CN108383937A - A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity and preparation method thereof - Google Patents
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity and preparation method thereof Download PDFInfo
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- CN108383937A CN108383937A CN201810168147.XA CN201810168147A CN108383937A CN 108383937 A CN108383937 A CN 108383937A CN 201810168147 A CN201810168147 A CN 201810168147A CN 108383937 A CN108383937 A CN 108383937A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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Abstract
The present invention discloses a kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity and preparation method thereof, belongs to acrylic acid ester emulsion field, in parts by mass, including following raw material：80 120 parts of water, 10 30 parts of methyl methacrylate, 20 40 parts of styrene, 0 30 parts of Isooctyl acrylate monomer, 2 10 parts of function monomer, 02 parts of cross-linking monomer, 2 10 parts of Protection glue, 26 parts of emulsifier, 15 parts of initiator, 03 parts of reductant-oxidant.The water-fast acrylic acid ester emulsion of hydrophobic high rigidity of the present invention is prepared using heating autoreaction method, and entire reaction carries out at a temperature of 25 95 DEG C, so entire reaction system can carry out under relatively mild environment, ensure that the stability of reaction；Entire reaction carries out in reaction kettle simultaneously, and only need to heat and stir and can prepare, and manufacturing procedure very simple greatly reduces the processing cost of acrylic acid ester emulsion.
Description
Technical field
The present invention relates to a kind of acrylic acid ester emulsions, and in particular to a kind of hydrophobic high rigidity is water-fast acrylic acid ester emulsion and its
Preparation method belongs to acrylic acid ester emulsion field.
Background technology
For acrylic acid ester emulsion as common lotion in current water-base resin in the world, the application in lacquer is especially wide
It is general.There are hardness height and water-fast, hydrophobic and the conflicting phenomenon of water resistance, mainly acrylic acid for traditional acrylic acid ester emulsion
Ester lotion is influenced by its TG, and the acrylic acid ester emulsion film-formation result of low TG is good, and compactness is high, it can be allowed to have excellent water-fast
Bai Xingneng, and since acrylic acid ester emulsion has the glutinous cold short characteristic of heat, the acrylic acid ester emulsion meeting under the higher environment of temperature
There is tacky situation.
In the prior art in order to solve this problem, it will usually by the way of improving polymer particle case hardness come gram
Take the tacky defect of acrylic acid ester emulsion high temperature.However, with polymer particle case hardness improve, molecule chain rigidity also with
Enhancing, so that the brittleness of paint film is increased；In addition, due to strand rigidity reinforced, under light irradiation the light resistance of strand compared with
Difference, the group on strand are susceptible to transport phenomena, greatly reduce the water-whitening resistance energy of paint film.Hardness and water-whitening resistance pair
It is conflicting performance for acrylic acid ester emulsion, the two cannot get both.And prepared by hydrophobic acrylic emulsion needs
Hydrophobic function monomer is added in journey, to allow lotion to be difficult to enter inside film in the soaked hydrone in the process that forms a film, reaches hydrophobic effect
Fruit, but there are a drawbacks for such lotion, the moisture exactly entered inside emulsion film equally is difficult to out, and brokenization lotion
Film emulsion particle packing of molecules causes water resistance to be deteriorated.
Therefore how to develop it is a not only have excellent hydrophobic performance, but also have excellent high rigidity, while also have it is good
The acrylic acid ester emulsion of water-whitening resistance is one of technical barrier of current acrylic acid ester emulsion industry.
Invention content
Not only had hydrophobic in view of the above existing problems in the prior art, the present invention provides a kind of, and but also there is excellent hardness,
There is the acrylic acid ester emulsion of excellent water-whitening resistance simultaneously.
Another mesh of the present invention is to provide a kind of preparation method of above-mentioned acrylic acid ester emulsion simple for process.
To achieve the goals above, a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity that the present invention uses, by mass parts
Meter, including following raw material：80-120 parts of water, 10-30 parts of methyl methacrylate, 20-40 parts of styrene, Isooctyl acrylate monomer 0-
30 parts, 2-10 parts of function monomer, 0-2 parts of cross-linking monomer, 2-10 parts of Protection glue, 2-6 parts of emulsifier, 1-5 parts of initiator, oxidation
0-3 parts of reducing agent.
The function monomer uses glycidyl methacrylate.
The cross-linking monomer uses vinyltrimethoxysilane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.
The emulsifier is acrylic fatty alcohol polyoxyethylene ether ammonium sulfate, one kind in dodecyl sodium sulfate or two
Person is with arbitrary than mixing.
The initiator is that ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or mentioned component are mixed with arbitrary proportion
It closes.
The reductant-oxidant uses one kind in tert-butyl hydroperoxide, sodium hydrogensulfite or mentioned component arbitrarily to compare
Example mixing.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 70-110 parts of water, methyl methacrylate, the benzene of formula ratio is added in reaction kettle successively
Ethylene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 0.5-2 part emulsifier, stir；
2) mixture that step 1) obtains is warming up to 80-85 DEG C, be added formula ratio initiator and 0.5-2 parts emulsification
Agent stirs；
3) mixture for obtaining step 2), temperature are maintained at 80-85 DEG C, while lasting stirring, react 10-20 minutes；
4) mixture for obtaining step 3) is kept the temperature at 80-85 DEG C, lasting to stir, and remaining emulsifier is added dropwise, and is added dropwise
Time is 4-5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 86-88 DEG C and keeps the temperature 0.5-1h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 80-82 DEG C, then is added dropwise with 5 parts of water dissolutions
0-1 parts of reductant-oxidant, time for adding are 10-20 minutes, then keep the temperature 10-20 minutes；
7) mixture made from step 6) is first cooled to 75-78 DEG C, and 5 parts of water dissolutions is added dropwise into reaction kettle again
0-2 parts of reductant-oxidant, be added dropwise 10-20 minutes, and keep the temperature 10-20 minutes；
8) mixture made from step 7) is cooled to 35-45 DEG C, 2-10 parts of Protection glues is added after filtering, obtain required third
Olefin(e) acid ester lotion.
Compared with prior art, the beneficial effects of the invention are as follows：
1, glycidyl methacrylate, methyl are added in the water-fast acrylic acid ester emulsion of hydrophobic high rigidity of the invention
Methyl acrylate, styrene, vinyltrimethoxysilane, Protection glue, glycidyl methacrylate are a kind of hydrophobic lists
Body is added in emulsion system, and isolation moisture when lotion drying and forming-film can be made to enter inside emulsion film；In addition, the present invention is added
A large amount of methyl methacrylates and styrene, methyl methacrylate and styrene are hard monomers, thus prepared propylene
Acid esters lotion TG higher, hardness are also just very high；And vinyltrimethoxysilane is a kind of organosiloxane, is greatly improved
The bond energy that the crosslink density of acrylic acid ester emulsion reaction system is connected with strand group makes lotion have excellent resistance to water-white
Property；Again, Protection glue is a kind of inorganic salts, protects the moisture of sol solution in evaporation, can be sent out with the emulsifier on emulsion particle surface
Biochemical reaction makes emulsion particle have better water resistance.
2, in the water-fast acrylic acid ester emulsion of hydrophobic high rigidity of the invention, emulsifier is added, methyl can be effectively solved
The problem of difficulty reaction when methyl acrylate, styrene are added dropwise, while solving glycidyl methacrylate and vinyl front three
Difficult the problem of incorporating reaction system of oxysilane is the emphasis place of the present invention.
3, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity of the invention is prepared using heating autoreaction method, and entire reaction exists
It is carried out at a temperature of 25-95 DEG C, so entire reaction system can carry out under relatively mild environment, ensure that the stabilization of reaction
Property；Entire reaction carries out in reaction kettle simultaneously, and only need to heat and stir and can prepare, manufacturing procedure very simple,
Greatly reduce the processing cost of acrylic acid ester emulsion.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, below by embodiment, to the present invention into
Row is further described.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
In limiting the scope of the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with the technology for belonging to the present invention
The normally understood meaning of technical staff in domain is identical, and used term is intended merely to retouch in the description of the invention herein
State the purpose of specific embodiment, it is not intended that in the limitation present invention.
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：80-120 parts of water, first
10-30 parts of base methyl acrylate, 20-40 parts of styrene, 0-30 parts of Isooctyl acrylate monomer, 2-10 parts of function monomer, cross-linking monomer
0-2 parts, 2-10 parts of Protection glue, 2-6 parts of emulsifier, 1-5 parts of initiator, 0-3 parts of reductant-oxidant, the present invention is by metering system
Sour methyl esters, styrene, Isooctyl acrylate monomer, function monomer and cross-linking monomer are added to the water, by sulfate be used as initiator into
Row polymerisation, the emulsification for being aided with emulsifier form required acrylic acid ester emulsion.
It is a kind of with thin that the function monomer, which uses glycidyl methacrylate, glycidyl methacrylate,
The function monomer of water functional group, hydrophobic functional group after completion of polymerization lotion film-forming when, play and hydrone do not allowed to enter breast
Effect inside liquid film.
The cross-linking monomer uses vinyltrimethoxysilane, have in the strand of vinyltrimethoxysilane compared with
Multi-active base group, active group occur with methyl methacrylate, styrene or Isooctyl acrylate monomer a large amount of during the reaction
Cross-linking reaction, formed cross linking membrane.
The content of lithium magnesium silicate is 40-60% in the Protection glue, it is a kind of inorganic salts.
The emulsifier is acrylic fatty alcohol polyoxyethylene ether ammonium sulfate, one kind in dodecyl sodium sulfate or two
For person with arbitrary than mixing, acrylic fatty alcohol polyoxyethylene ether ammonium sulfate is response type anion surfactant, is had good
Good emulsification, foaming, stabilization performance.
The initiator is that ammonium persulfate, potassium peroxydisulfate, one kind in sodium peroxydisulfate or mentioned component are mixed with arbitrary proportion
It closes.Because mentioned component is persulfate, and these persulfates are aqueous, so can assign breast after the completion of chemical reaction
The excellent water resistance of liquid.
The reductant-oxidant uses one kind in tert-butyl hydroperoxide, sodium hydrogensulfite or mentioned component arbitrarily to compare
Example mixing.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, successively in reaction kettle be added 70-110 parts water, methyl methacrylate, styrene, third
The different monooctyl ester of olefin(e) acid, function monomer, cross-linking monomer and 0.5-2 parts of emulsifiers, stir；
2) mixture that step 1) obtains is warming up to 80-85 DEG C, be added formula ratio initiator and 0.5-2 parts emulsification
Agent stirs；
3) mixture for obtaining step 2), temperature are maintained at 80-85 DEG C, while lasting stirring, react 10-20 minutes；
4) mixture for obtaining step 3) is kept the temperature at 80-85 DEG C, lasting to stir, and remaining emulsifier is added dropwise, and is added dropwise
Time is 4-5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 86-88 DEG C and keeps the temperature 0.5-1h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 80-82 DEG C, then is added dropwise with 5 parts of water dissolutions
0-1 parts of reductant-oxidant, time for adding are 10-20 minutes, then keep the temperature 10-20 minutes；
7) mixture made from step 6) is first cooled to 75-78 DEG C, and 5 parts of water dissolutions is added dropwise into reaction kettle again
0-2 parts of reductant-oxidant, be added dropwise 10-20 minutes, and keep the temperature 10-20 minutes；
8) mixture made from step 7) is cooled to 35-45 DEG C, 2-10 parts of Protection glues is added after filtering, obtain required third
Olefin(e) acid ester lotion.
It (after sample film, in 50 DEG C of baking ovens after drying fully, is soaked in 20-50 DEG C of deionized water by hydrophobic test
4-24h is steeped, sees whether emulsion film increases weight, is blistered), acrylic acid ester emulsion of the invention does not increase weight, not blistering.
(a certain amount of natural colour sand, coalescents, antifreezing agent, fungicide, defoaming are added in sample by hardness test
Agent；A rectangular-shape is made with mold after stirring evenly, and 12- is impregnated in pure water after maintenance 16h in 50 DEG C of baking oven
For 24 hours, with mechanical testing instrument test sample intensity, see whether sample feels like jelly, deform), acrylic acid ester emulsion of the invention is not sent out
It is soft, it is indeformable.
By resistance to water-white test (after sample film is fully dry, sample is impregnated in 70-90 DEG C of tap water 4-24 hours,
See whether paint film changes colour, falls off), acrylic acid ester emulsion of the invention is non-discolouring, does not fall off.
Thus it proves, this lotion is the acrylic acid ester emulsion hydrophobic, hardness is high, water-fast.
Embodiment 1
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：80 parts of water, methyl-prop
10 parts of e pioic acid methyl ester, 20 parts of styrene, 2 parts of function monomer, 2 parts of Protection glue, 2 parts of emulsifier, 1 part of initiator, reductant-oxidant 2
Part.
The function monomer uses glycidyl methacrylate.The cross-linking monomer uses vinyl trimethoxy silicon
Alkane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.
The emulsifier is acrylic fatty alcohol polyoxyethylene ether ammonium sulfate.The initiator is ammonium persulfate.
The reductant-oxidant uses tert-butyl hydroperoxide.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 70 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 0.5 part of emulsifier, stir；
2) mixture that step 1) obtains is warming up to 80 DEG C, the initiator and 0.5 part of emulsifier of formula ratio is added, fully
It stirs evenly；
3) mixture for obtaining step 2), temperature are maintained at 80 DEG C, while lasting stirring, react 10 minutes；
4) mixture for obtaining step 3) is kept the temperature at 80 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 4 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 86 DEG C and keeps the temperature 0.5h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 80 DEG C, then the oxygen with 5 parts of water dissolutions is added dropwise
Change 1 part of reducing agent, time for adding is 10 minutes, then keeps the temperature 10 minutes；
7) mixture made from step 6) is first cooled to 75 DEG C, and is added dropwise into reaction kettle again with 5 parts of water dissolutions
1 part of reductant-oxidant is added dropwise 10 minutes, and keeps the temperature 10 minutes；
8) mixture made from step 7) is cooled to 35 DEG C, 2 parts of Protection glues is added after filtering, obtain required acrylate
Lotion.
After tested, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity that prepared by the present invention, it is hydrophobic detection (50 DEG C of deionized waters,
24h)：It does not increase weight, it is not blistering；Hardness determination (50 DEG C of tap water, for 24 hours)：High rigidity is not felt like jelly；Resistance to water-white detection (90 DEG C of distillations
Water, 12h)：It is non-discolouring, it does not fall off.
Embodiment 2
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：90 parts of water, methyl-prop
15 parts of e pioic acid methyl ester, 25 parts of styrene, 10 parts of Isooctyl acrylate monomer, 4 parts of function monomer, 0.5 part of cross-linking monomer, Protection glue 4
Part, 3 parts of emulsifier, 2 parts of initiator, 3 parts of reductant-oxidant.
The function monomer uses glycidyl methacrylate.The cross-linking monomer uses vinyl trimethoxy silicon
Alkane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.The emulsifier is dodecyl sodium sulfate.
The initiator is potassium peroxydisulfate.The reductant-oxidant uses sodium hydrogensulfite.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 80 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 1 part of emulsifier, stir；
2) mixture that step 1) obtains is warming up to 82 DEG C, the initiator and 1 part of emulsifier of formula ratio is added, fully stirs
It mixes uniformly；
3) mixture for obtaining step 2), temperature are maintained at 82 DEG C, while lasting stirring, react 12 minutes；
4) mixture for obtaining step 3) is kept the temperature at 82 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 4.5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 86 DEG C and keeps the temperature 0.5h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 80 DEG C, then the oxygen with 5 parts of water dissolutions is added dropwise
Change 1 part of reducing agent, time for adding is 12 minutes, then keeps the temperature 12 minutes；
7) mixture made from step 6) is first cooled to 75 DEG C, and is added dropwise into reaction kettle again with 5 parts of water dissolutions
2 parts of reductant-oxidant is added dropwise 12 minutes, and keeps the temperature 12 minutes；
8) mixture made from step 7) is cooled to 35 DEG C, 4 parts of Protection glues is added after filtering, obtain required acrylate
Lotion.
After tested, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity that prepared by the present invention, it is hydrophobic detection (50 DEG C of deionized waters,
24h)：It does not increase weight, it is not blistering；Hardness determination (50 DEG C of tap water, for 24 hours)：High rigidity is not felt like jelly；Resistance to water-white detection (90 DEG C of distillations
Water, 12h)：It is non-discolouring, it does not fall off.
Embodiment 3
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：100 parts of water, methyl-prop
20 parts of e pioic acid methyl ester, 30 parts of styrene, 15 parts of Isooctyl acrylate monomer, 6 parts of function monomer, 1 part of cross-linking monomer, 6 parts of Protection glue,
4 parts of emulsifier, 3 parts of initiator, 3 parts of reductant-oxidant.
The function monomer uses glycidyl methacrylate.The cross-linking monomer uses vinyl trimethoxy silicon
Alkane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.
The emulsifier is in acrylic fatty alcohol polyoxyethylene ether ammonium sulfate, dodecyl sodium sulfate according to 1:1 is mixed
It closes.
The initiator is ammonium persulfate, potassium peroxydisulfate using 2:1 mixing.The reductant-oxidant uses t-butyl peroxy
Change hydrogen.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 90 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 1 part of emulsifier, stir；
2) mixture that step 1) obtains is warming up to 83 DEG C, the initiator and 1 part of emulsifier of formula ratio is added, fully stirs
It mixes uniformly；
3) mixture for obtaining step 2), temperature are maintained at 83 DEG C, while lasting stirring, react 15 minutes；
4) mixture for obtaining step 3) is kept the temperature at 83 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 4.5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 87 DEG C and keeps the temperature 0.8h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 81 DEG C, then the oxygen with 5 parts of water dissolutions is added dropwise
Change 1 part of reducing agent, time for adding is 15 minutes, then keeps the temperature 15 minutes；
7) mixture made from step 6) is first cooled to 76 DEG C, and is added dropwise into reaction kettle again with 5 parts of water dissolutions
2 parts of reductant-oxidant is added dropwise 15 minutes, and keeps the temperature 15 minutes；
8) mixture made from step 7) is cooled to 40 DEG C, 6 parts of Protection glues is added after filtering, obtain required acrylate breast
Liquid.
After tested, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity that prepared by the present invention, it is hydrophobic detection (50 DEG C of deionized waters,
24h)：It does not increase weight, it is not blistering；Hardness determination (50 DEG C of tap water, for 24 hours)：High rigidity is not felt like jelly；Resistance to water-white detection (90 DEG C of distillations
Water, 12h)：It is non-discolouring, it does not fall off.
Embodiment 4
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：110 parts of water, methyl-prop
25 parts of e pioic acid methyl ester, 35 parts of styrene, 25 parts of Isooctyl acrylate monomer, 8 parts of function monomer, 1.5 parts of cross-linking monomer, Protection glue 8
Part, 5 parts of emulsifier, 4 parts of initiator, 2 parts of reductant-oxidant.
The function monomer uses glycidyl methacrylate.The cross-linking monomer uses vinyl trimethoxy silicon
Alkane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.
The emulsifier is acrylic fatty alcohol polyoxyethylene ether ammonium sulfate.The initiator is potassium peroxydisulfate.
The reductant-oxidant uses tert-butyl hydroperoxide.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 100 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 1.5 parts of emulsifiers, stir；
2) mixture that step 1) obtains is warming up to 84 DEG C, the initiator and 1.5 parts of emulsifiers of formula ratio is added, fully
It stirs evenly；
3) mixture for obtaining step 2), temperature are maintained at 84 DEG C, while lasting stirring, react 15 minutes；
4) mixture for obtaining step 3) is kept the temperature at 84 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 4.5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 88 DEG C and keeps the temperature 1h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 82 DEG C, then the oxygen with 5 parts of water dissolutions is added dropwise
Change 0.5 part of reducing agent, time for adding is 18 minutes, then keeps the temperature 18 minutes；
7) mixture made from step 6) is first cooled to 78 DEG C, and is added dropwise into reaction kettle again with 5 parts of water dissolutions
1.5 parts of reductant-oxidant is added dropwise 18 minutes, and keeps the temperature 18 minutes；
8) mixture made from step 7) is cooled to 40 DEG C, 8 parts of Protection glues is added after filtering, obtain required acrylate
Lotion.
After tested, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity that prepared by the present invention, it is hydrophobic detection (50 DEG C of deionized waters,
24h)：It does not increase weight, it is not blistering；Hardness determination (50 DEG C of tap water, for 24 hours)：High rigidity is not felt like jelly；Resistance to water-white detection (90 DEG C of distillations
Water, 12h)：It is non-discolouring, it does not fall off.
Embodiment 5
A kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, in parts by mass, including following raw material：120 parts of water, methyl-prop
30 parts of e pioic acid methyl ester, 40 parts of styrene, 30 parts of Isooctyl acrylate monomer, 10 parts of function monomer, 2 parts of cross-linking monomer, Protection glue 10
Part, 6 parts of emulsifier, 5 parts of initiator, 2.5 parts of reductant-oxidant.
The function monomer uses glycidyl methacrylate.The cross-linking monomer uses vinyl trimethoxy silicon
Alkane.
The content of lithium magnesium silicate is 40-60% in the Protection glue.The emulsifier is dodecyl sodium sulfate.
The initiator is ammonium persulfate.
The reductant-oxidant is using tert-butyl hydroperoxide, sodium hydrogensulfite according to 1:1 mixing.
In addition, the present invention also provides a kind of preparation methods of the hydrophobic water-fast acrylic acid ester emulsion of high rigidity, specifically
Include the following steps：
1) under normal temperature state, 110 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer and 2 parts of emulsifiers, stir；
2) mixture that step 1) obtains is warming up to 85 DEG C, the initiator and 2 parts of emulsifiers of formula ratio is added, fully stirs
It mixes uniformly；
3) mixture for obtaining step 2), temperature are maintained at 85 DEG C, while lasting stirring, react 20 minutes；
4) mixture for obtaining step 3) is kept the temperature at 85 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 88 DEG C and keeps the temperature 1h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 82 DEG C, then the oxygen with 5 parts of water dissolutions is added dropwise
Change 1 part of reducing agent, time for adding is 20 minutes, then keeps the temperature 20 minutes；
7) mixture made from step 6) is first cooled to 78 DEG C, and is added dropwise into reaction kettle again with 5 parts of water dissolutions
1.5 parts of reductant-oxidant is added dropwise 20 minutes, and keeps the temperature 20 minutes；
8) mixture made from step 7) is cooled to 45 DEG C, 10 parts of Protection glues is added after filtering, obtain acrylic acid ester emulsion.
After tested, the water-fast acrylic acid ester emulsion of hydrophobic high rigidity that prepared by the present invention, it is hydrophobic detection (50 DEG C of deionized waters,
24h)：It does not increase weight, it is not blistering；Hardness determination (50 DEG C of tap water, for 24 hours)：High rigidity is not felt like jelly；Resistance to water-white detection (90 DEG C of distillations
Water, 12h)：It is non-discolouring, it does not fall off.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (8)
1. a kind of water-fast acrylic acid ester emulsion of hydrophobic high rigidity, which is characterized in that in parts by mass, including following raw material：Water 80-
120 parts, 10-30 parts of methyl methacrylate, 20-40 parts of styrene, 0-30 parts of Isooctyl acrylate monomer, 2-10 parts of function monomer,
0-2 parts of cross-linking monomer, 2-10 parts of Protection glue, 2-6 parts of emulsifier, 1-5 parts of initiator, 0-3 parts of reductant-oxidant.
2. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the function list
Body uses glycidyl methacrylate.
3. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the crosslinking is single
Body uses vinyltrimethoxysilane.
4. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the Protection glue
The content of middle lithium magnesium silicate is 40-60%.
5. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the emulsifier
For one or both of acrylic fatty alcohol polyoxyethylene ether ammonium sulfate, dodecyl sodium sulfate with arbitrary than mixing.
6. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the initiator
For in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate one kind or mentioned component mixed with arbitrary proportion.
7. a kind of hydrophobic water-fast acrylic acid ester emulsion of high rigidity according to claim 1, which is characterized in that the oxidation is also
Former agent uses one kind in tert-butyl hydroperoxide, sodium hydrogensulfite or mentioned component to be mixed with arbitrary proportion.
8. a kind of preparation method of any one of claim 1-7 hydrophobic water-fast acrylic acid ester emulsions of high rigidity, feature exist
In specifically including following steps：
1) under normal temperature state, 70-110 parts of water, the methyl methacrylate of formula ratio, benzene second is added in reaction kettle successively
Alkene, Isooctyl acrylate monomer, function monomer, cross-linking monomer, 0.5-2 part emulsifier, stir；
2) mixture that step 1) obtains is warming up to 80-85 DEG C, the initiator and 0.5-2 parts of emulsifiers of formula ratio is added, fills
Divide and stirs evenly；
3) mixture for obtaining step 2), temperature are maintained at 80-85 DEG C, while lasting stirring, react 10-20 minutes；
4) mixture for obtaining step 3) is kept the temperature at 80-85 DEG C, lasting to stir, and remaining emulsifier, time for adding is added dropwise
It is 4-5 hours；
5) after completion of dropwise addition, reaction kettle is warming up to 86-88 DEG C and keeps the temperature 0.5-1h；
6) after keeping the temperature, the mixture that step 5) is obtained first is cooled to 80-82 DEG C, then the oxidation with 5 parts of water dissolutions is added dropwise
0-1 parts of reduction, time for adding are 10-20 minutes, then keep the temperature 10-20 minutes；
7) mixture made from step 6) is first cooled to 75-78 DEG C, and the oxygen of 5 parts of water dissolutions is added dropwise into reaction kettle again
Change 0-2 parts of reduction, is added dropwise 10-20 minutes, and keep the temperature 10-20 minutes；
8) mixture made from step 7) is cooled to 35-45 DEG C, 2-10 parts of Protection glues is added after filtering, obtain required acrylic acid
Ester lotion.
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Application publication date: 20180810 |