles through breakdown of emulsion, drying.
Wherein, monomer A: monomers B: monomer C mass ratio is 5:60:35, and modified silicasol is the sodium type, solid content 30 ± 1%, and consumption is (with SiO
2Meter, down together) be 8% of (monomer A+monomers B+monomer C) total mass; Monomer A in the step (2): the distilled water mass ratio is 20:80, monomers B in the step (3): distilled water mass ratio 40:60, monomer C in the step (4): the distilled water mass ratio is 30:70.
Embodiment two:
(1) with composite modifier γ-(methacryloxypropyl) propyl trimethoxy silicane+3-(2,3-epoxy third oxygen) propyl trimethoxy silicane+γ-An Bingjisanyiyangjiguiwan (mass ratio of two kinds of properties-correcting agent is 1:1) adds in the silicon sol, the properties-correcting agent consumption is 6.0% of a silicon sol total amount, also reacted 8 hours under the stirring at 45 ℃, obtain modified silicasol.
(2) with distilled water be solvent, add monomer A (butyl acrylate) successively, initiator potassium persulfate is (consumption be monomer A quality 0.5%), emulsifier sodium lauryl sulfate (consumption be monomer A quality 4.0%), also continue under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(3) with monomers B (forming by mass ratio 4:1), linking agent N, N by butyl acrylate, vinylbenzene
,-methylene-bisacrylamide (consumption be monomers B quality 0.08%), initiator potassium persulfate (consumption is 0.22 % of monomers B quality), emulsifier sodium lauryl sulfate (consumption be monomers B quality 0.6%) adds successively to stir in the distilled water and obtains pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (2), also continue to react 1 hour under the stirring at 75 ℃, obtain examining emulsion;
(4) monomer C(is made up of by mass ratio 2:1 methyl methacrylate, vinylbenzene), linking agent N, N
,-methylene-bisacrylamide (consumption is 0.4 % of monomer C quality), initiator potassium persulfate (consumption be monomer C quality 0.1%), compound emulsifying agent is (by sodium lauryl sulphate, reactive emulsifier alkyl phenol ether ammonium sulfate is pressed mass ratio 70:30 and is formed, the compound emulsifying agent consumption be monomer C quality 2.0%) modified silicasol that obtains with step (1) joins successively to stir in the distilled water and obtains pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (3), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure polyacrylic ester (ACR)/silicon sol composite emulsion;
(5) above-mentioned ACR/ silicon sol composite emulsion obtains ACR/ silicon sol composite particles through breakdown of emulsion, drying.
Above-mentioned monomer A: monomers B: monomer C mass ratio is 10:70:20, modified silicasol is the sodium type, solid content 30 ± 1%, consumption is 18.0% of (monomer A+monomers B+monomer C) total mass, monomer A in the step (2): the distilled water mass ratio is 20:80, monomers B in the step (3): distilled water mass ratio 40:60, monomer C in the step (4): the distilled water mass ratio is 30:70.
Embodiment three:
(1) with composite modifier γ-(methacryloxypropyl) propyl trimethoxy silicane+3-(2,3-epoxy third oxygen) propyl trimethoxy silicane+γ-An Bingjisanyiyangjiguiwan (mass ratio of two kinds of properties-correcting agent is 1:1) adds in the silicon sol, the properties-correcting agent consumption is 8.0% of a silicon sol total amount, also reacted 5 hours under the stirring at 60 ℃, obtain modified silicasol.
(2) with distilled water be solvent, add monomer A (butyl acrylate) successively, initiator potassium persulfate is (consumption be monomer A quality 0.7%), emulsifier sodium lauryl sulfate (consumption be monomer A quality 5.0%), also continue under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(3) with monomers B (forming by mass ratio 4:1), linking agent N, N by butyl acrylate, vinylbenzene
,-methylene-bisacrylamide (consumption be monomers B quality 0.05%), initiator potassium persulfate (consumption be monomers B quality 0.12%), emulsifier sodium lauryl sulfate (consumption be monomers B quality 1.0%) adds successively to stir in the distilled water and obtains pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (2), also continue to react 1 hour under the stirring at 75 ℃, obtain examining emulsion;
(4) monomer C(is made up of by mass ratio 2:1 methyl methacrylate, vinylbenzene), linking agent N, N
,-methylene-bisacrylamide (consumption be monomer C quality 0.3%), initiator potassium persulfate (consumption be monomer C quality 0.10%), compound emulsifying agent is (by sodium lauryl sulphate, reactive emulsifier alkyl phenol ether ammonium sulfate is pressed mass ratio 70:30 and is formed, the compound emulsifying agent consumption be monomer C quality 1.0%) modified silicasol that obtains with step (1) joins successively to stir in the distilled water and obtains pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (3), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure polyacrylic ester (ACR)/silicon sol composite emulsion;
(5) above-mentioned ACR/ silicon sol composite emulsion obtains ACR/ silicon sol composite particles through breakdown of emulsion, drying.
Above-mentioned monomer A: monomers B: monomer C mass ratio is 6:65:29, modified silicasol is the sodium type, solid content 30 ± 1%, consumption is 13.0% of (monomer A+monomers B+monomer C) total mass, monomer A in the step (2): the distilled water mass ratio is 20:80, monomers B in the step (3): distilled water mass ratio 40:60, monomer C in the step (4): the distilled water mass ratio is 30:70.
Comparative example (not adding modified silicasol):
(1) with distilled water is solvent, add monomer A (butyl acrylate) successively, initiator potassium persulfate is (consumption be monomer A quality 0.8%), emulsifier sodium lauryl sulfate (consumption be monomer A quality 3.0%), also continue under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(2) with monomers B (forming by mass ratio 4:1), linking agent N, N by butyl acrylate, vinylbenzene
,-methylene-bisacrylamide (consumption be monomers B quality 0.05%), initiator potassium persulfate (consumption be monomers B quality 0.2%), emulsifier sodium lauryl sulfate (consumption is 0.8 % of monomers B quality) adds successively in the distilled water to stir and obtains pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (1), also continue to react 1 hour under the stirring at 75 ℃, obtain examining emulsion;
(3) monomer C(is made up of by mass ratio 2:1 methyl methacrylate, vinylbenzene), linking agent N, N
,-methylene-bisacrylamide (consumption be monomer C quality 0.5%), initiator potassium persulfate (consumption is 0.1 % of monomer C quality), compound emulsifying agent (is made up of by mass ratio 70:30 sodium lauryl sulphate, reactive emulsifier alkyl phenol ether ammonium sulfate, the compound emulsifying agent consumption be monomer C quality 1.8%) join successively in the distilled water to stir and obtain pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (2), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure polyacrylic ester (ACR) emulsion;
(4) above-mentioned ACR emulsion obtains the ACR particle through breakdown of emulsion, drying.
Above-mentioned monomer A: monomers B: monomer C mass ratio is 5:55:40, and monomer A in the step (1): the distilled water mass ratio is 20:80, monomers B in the step (2): distilled water mass ratio 40:60, monomer C in the step (3): the distilled water mass ratio is 30:70.
The invention process effect and application performance effect
The foregoing description and comparative example product are used for complex compounding (prescription the sees Table 1) sample preparation of PVC, carry out following performance test respectively:
Shock resistance test: be cut into the test with notched test piece batten by the GB/T1843-2008 standard with omnipotent sampling machine, adopt radial-boom impact tester to carry out impact test (probe temperature: 23 ℃).
Erichsen test: undertaken by the GB/T1040-2006 standard-required, draw speed is the 20mm/min(probe temperature: 23 ℃).
Vicat softening point test: test by the GB1633-79 standard-required.
Test result is as shown in table 2.
Table 1 the invention process effect test recipe
| Component | PVC | Calcium zinc heat stabilizer | CaCO 3 | Product of the present invention | CPE |
| Umber | 100 | 4.5 | 10.0 | 2.5 | 8.0 |
Table 2 the invention process effect
| Project | Embodiment one | Embodiment two | Embodiment three | Comparative example |
| Median size (nm) | 135 | 126 | 140 | 120 |
| Shock strength (KJ/m 2） | 65.9 | 66.2 | 63.1 | 64.8 |
| 23 ℃ of tensile strengths (MPa) | 49.5 | 48.7 | 50.3 | 41.1 |
| Vicat softening point (℃) | 90.3 | 88.8 | 89.0 | 82.1 |
Claims (8)
1. the preparation method of a Polyacrylate matrix material is characterized in that comprising the steps:
(1) adopts γ-(methacryloxypropyl) propyl trimethoxy silicane, 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane, two kinds in the γ-An Bingjisanyiyangjiguiwan as properties-correcting agent, at 40 ~ 60 ℃ silicon sol is carried out surface modification, in 5 ~ 8 hours reaction times, obtain modified silicasol, the properties-correcting agent consumption is 1.0%～12.0% of a silicon sol total amount, and wherein the mass ratio of two kinds of properties-correcting agent is 1:1;
(2) with distilled water be solvent, butyl acrylate is as monomer A, Potassium Persulphate is an initiator, consumption is 0.1～0.8% of a monomer A quality, sodium lauryl sulphate is as emulsifying agent, and consumption is 0.5～5.0% of a monomer A quality, also continues under the stirring at 70 ℃, reacted preparation seed latex 0.5 hour;
(3) be monomers B with butyl acrylate and vinylbenzene, wherein butyl acrylate and cinnamic mass ratio are 4:1, N, N
,-methylene-bisacrylamide is as linking agent, consumption is 0.02～0.1% of a monomers B quality, Potassium Persulphate is as initiator, consumption is 0.05～0.3% of a monomers B quality, and sodium lauryl sulphate is as emulsifying agent, and consumption is 0.1～1.0% of a monomers B quality, said components added in the distilled water to stir obtain pre-emulsion I, pre-emulsion I is added drop-wise in the seed latex of step (2), also continues to react 1 hour under the stirring, obtain examining emulsion at 75 ℃;
(4) be monomer C with methyl methacrylate and vinylbenzene, methyl methacrylate and cinnamic mass ratio are 2:1, N, N
,-methylene-bisacrylamide is as linking agent, and consumption is 0.1～0.5% of a monomer C quality, and Potassium Persulphate is as initiator, and consumption is 0.05～0.3% of a monomer C quality; Adopting sodium lauryl sulphate and reactive emulsifier alkyl phenol ether ammonium sulfate is compound emulsifying agent, the mass ratio of sodium lauryl sulphate and reactive emulsifier alkyl phenol ether ammonium sulfate is 70:30, the compound emulsifying agent consumption is 0.1～2.0% of a monomer C quality, said components and modified silicasol joined to stir in the distilled water obtain pre-emulsion II, pre-emulsion II is added drop-wise in the nuclear emulsion of step (3), reacted 2 hours down and under continuing to stir at 85 ℃, make nucleocapsid structure Polyacrylate composite emulsion;
(5) nucleocapsid structure Polyacrylate composite emulsion obtains nucleocapsid structure Polyacrylate matrix material through breakdown of emulsion, drying.
2. preparation method according to claim 1 is characterized in that: monomer A in the above-mentioned steps (1) (2) (3) (4): monomers B: monomer C mass ratio is 5 ~ 10:50 ~ 70:20 ~ 40, with SiO
2Meter modified silicasol consumption is 5.0～20.0% of monomer A+monomers B+monomer C total mass.
3. preparation method according to claim 1 is characterized in that: used silicon sol is the sodium type in the above-mentioned steps (1), solid content 30 ± 1%.
4. preparation method according to claim 1 is characterized in that: monomer A in the above-mentioned steps (2): the distilled water mass ratio is 20:80.
5. preparation method according to claim 1 is characterized in that: monomers B in the above-mentioned steps (3): distilled water mass ratio 40:60.
6. preparation method according to claim 1 is characterized in that: monomer C in the above-mentioned steps (4): the distilled water mass ratio is 30:70.
7. preparation method according to claim 1 is characterized in that: the particle diameter of nucleocapsid structure Polyacrylate matrix material is at 100 ~ 150nm in the above-mentioned steps (5).
8. the Polyacrylate matrix material of preparation method's preparation as claimed in claim 1 is applied to the processing of polyvinyl chloride as impact modifier.
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