CN105367697A - Silicone acrylic emulsion having core-shell structure and preparation method thereof - Google Patents
Silicone acrylic emulsion having core-shell structure and preparation method thereof Download PDFInfo
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- CN105367697A CN105367697A CN201510825107.4A CN201510825107A CN105367697A CN 105367697 A CN105367697 A CN 105367697A CN 201510825107 A CN201510825107 A CN 201510825107A CN 105367697 A CN105367697 A CN 105367697A
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Abstract
The invention relates to a silicone acrylic emulsion having a core-shell structure and a preparation method thereof. The silicone acrylic emulsion comprises the following components: methyl methacrylate, butyl acrylate, styrene, acrylic acid, a polymerisable environment-friendly emulsifier, an initiator, water, organosilicon and ammoniacal liquor. The silicone acrylic emulsion has the following advantages that a soap-free emulsion is employed for polymerization, the selected polymerisable environment-friendly emulsifier does not contain APE and formaldehyde, the emulsifier participates in a monomer polymerization process, emulsifier impurity in the silicone acrylic emulsion can be reduced, water resistance of the emulsion is greatly increased; in addition, the silicone acrylic emulsion has excellent characteristics of an acrylate polymer and an organosilicon polymer, the organosilicon monomer is employed for modifying the acrylate polymer, so that the disadvantages of poor water resistance performance, brittle condition due to low temperature and viscosifying/strength losing due to high temperature can be overcome. The organosilicon polymer as a shell can enhance the high/low temperature-resistant performance of the emulsion, and has the advantages of low surface energy and good water resistance performance.
Description
Technical field
The present invention relates to technical field of aqueous paint, be specifically related to a kind of nucleocapsid structure organosilicon crylic acid latex and preparation method thereof.
Background technology
Polyacrylate dispersion is due to abundant raw material source, inexpensive, advantages such as good film-forming property, intensity are high, good weatherability, strong adhesion and be widely used in inner wall of building, exterior wall, ceiling and ground application emulsion paint and produce.Although acrylic resin has excellent film-forming properties and weathering resistance, water vapour permeability and shortcoming limits its application in building external paint field such as water tolerance is poor, low-temperature flexibility is poor.
Compared with polyacrylic ester, silicone resin is with siloxane bond (Si-O-Si) for major key, and its bond energy is 452.5kJ/mol, higher than carbon-carbon bond, bond distance is longer than carbon-carbon bond, and thus main chain has the kindliness of height, and its high-and low-temperature resistance performance, ultraviolet light and aging performance are excellent especially; The most significant two fundamental propertys are high oxidation resistance and low surface energy, and because surface tension is little, water and other dirt not easily adhere to, so silicone resin has good moistureproofness, water resistant and steam.But the Intermolecular Forces of polysiloxane is little, and cohesive energy density(CED) is low, thus low strength, to the poor adhesion of the base materials such as metal, rubber and plastics, and cost ratio polyacrylic ester is much higher.These deficiencies limit its application.
Organosilicon crylic acid latex had both remained the superiority of acrylic ester polymer and organosilicon polymer, supplement again their respective defects, it is predicted, organic silicone modified acrylate coating material be development in recent years the soonest, have DEVELOPMENT PROSPECT most, and one of high performance outer wall paint kind being also in the research and development stage.Existing many polysiloxane-acrylic ester emulsions reach practical value at present, and its theoretical investigation, also by the polymer blending of macroscopic view, develops into submicroscopic composite polymer latex.
Silicone-acrylate core shell structure emulsion is prepared by seed emulsion polymerization, and according to the difference of seed emulsion composition, can to obtain polysiloxane be respectively shell and polyacrylic ester is the emulsion of core, and its nucleocapsid has different functions.Core-shell polymer has better film-forming properties, stability, binding property and mechanical property than common emulsion blending thing or random copolymers, and thus at tackiness agent, anticorrosion or decorative paint, and the field such as sensitive materials has a wide range of applications.
Summary of the invention
The invention provides a kind of nucleocapsid structure organosilicon crylic acid latex and preparation method thereof, it has the good characteristic of both acrylic ester polymer and organosilicon polymer concurrently, adopt organosilane monomer modified polyacrylate, overcome acrylic ester polymer poor water resistance and low temperature becomes fragile, high temperature becomes sticky loses strong shortcoming.The high and low temperature resistance of emulsion of the present invention is good, hydrophobicity is good, moistureproofness is good, water resisting property is good, wear resistance is good.In addition, the present invention adopts the agent of polymerizable environment protective emulsive, decreases the emulsifying agent impurity in organosilicon crylic acid latex, and substantially increases the water tolerance of emulsion.
Technical solution of the present invention is as follows:
One) scheme one:
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
Described polymerisable emulsifier is the mixture mixed according to the mass ratio of 1-2:1-2 by polymerizable negative ion emulsifying agent and polymerizable nonionic emulsifying agent.
Further, described polymerizable negative ion emulsifying agent refers to the long chain alkylammonium salts containing propenyl, and described polymerizable nonionic emulsifying agent is containing the long-chain alkyl alcohol of propenyl.
Allyl group can participate in the polymerization of Acrylic Acid Monomer, decreases the emulsifying agent monomelic impurities in the organosilicon crylic acid latex of preparation, owing to not containing emulsifying agent impurity in organosilicon crylic acid latex, can substantially increase the water tolerance of emulsion.
Further, described initiator is the one in ammonium persulphate or Potassium Persulphate.
Further, described organosilicon is mixed by eight or the four basic ring tetrasiloxanes of 0.70-1.20 part, the vinyltriethoxysilane of 0.70-1.50 part and the γ-methacryloxypropyl trimethoxy silane of 0.70-1.50 part.
Vinyltriethoxysilane and γ-methacryloxypropyl trimethoxy silane are put into methoxyl group and oxyethyl group in water solution system and are easy to hydrolysis and become silanol, there is copolymerzation with cross-linking in its dehydration, and effectively can open the ring of octamethylcyclotetrasiloxane, make it effectively be grafted in acrylate copolymer, complete silicone modified polyacrylate.
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
The Acrylic Acid Monomer of the butyl acrylate of the methyl methacrylate of the initiator of the polymerisable emulsifier of the water of 60.00-75.00 part, 2.29-3.97 part, 0.45-0.70 part, 10.00-15.00 part, 60.00-70.00 part, the vinylbenzene of 65.00-75.00 part and 2.00-5.00 part is joined in reactor A, disperses within 20-30 minute, to obtain Acrylic Acid Monomer pre-emulsification storing solution under the mixing speed of 1000-1200r/min;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300-400r/min, in reactor B, add the water of 60.00-75.00 part and the polymerisable emulsifier of 1.40-2.70 part, then 75-80 DEG C is warmed up to, then initiator solution and 5-10% step 1 is added) the Acrylic Acid Monomer pre-emulsification storing solution prepared,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 20-30 minute more afterwards;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip initiator solution and 80-85% step 1) the Acrylic Acid Monomer pre-emulsification storing solution prepared, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 1.5-2 hour, the time for adding of described initiator solution is 1.5-2 hour, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, raised temperature is to 82-85 DEG C, and then insulation reaction 20-30 minute, obtain nucleocapsid structure ACRYLIC EMULSION;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then by step 1) remainder of Acrylic Acid Monomer pre-emulsification storing solution prepared mixes with 2.10-4.20 part organosilicon, at 82-85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION that is prepared from, time for adding is 20-30 minute, then insulation reaction 2-3 hour at 82-85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.00-1.20 part, filter, discharging;
Step 2) and step 3) described in initiator solution be all mixed by the water of the initiator of 0.20-0.30 part and 8.00-12.00 part.
Inventive principle of the present invention is as follows:
The present invention is using methyl methacrylate (MMA), butyl acrylate (BA), vinylbenzene (St), vinylformic acid (AA) monomer copolymer as seed emulsion, with the multipolymer of eight or four basic ring tetrasiloxanes (D4), vinyltriethoxysilane (A-171), γ-methacryloxypropyl trimethoxy silane (A-174NT) and Acrylic Acid Monomer for shell, prepare the organosilicon-modified acrylate emulsion with nucleocapsid structure.The polymerizable environment protective emulsive agent selected, not containing APE and formaldehyde, emulsifying agent participates in the polymerization process of monomer, decrease the emulsifying agent impurity in organosilicon crylic acid latex, in addition, organosilicon crylic acid latex has the good characteristic of both acrylic ester polymer and organosilicon polymer concurrently, adopts organosilane monomer modified polyacrylate, overcomes acrylic ester polymer poor water resistance and low temperature becomes fragile, high temperature becomes sticky loses strong shortcoming.Organosilicon polymer as shell substantially increase emulsion high and low temperature resistance and due to organosilyl surface can low therefore emulsion hydrophobicity good, moistureproofness is good, water resisting property good, wear resistance is good.
The present invention compared with prior art, has the following advantages:
1) adopt emulsifier-free emulsion polymerization, select polymerisable emulsifier, not containing APE and formaldehyde, and emulsifying agent participates in the polymerization process of monomer, decreases the emulsifying agent impurity in organosilicon crylic acid latex, and substantially increases the water tolerance of emulsion;
2) adopt organosilicon to modification of acrylate emulsions, siloxane bond (Si-O-Si) key is introduced in acrylic ester polymer, because its bond energy is higher and have low surface energy than carbon-carbon bond, therefore organosilicon acrylic resin high-and low-temperature resistance excellent performance and hydrophobicity is good, has good moistureproofness, water resistant and steam;
3) the present invention adopts the mode of seeded emulsion polymerization to prepare the organosilicon crylic acid latex with nucleocapsid structure, and this is different from general multipolymer and blend.In same materials composition situation, because organosilicon polymer is in shell completely, the nucleocapsid structure of emulsion particle can significantly improve wear-resisting, water-fast, weather-proof, the antifouling property of polymer emulsion.
Embodiment
Below in conjunction with embodiment, embodiment, content of the present invention is described in detail:
(1) embodiment
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
The Acrylic Acid Monomer of the butyl acrylate of the methyl methacrylate of the initiator of the polymerisable emulsifier of the water of 60.00-75.00 part, 2.29-3.97 part, 0.45-0.70 part, 10.00-15.00 part, 60.00-70.00 part, the vinylbenzene of 65.00-75.00 part and 2.00-5.00 part is joined in reactor A, disperses within 20-30 minute, to obtain Acrylic Acid Monomer pre-emulsification storing solution under the mixing speed of 1000-1200r/min;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300-400r/min, in reactor B, add the water of 60.00-75.00 part and the polymerisable emulsifier of 1.40-2.70 part, then 75-80 DEG C is warmed up to, then initiator solution and 5-10% step 1 is added) the Acrylic Acid Monomer pre-emulsification storing solution prepared,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 20-30 minute more afterwards;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip initiator solution and 80-85% step 1) the Acrylic Acid Monomer pre-emulsification storing solution prepared, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 1.5-2 hour, the time for adding of described initiator solution is 1.5-2 hour, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, raised temperature is to 82-85 DEG C, and then insulation reaction 20-30 minute, obtain nucleocapsid structure ACRYLIC EMULSION;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then by step 1) remainder of Acrylic Acid Monomer pre-emulsification storing solution prepared mixes with 2.10-4.20 part organosilicon, at 82-85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION that is prepared from, time for adding is 20-30 minute, then insulation reaction 2-3 hour at 82-85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.00-1.20 part, filter, discharging;
Step 2) and step 3) described in initiator solution be all mixed by the water of the initiator of 0.20-0.30 part and 8.00-12.00 part.
(2) embodiment:
Embodiment 1
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
Join in reactor A by the Acrylic Acid Monomer of the water of 60.00 parts, the polymerisable emulsifier of 2.29 parts, the initiator of 0.45 part, the methyl methacrylate of 10.00 parts, the butyl acrylate of 70.00 parts, the vinylbenzene of 75.00 parts and 2.00 parts, under the mixing speed of 1000r/min, dispersion obtains Acrylic Acid Monomer pre-emulsification storing solution for 20 minutes;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300r/min, in reactor B, add the water of 60.00 parts and the polymerisable emulsifier of 1.40 parts, then 75 DEG C are warmed up to, then Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution of 5% is added,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 20 minutes more afterwards;
Described initiator solution is mixed by the initiator of 0.20 part and the water of 8.00 parts;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, 80% Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution dripped, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 1.5 hours, the time for adding of described initiator solution is 1.5 hours, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, and raised temperature to 82 DEG C, and then insulation reaction 20 minutes, obtain nucleocapsid structure ACRYLIC EMULSION;
Described initiator solution is mixed by the initiator of 0.20 part and the water of 8.00 parts;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then remaining Acrylic Acid Monomer pre-emulsification storing solution is mixed with 2.50 parts of organosilicons, at 82 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION reactor B that is prepared from, time for adding is 20 minutes, then insulation reaction 2 hours at 82 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.00 parts, filter, discharging.
Embodiment 2
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
The Acrylic Acid Monomer of the water of 75.00 parts, the polymerisable emulsifier of 3.97 parts, the initiator of 0.70 part, the methyl methacrylate of 15.00 parts, the butyl acrylate of 60.00 parts, the vinylbenzene of 65.00 parts and 5.00 parts is joined in reactor A, disperses within 20-30 minute, to obtain Acrylic Acid Monomer pre-emulsification storing solution under the mixing speed of 1200r/min;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 400r/min, in reactor B, add the water of 75.00 parts and the polymerisable emulsifier of 2.70 parts, then 80 DEG C are warmed up to, then Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution of 10% is added,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 30 minutes more afterwards;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip 85% Acrylic Acid Monomer pre-emulsification storing solution and initiator solution, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 2 hours, the time for adding of described initiator solution is 1.5 hours, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, and raised temperature to 85 DEG C, and then insulation reaction 30 minutes, obtain nucleocapsid structure ACRYLIC EMULSION;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then remaining Acrylic Acid Monomer pre-emulsification storing solution is mixed with 4.20 parts of organosilicons, at 85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION reactor B that is prepared from, time for adding is 30 minutes, then insulation reaction 3 hours at 85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.20 parts, filter, discharging.
Embodiment 3
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
Join in reactor A by the Acrylic Acid Monomer of the water of 70.00 parts, the polymerisable emulsifier of 3 parts, the initiator of 0.60 part, the methyl methacrylate of 11.75 parts, the butyl acrylate of 65.00 parts, the vinylbenzene of 69.14 parts and 2.16 parts, under the mixing speed of 1100r/min, dispersion obtains Acrylic Acid Monomer pre-emulsification storing solution for 25 minutes;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300r/min, in reactor B, add the water of 70.00 parts and the polymerisable emulsifier of 2 parts, then 80 DEG C are warmed up to, then Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution of 10% is added,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 30 minutes more afterwards;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip 85% Acrylic Acid Monomer pre-emulsification storing solution and initiator solution, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 2 hours, the time for adding of described initiator solution is 1.5 hours, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, and raised temperature to 85 DEG C, and then insulation reaction 30 minutes, obtain nucleocapsid structure ACRYLIC EMULSION;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then remaining Acrylic Acid Monomer pre-emulsification storing solution is mixed with 2.70 parts of organosilicons, at 85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION reactor B that is prepared from, time for adding is 30 minutes, then insulation reaction 3 hours at 85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.20 parts, filter, discharging.
Embodiment 4
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
Join in reactor A by the Acrylic Acid Monomer of the water of 75.00 parts, the polymerisable emulsifier of 3.5 parts, the initiator of 0.6 part, the methyl methacrylate of 15.00 parts, the butyl acrylate of 60.00 parts, the vinylbenzene of 70.00 parts and 4.00 parts, under the mixing speed of 1200r/min, dispersion obtains Acrylic Acid Monomer pre-emulsification storing solution for 30 minutes;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 400r/min, in reactor B, add the water of 75.00 parts and the polymerisable emulsifier of 2.20 parts, then 80 DEG C are warmed up to, then Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution of 7% is added,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 30 minutes more afterwards;
Described initiator solution is mixed by the initiator of 0.21 part and the water of 10.00 parts;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip 85% Acrylic Acid Monomer pre-emulsification storing solution and initiator solution, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 1.5 hours, the time for adding of described initiator solution is 1 hour, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, and raised temperature to 85 DEG C, and then insulation reaction 30 minutes, obtain nucleocapsid structure ACRYLIC EMULSION;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then remaining Acrylic Acid Monomer pre-emulsification storing solution is mixed with 2.10 parts of organosilicons, at 85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION reactor B that is prepared from, time for adding is 20 minutes, then insulation reaction 2 hours at 85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.20 parts, filter, discharging.
Embodiment 5
A kind of nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
A preparation method for nucleocapsid structure organosilicon crylic acid latex, it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
Join in reactor A by the Acrylic Acid Monomer of the water of 75.00 parts, the polymerisable emulsifier of 3.5 parts, the initiator of 0.60 part, the methyl methacrylate of 13.00 parts, the butyl acrylate of 68.10 parts, the vinylbenzene of 67.25 parts and 3.15 parts, under the mixing speed of 1200r/min, dispersion obtains Acrylic Acid Monomer pre-emulsification storing solution for 30 minutes;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300-400r/min, in reactor B, add the water of 75.00 parts and the polymerisable emulsifier of 2.5 parts, then 80 DEG C are warmed up to, then Acrylic Acid Monomer pre-emulsification storing solution and the initiator solution of 10% is added,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 30 minutes more afterwards;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip 85% Acrylic Acid Monomer pre-emulsification storing solution and initiator solution, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 2 hours, the time for adding of described initiator solution is 1.5 hours, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, and raised temperature to 85 DEG C, and then insulation reaction 30 minutes, obtain nucleocapsid structure ACRYLIC EMULSION;
Described initiator solution is mixed by the initiator of 0.30 part and the water of 12.00 parts;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then remaining Acrylic Acid Monomer pre-emulsification storing solution is mixed with 3.40 parts of organosilicons, at 85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION reactor B that is prepared from, time for adding is 30 minutes, then insulation reaction 3 hours at 85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.20 parts, filter, discharging.
In above each embodiment:
Described initiator is ammonium persulphate, methyl methacrylate, butyl acrylate, vinylbenzene, vinylformic acid, preferably Aladdin reagent.
Described organosilicon vinyltriethoxysilane (A-171), γ-methacryloxypropyl trimethoxy silane (A-174NT) preferably Mai Tu new high-tech material company limited.
Described organosilicon eight or four basic ring tetrasiloxane (D4) is Beijing Rui Chen chemical assistant company limited preferably.
Described anionic emulsifier is containing the SR-10 of the preferred Ai Dike trade Co., Ltd of long chain alkylammonium salts of propenyl.
Described nonionic emulsifying agent is containing the ER-10 of the preferred Ai Dike trade Co., Ltd of long-chain alkyl alcohol of propenyl.
The performance tests such as solid content, size, hardness of paint film, water-intake rate, contact angle are carried out to the organosilicon crylic acid latex of nucleocapsid structure.
Solid content is tested: the quality accurately taking blank flat disk is M
0, take about 1g sample, the quality of sample disk is pacifically M altogether
2, sample is heated 1h in 120 ± 2 DEG C of baking ovens.After in moisture eliminator, be cooled to room temperature, again weigh the quality M altogether of remaining sample and flat disk
1, all weighings are accurately to 0.1mg.
The percentage ratio (X) of solid content is calculated as follows:
X＝100×(M1-M0)/(M2-M0)
Measure twice, measurement result is averaged, and report test result is to a decimal.
Sreen analysis: adopt Malvern company 3000SHA type nano-particle size analysis instrument test emulsion particle diameter.
Hardness: test according to GB/T6739 regulation.
Water-intake rate measures: obtained uniform film on a glass, takes off, weighs, then in water, soak 24h, take out, blot surface-moisture, again weigh with filter paper, calculate water-intake rate.
Contact angle determination: adopt Germany's gram scholar Lu DSA30 contact angle tester test paint film contact angle.
Through the test to each embodiment, the detection data results of nucleocapsid structure organosilicon crylic acid latex of the present invention is as shown in following table:
Obviously can find out from table one, various embodiments of the present invention all have good hardness under difficult environmental conditions, contact angle is large, hydrophobicity good, water-intake rate is low, there is good using value.
The experimental data of each embodiment test of the organosilicon crylic acid latex of table one, nucleocapsid structure
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Paint film appearance | Transparent | Transparent | Transparent | Transparent | Transparent |
| Solid content (%) | 51.87 | 49.87 | 50.99 | 46.71 | 50.75 |
| Hardness | HB+ | F+ | HB+ | HB+ | F+ |
| Water-intake rate (%) | 15 | 5 | 17 | 22 | 13 |
| Particle diameter (nm) | 105.62 | 111.89 | 100.20 | 101.79 | 105.79 |
| Contact angle | 78.38 | 89.18 | 83.62 | 76.60 | 88.82 |
| Thermostability | Without exception | Without exception | Without exception | Without exception | Without exception |
| Freeze-thaw stability | Without exception | Without exception | Without exception | Without exception | Without exception |
In sum, the nucleocapsid structure of various embodiments of the present invention organosilicon crylic acid latex has good hardness, contact angle is large, hydrophobicity good, water-intake rate is low, there is good using value.
Above-mentioned embodiment is just explained in detail technical scheme of the present invention; the present invention has more than and is only confined to above-described embodiment; those skilled in the art should be understood that; every improvement on basis of the present invention according to above-mentioned principle and spirit, substitute, all should within protection scope of the present invention.
Claims (5)
1. a nucleocapsid structure organosilicon crylic acid latex, is characterized in that: it is formulated by following ratio of weight and number by following component:
Described polymerisable emulsifier is the mixture mixed according to the mass ratio of 1-2:1-2 by polymerizable negative ion emulsifying agent and polymerizable nonionic emulsifying agent.
2. nucleocapsid structure organosilicon crylic acid latex according to claim 1, is characterized in that: described polymerizable negative ion emulsifying agent is the long chain alkylammonium salts containing propenyl, and described polymerizable nonionic emulsifying agent is the long-chain alkyl alcohol containing propenyl.
3. nucleocapsid structure organosilicon crylic acid latex according to claim 1, is characterized in that: described initiator is the one in ammonium persulphate or Potassium Persulphate.
4. nucleocapsid structure organosilicon crylic acid latex according to claim 1, is characterized in that: described organosilicon is mixed by eight or the four basic ring tetrasiloxanes of 0.70-1.20 part, the vinyltriethoxysilane of 0.70-1.50 part and the γ-methacryloxypropyl trimethoxy silane of 0.70-1.50 part.
5. a preparation method for the nucleocapsid structure organosilicon crylic acid latex according to any one of claim 1-4, is characterized in that: it is prepared from according to following step of sequentially carrying out by the raw material of following weight proportioning:
1) Acrylic Acid Monomer pre-emulsification storing solution is prepared:
The Acrylic Acid Monomer of the butyl acrylate of the methyl methacrylate of the initiator of the polymerisable emulsifier of the water of 60.00-75.00 part, 2.29-3.97 part, 0.45-0.70 part, 10.00-15.00 part, 60.00-70.00 part, the vinylbenzene of 65.00-75.00 part and 2.00-5.00 part is joined in reactor A, disperses within 20-30 minute, to obtain Acrylic Acid Monomer pre-emulsification storing solution under the mixing speed of 1000-1200r/min;
2) seed emulsion is prepared:
Under room temperature and stir speed (S.S.) are 300-400r/min, in reactor B, add the water of 60.00-75.00 part and the polymerisable emulsifier of 1.40-2.70 part, then 75-80 DEG C is warmed up to, then initiator solution and 5-10% step 1 is added) the Acrylic Acid Monomer pre-emulsification storing solution prepared,, to reaction flask, there is blue light, obtain seed emulsion in insulation reaction 20-30 minute more afterwards;
3) preparation of nucleocapsid structure ACRYLIC EMULSION:
Then in above-mentioned steps 2) in the seed emulsion that is prepared from, drip initiator solution and 80-85% step 1) the Acrylic Acid Monomer pre-emulsification storing solution prepared, described Acrylic Acid Monomer pre-emulsification storing solution time for adding is 1.5-2 hour, the time for adding of described initiator solution is 1.5-2 hour, described Acrylic Acid Monomer pre-emulsification storing solution and initiator solution are added dropwise to complete simultaneously, after being added dropwise to complete, raised temperature is to 82-85 DEG C, and then insulation reaction 20-30 minute, obtain nucleocapsid structure ACRYLIC EMULSION;
4) nucleocapsid structure organosilicon crylic acid latex is prepared:
Then by step 1) remainder of Acrylic Acid Monomer pre-emulsification storing solution prepared mixes with 2.10-4.20 part organosilicon, at 82-85 DEG C, mixed solution is added dropwise to above-mentioned steps 3) in the nucleocapsid structure ACRYLIC EMULSION that is prepared from, time for adding is 20-30 minute, then insulation reaction 2-3 hour at 82-85 DEG C, is then cooled to room temperature, adds the ammoniacal liquor of 1.00-1.20 part, filter, discharging;
Step 2) and step 3) described in initiator solution be all mixed by the water of the initiator of 0.20-0.30 part and 8.00-12.00 part.
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| CN112011315B (en) * | 2020-09-14 | 2021-05-28 | 中国石油大学(华东) | Inorganic/polymer composite material plugging agent for ultrahigh-temperature-resistant oil-based drilling fluid and preparation method and application thereof |
| CN112011315A (en) * | 2020-09-14 | 2020-12-01 | 中国石油大学(华东) | Inorganic/polymer composite material plugging agent for ultrahigh-temperature-resistant oil-based drilling fluid and preparation method and application thereof |
| CN115894771A (en) * | 2022-03-18 | 2023-04-04 | 上海启梦胶粘制品有限公司 | Acrylic latex and preparation method thereof |
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| CN115960509A (en) * | 2023-01-06 | 2023-04-14 | 德爱威（中国）有限公司 | Water-based flame-retardant interior wall latex paint and preparation method thereof |
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