CN105859987A - Hydrogenated silicon oil modified silica sol/core-shell type polyacrylic acid emulsion and preparation method thereof - Google Patents
Hydrogenated silicon oil modified silica sol/core-shell type polyacrylic acid emulsion and preparation method thereof Download PDFInfo
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- CN105859987A CN105859987A CN201610238215.6A CN201610238215A CN105859987A CN 105859987 A CN105859987 A CN 105859987A CN 201610238215 A CN201610238215 A CN 201610238215A CN 105859987 A CN105859987 A CN 105859987A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/10—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to inorganic materials
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Abstract
The invention relates to a hydrogenated silicon oil modified silica sol/core-shell type polyacrylic acid emulsion and a preparation method thereof. The method includes the step A of preparing silica sol modified by hydrogenated silicon oil, the step B of adding silica sol modified by hydrogenated silicon oil, deionized water, initiator, emulsifier and a buffering agent solution into a reactor, raising the temperature to 75-80 DEG C, and dropwise adding part of monomer pre-emulsion to prepare a seed emulsion, and the step C of dropwise adding shell layer monomer pre-emulsion and an initiator solution to the seed emulsion, raising the temperature to 85+/-2 DEG C, and keeping the temperature to obtain the hydrogenated silicon oil modified silica sol/core-shell type polyacrylic acid emulsion. The obtained polyacrylic acid emulsion is low in water absorption rate and high in dilution stability and freeze-thaw stability.
Description
Technical field
The invention belongs to polymer substance synthesis field, relate to emulsion polymerization technology, be specifically related to a kind of hydrogenation silicone oil modified silicon molten
Glue/hud typed polyacrylate emulsion and preparation method thereof.
Background technology
Acrylic emulsion is the common name of the copolymer of various acrylic monomers class, is widely used in all trades and professions, and it paints industry at wood
In particularly important.
There is the shortcoming that resistance to water is the best in traditional acrylic emulsion, and can add certain during acrylic emulsion is polymerized
The emulsifying agent of amount, when this acrylic emulsion is used to application, remaining emulsifying agent therein can affect again the performance of film further
The resistance to water, the adhesive force that cause smearing are the best, and gloss is undesirable.
Although the performance of existing acrylic emulsion is improved, but still the use demand of people can not be met, so how to solve
Certainly technical shortcoming is the problem that existing acrylic emulsion field is to be solved.
Summary of the invention
It is an object of the invention to be for the deficiencies in the prior art, it is provided that a kind of hydrogenation silicone oil modified silicasol/hud typed polypropylene
Yogurt liquid and preparation method thereof, the hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion of the present invention, have good water-fast
Property and stability, and production method is simple, low cost.
The hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion of the present invention, it is passed through free radical polymerization by following component
Forming, described component and weight proportion thereof are as follows: 20～30 parts of methyl methacrylates, 1～2 part of composite emulsifier, 20～30
Part butyl acrylate, 0.5～3 part of acrylic acid, 0.1～0.3 part of potassium peroxydisulfate, 3～6 parts of hydrogenation silicone oil modified silicasols, 48～
52 parts of deionized waters.
The hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion of the present invention, is formed by free radical polymerization, described group
Divide and weight proportion is as follows: 20～30 parts of methyl methacrylates, 1～2 part of composite emulsifier, 20～30 parts of acrylic acid fourths
Ester, 0.5～3 part of acrylic acid, 0.1～0.3 part of initiator, 3～6 parts of hydrogenations silicone oil modified silicasol, 48～52 parts of deionizations
Water.
The preparation method of the hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion of the present invention, comprises the following steps:
A, hydrogenation silicone oil modified silicasol: adding hydrogenation silicone oil, Ludox, deionized water in the reactor, regulation pH value is extremely
3～4, then heat to 80 ± 1 DEG C, after reaction the silicon oil modified Ludox of hydrogenation；
B, the synthesis of seed emulsion stratum nucleare structure: add the silicon oil modified Ludox of hydrogenation, deionized water, buffering in the reactor
Agent solution, the initiator of 1/3, the composite emulsifier of 1/3, be warming up to 75 DEG C～80 DEG C, drips nuclear layer monomer pre-emulsion,
Insulation a period of time prepares seed emulsion；
C, the synthesis of sheath polymers: in the emulsion of step B gained, drip shell monomers pre-emulsion, remaining initiator
Solution, is warming up to 85 ± 2 DEG C simultaneously, is down to room temperature after insulation a period of time, with saturated sodium bicarbonate solution regulation pH value to 7～
Discharging after 8.
In step, the response time is 7.5h～8.5h, and hydrogenation silicon oil dosage is the 3.0%～3.5% of Ludox quality.
In stepb, temperature retention time is 30～60 minutes.
By whole monomers (20～30 parts of methyl methacrylates, 20～30 parts of butyl acrylate, 0.5～3 part of acrylic acid), go
Ionized water and 2/3 composite emulsifier add and flask stir certain time under certain stir speed (S.S.) until without two-phase laminated flow,
Preparing monomer pre-emulsion, in stepb, the monomer pre-emulsion of 1/4～1/2 is as stratum nucleare pre-emulsion, remaining monomer
Pre-emulsion is as shell pre-emulsion.
In step C, dropping shell monomers pre-emulsion, the time of initiator solution are 2～3h, then insulation 2.5～3.5h.
Buffer agent solution described in stepb be the one in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, hydrochloric acid or
Several it is mixed to prepare.
Initiator solution described in stepb is that one or both in potassium peroxydisulfate, Ammonium persulfate. are mixed to prepare.
Composite emulsifier described in step B is anionic emulsifier SDS and the mixture of nonionic emulsifier OP-10,
And the mass ratio of the two is 3:1～1:3.
A kind of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion of the present invention and preparation method thereof, production method is simple,
Low cost and environmental protection, compare Conventional acrylic emulsion, resistance to water is greatly improved and also the hydrogenation silicone oil modified silicasol of the present invention/
Hud typed polyacrylate emulsion dilution stability, freeze-thaw stability are high.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail.
Embodiment 1
Hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion, comprises the following raw material according to weight portion number scale: 29 parts of first
Base acrylic acid methyl ester., 2 parts of composite emulsifiers, 20 parts of butyl acrylate, 1 part of acrylic acid, 0.2 part of potassium peroxydisulfate, 5 parts of hydrogenations
Silicon oil modified Ludox, 42 parts of deionized waters, 1 part of saturated sodium bicarbonate solution.Wherein composite emulsifier is by mass ratio
SDS:OP-10=1 1 mixes.
The preparation of hydrogenation silicone oil modified silicasol: add 20g Ludox, 20g deionized water in the reactor, add quality
Mark is the hydrogenation silicone oil of Ludox 3.5%, simultaneously with a small amount of 5% hydrochloric acid solution regulate pH value to 3～4, then heat to 80
± 1 DEG C, after reaction 8h the silicon oil modified Ludox of hydrogenation；
The pre-emulsification of monomer: by whole monomers (29 parts of methyl methacrylates, 20 parts of butyl acrylate, 1 part of acrylic acid),
Deionized water and 2/3 composite emulsifier add in flask, under 300r/min stir speed (S.S.), stir 40min, can be prepared by list
Body pre-emulsion.
The synthesis of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion: the silicon adding hydrogenation silicon oil modified in reactor is molten
Glue and the deionized water of Ludox equivalent, saturated sodium bicarbonate solution, the potassium peroxydisulfate of 1/3, the composite emulsifier of 1/3, so
After under the stir speed (S.S.) of 200r/min, be to slowly warm up to 75 DEG C～80 DEG C, afterwards in 1h drip 1/3 monomer pre-emulsion,
It is incubated 30min after dropping, then can prepare seed emulsion；Then in 2h, drip remaining monomer pre-emulsion, remaining
Initiator solution, is warming up to 85 ± 2 DEG C simultaneously, drips insulation 3h, is down to room temperature afterwards, molten with residue saturated sodium bicarbonate
Liquid regulation pH value filters discharging behind 7～8.
Embodiment 2
Hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion, comprises the following raw material according to weight portion number scale: 25 parts of first
Base acrylic acid methyl ester., 2 parts of composite emulsifiers, 24 parts of butyl acrylate, 1 part of acrylic acid, 0.2 part of potassium peroxydisulfate, 5 parts of hydrogenations
Your solution of silicon oil modified Ludox, 42 parts of deionized waters, 1 part of saturated sodium bicarbonate.Wherein emulsifying agent is by mass ratio
SDS:OP-10=1 1 mixes.Hydrogenation silicone oil modified silicasol and hydrogenation silicone oil modified silicasol/hud typed polypropylene yogurt
The preparation method of liquid is same as in Example 1.
Embodiment 3
Hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion, comprises the following raw material according to weight portion number scale: 29 parts of first
Base acrylic acid methyl ester., 2 parts of composite emulsifiers, 20 parts of butyl acrylate, 1 part of acrylic acid, 0.2 part of potassium peroxydisulfate, 5 parts of hydrogenations
Your solution of silicon oil modified Ludox, 42 parts of deionized waters, 1 part of saturated sodium bicarbonate.Wherein emulsifying agent is by mass ratio
SDS:OP-10=2 1 mixes.Hydrogenation silicone oil modified silicasol and hydrogenation silicone oil modified silicasol/hud typed polypropylene yogurt
The preparation method of liquid is same as in Example 1.
The finished product prepared by example 1-3 carries out following table properties test, the results are shown in Table 1
Table 1 performance test data
| Performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Water absorption rate | 3.5% | 4.2% | 2.9% |
| Dilution stability | Pass through | Pass through | Pass through |
| Freeze-thaw stability | 5 times | 5 times | 5 times |
As seen from the above table, the present invention has preferable resistance to water, dilution stability and freeze-thaw stability.
The above, the only present invention preferably detailed description of the invention, these detailed description of the invention are all based on entirety structure of the present invention
Different implementations under Siing, and protection scope of the present invention is not limited thereto, any technology people being familiar with the art
Member in the technical scope that the invention discloses, the change that can readily occur in or replacement, all should contain protection scope of the present invention it
In.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. hydrogenate a preparation method for silicone oil modified silicasol/hud typed polyacrylate emulsion, first with hydrogenation silicone oil modified silicasol,
Then to hydrogenate silicon oil modified Ludox and partial monosomy pre-emulsion polymerization preparation seed emulsion, then breast pre-with remaining monomer
Change liquid polymerization shell, concretely comprise the following steps:
A, hydrogenation silicone oil modified silicasol: in the reactor add hydrogenation silicone oil, Ludox, deionized water, regulation pH value to 3～4,
Then heat to 80 ± 1 DEG C, after reaction the silicon oil modified Ludox of hydrogenation；
B, the synthesis of seed emulsion stratum nucleare structure: add the silicon oil modified Ludox of hydrogenation, deionized water, buffer agent in the reactor molten
Liquid, the initiator of 1/3, the composite emulsifier of 1/3, nuclear layer monomer pre-emulsion, after be warming up to 75 DEG C～80 DEG C reactions, protect
The temperature regular hour, prepare seed emulsion；
C, the synthesis of sheath polymers: in the emulsion of step B gained, drip shell monomers pre-emulsion, remaining initiator solution,
It is warming up to 85 ± 2 DEG C simultaneously, after insulation a period of time, is down to room temperature, discharging after regulation pH value to 7～8.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
In: in step, the response time is 7.5h～8.5h, and hydrogenation silicon oil dosage is the 3.0%～3.5% of Ludox quality.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
In: the composite emulsifier of whole monomers, deionized water and 2/3 is added flask stirs under certain stir speed (S.S.) a timing
Between until without two-phase laminated flow, prepare monomer pre-emulsion, the monomer pre-emulsion of 1/4～1/2 is as stratum nucleare pre-emulsion, remaining
Monomer pre-emulsion as shell pre-emulsion.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
In: in stepb, temperature retention time 30～60 minutes.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
In: in step C, dropping shell monomers pre-emulsion, the time of initiator solution are 2～3h, then insulation 2.5～3.5h.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
In: described buffer agent solution is one or more the mixing systems in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, hydrochloric acid
?.
The preparation method of hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 1, its feature exists
It is that one or both in potassium peroxydisulfate, Ammonium persulfate. are mixed to prepare in: described initiator solution.
8. hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion, its component and weight proportion thereof are as follows: 20～30 parts of first
Base acrylic acid methyl ester., 1～2 part of composite emulsifier, 20～30 parts of butyl acrylate, 0.5～3 part of acrylic acid, 0.1～0.3 part
Potassium peroxydisulfate, 3～6 parts of hydrogenations silicone oil modified silicasol, 48～52 parts of deionized waters.
Hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion the most according to claim 8, it is characterised in that: described
Composite emulsifier is anionic emulsifier SDS and the mixture of nonionic emulsifier OP-10, and the mass ratio of the two is
3:1～1:3.
10. hydrogenation silicone oil modified silicasol/hud typed polyacrylate emulsion that prepared by the preparation method described in claim 1-7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1667004A (en) * | 2005-02-28 | 2005-09-14 | 仪征多科特水性化学品有限责任公司 | Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint and method for preparing same |
| CN102391412A (en) * | 2011-08-30 | 2012-03-28 | 中科院广州化学有限公司 | Organosilicon-modified acrylate core-shell emulsion capable of filming at room temperature and preparation method as well as application thereof |
| CN102786644A (en) * | 2012-08-21 | 2012-11-21 | 陕西科技大学 | Preparation method of acrylic resin finishing agent modified by nano silicon dioxide (SiO2)-coated multi-walled carbon nanotubes |
| CN104530302A (en) * | 2014-12-11 | 2015-04-22 | 华南理工大学 | Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion |
| CN104650625A (en) * | 2015-02-09 | 2015-05-27 | 江苏荣昌新材料科技有限公司 | Method for modifying nanometer silicon dioxide by using hydrogenated silicon oil |
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2016
- 2016-04-15 CN CN201610238215.6A patent/CN105859987B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1667004A (en) * | 2005-02-28 | 2005-09-14 | 仪征多科特水性化学品有限责任公司 | Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint and method for preparing same |
| CN102391412A (en) * | 2011-08-30 | 2012-03-28 | 中科院广州化学有限公司 | Organosilicon-modified acrylate core-shell emulsion capable of filming at room temperature and preparation method as well as application thereof |
| CN102786644A (en) * | 2012-08-21 | 2012-11-21 | 陕西科技大学 | Preparation method of acrylic resin finishing agent modified by nano silicon dioxide (SiO2)-coated multi-walled carbon nanotubes |
| CN104530302A (en) * | 2014-12-11 | 2015-04-22 | 华南理工大学 | Silica sol/polyacrylic ester emulsion with high silicon content and preparation method of silica sol/polyacrylic ester emulsion |
| CN104650625A (en) * | 2015-02-09 | 2015-05-27 | 江苏荣昌新材料科技有限公司 | Method for modifying nanometer silicon dioxide by using hydrogenated silicon oil |
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