CN100999583A - Mfg. process of organic silican polymer emulsion - Google Patents
Mfg. process of organic silican polymer emulsion Download PDFInfo
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- CN100999583A CN100999583A CN 200610161356 CN200610161356A CN100999583A CN 100999583 A CN100999583 A CN 100999583A CN 200610161356 CN200610161356 CN 200610161356 CN 200610161356 A CN200610161356 A CN 200610161356A CN 100999583 A CN100999583 A CN 100999583A
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Abstract
The process of preparing polysilicone emulsion includes the following steps: 1. dissolving emulsifier of 0.05-5 weight portions and catalyst of 0.05-5 weight portions in water of 100 weight portions, dropping siloxane monomer of 10-40 weight portions while stirring and further stirring for 0.5-3 hr to form monomer emulsion; and ultrasonic treatment for 1-15 min to obtain fine siloxane monomer emulsion of 100-500 nm size; and 2. polymerizing the fine siloxane monomer emulsion in a reactor at 30-90 deg.c for 3-10 hr to obtain polysilicone emulsion. Thus prepared polysilicone emulsion has high stability, and the process is simple and high in conversion rate.
Description
Technical field
The present invention relates to a kind of manufacture method of organic silican polymer emulsion, especially be particularly related to a kind of manufacture method of silicone polymer emulsion.
Background technology
Characteristics such as the low surface energy that organosilicon polymer had, low temperature kindliness, high temperature resistant and biocompatibility make it have very wide purposes.
The preparation method of traditional organic silicon emulsion mainly contains two kinds, the emulsification (silicone oil emulsification method) of letex polymerization of organosilane monomer (emulsion polymerization) and silicone oil, but the two all has himself unsurmountable shortcoming.With regard to emulsion polymerization, because organosilane monomer is water-soluble extremely low, monomer is difficult to be diffused into polymerization site by water from monomer droplet in the polymerization process, causes the floating oil phenomenon occurring in the polymerization later stage, can't prepare stable small particle size organic silican polymer emulsion.With regard to the silicone oil emulsification method, the emulsification of silicone oil expends a large amount of emulsifying agents and energy, and the stability of the organic silicon emulsion of preparing is also lower.Organosilicon polymer derives from the hydrolytic condensation polymerization of organochlorosilane and the ring-opening polymerization of cyclosiloxane usually, adopts emulsion polymerization can make corresponding organic silican polymer emulsion.
Purpose of the present invention is to adopt a kind of new technology to prepare organic silican polymer emulsion.
Summary of the invention
Method of the present invention has solved the difficulty on the organosilane monomer mass transfer in the conventional emulsion polymerization method, overcome emulsion polymerization of the prior art and floating oil in reaction, occurs, the shortcoming of the organic silican polymer emulsion poor stability that makes reaches the purpose for preparing stable tiny particle diameter organic silican polymer emulsion.
The technical solution used in the present invention is as follows:
A kind of manufacture method of organic silican polymer emulsion may further comprise the steps:
A) preparation of siloxanyl monomers miniemulsion: with the catalyst dissolution of the emulsifying agent of 0.05-5 part quality and 0.05-5 part quality in the water of 100 parts of quality, under agitation drip the siloxanyl monomers of 10-40 part quality, drip the back and continue to stir 0.5-3 hour, form monomer pre-emulsion; Monomer pre-emulsion is placed under the ultrasonic wave effect 1-15 minute, to monomer droplet be the 100-500 nanometer, make the siloxanyl monomers miniemulsion;
B) polymerization of siloxanyl monomers miniemulsion: with steps A) resulting siloxanyl monomers miniemulsion input reactor carries out polyreaction, and temperature of reaction 30-90 ℃, reacted 3-10 hour, make organic silican polymer emulsion.
As indicated above, the preparation method of two kinds of traditional organic silicon emulsions, promptly emulsion polymerization and silicone oil emulsification method all have himself unsurmountable shortcoming.For water-soluble extremely low organosilane monomer, adopt emulsion polymerization to prepare organic silicon emulsion, monomer is difficult to be diffused into polymerization site by water from monomer droplet in polymerization process, causes the floating oil phenomenon occurring in the polymerization later stage, can't prepare stable small particle size organic silican polymer emulsion.The stability of the prepared organic silicon emulsion that goes out of silicone oil emulsification method is also lower.
The present invention adopts the method for mini-emulsion polymerization to prepare organic silican polymer emulsion.The nucleation mode of mini-emulsion polymerization method is different with conventional emulsion polymerization, is particularly suitable for water-soluble low monomeric polymerization, can overcome the difficulty of monomer mass transfer in the polymerization process effectively, and can prepare the organic silican polymer emulsion of expection polymkeric substance particle diameter.
Ultimate principle of the present invention is that water-soluble extremely low organosilane monomer successively by pre-emulsification and ultrasonic emulsification stage processing, is dispersed into the organosilane monomer miniemulsion, carries out monomeric polymerization again.In the organosilane monomer miniemulsion, under the effect of catalyzer, organosilane monomer causes the generation active centre in the emulsifying agent layer on drop surface, polyreaction is carried out in monomer droplet, each monomer droplet all is a nano level reactor, the size of the organic silican polymer emulsion particle that finally obtains and organosilane monomer drop big or small similar.Mini-emulsion polymerization has been avoided the conveying of organosilane monomer at aqueous phase, and layering or floating oil phenomenon can not appear in having good stability of the organic silican polymer emulsion that finally obtains.
Among the present invention, described organosilane monomer refers to siloxanyl monomers, and described organic silican polymer emulsion refers to silicone polymer emulsion.Siloxanyl monomers includes but not limited to octamethylcyclotetrasiloxane (D
4), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (D
4 V), tetramethyl-tetrahydrochysene cyclotetrasiloxane (D
4 H), hexamethyldisiloxane (MM), tetramethyl divinyl disiloxane (M
2 V) or tetramethyl-dihydro sily oxide (M
2 H) wait siloxanyl monomers or their mixture.
Described emulsifying agent comprises cationic surfactant and aniorfic surfactant.Cats product such as N-alkyl monoethanolamine salt, N-alkyl diethanolamine salt and polyethylene polyamines salt, alkyl quaternary amine salt, two alkyl quaternary amine salt, pyridinium salt, imidazoline type, morpholine type cats product etc.; Anion surfactant such as C
12-C
18Sodium alkyl sulfate, C
12-C
18Sodium alkyl benzene sulfonate, polyxyethylated alkylphenol vitriol, Succinic Acid modification polyxyethylated alkylphenol anion surfactant etc.
Described catalyzer comprises an acidic catalyst and basic catalyst.An acidic catalyst such as sulfuric acid, hydrochloric acid and Phenylsulfonic acid etc., the common ground that they had is that proton H can both be provided
+And has better water solubility; Basic catalyst such as sodium hydroxide, potassium hydroxide, calcium hydroxide etc., its common ground is that hydroxide ion OH can be provided
-And has better water solubility.
Steps A) preparation of organosilane monomer miniemulsion comprises pre-emulsification and two stages of ultrasonic emulsification.Pre-emulsification is about to organosilane monomer and is added dropwise in the aqueous solution that is dissolved with emulsifying agent, fully stirs, and formation monomer droplet size is tens of microns a monomer pre-emulsion.Then monomer pre-emulsion is carried out ultrasonic emulsification, promptly act on monomer pre-emulsion with ultrasonic wave, ultrasonication 1-15 minute, then monomer droplet progressively was reduced to the 100-500 nanometer, thereby can obtain enough stability, obtained stable organosilane monomer miniemulsion.The mode of ultrasonic wave effect can be inserted the ultrasonic wave rod in pre-emulsion, open ultrasonic generator.
According to the present invention, the prescription of described each material is that in the water of 100 parts of quality, tensio-active agent is 0.05-5 part quality, can be 0.05 part, 0.075 part, 0.1 part, 0.3 part, 0.7 part, 1.5 parts, 3 parts or 5 parts such as mass fraction; Catalyzer is 0.05-5 part quality, can be 0.05 part, 0.075 part, 0.1 part, 0.3 part, 0.7 part, 1.5 parts, 3 parts, 5 parts such as mass fraction; Organosilane monomer is 10-40 part quality, can be 10 parts, 20 parts, 25 parts, 30 parts, 40 parts as mass fraction.
Step B) the organosilane monomer miniemulsion that obtains is carried out polymerization.The present invention adopts miniemulsion still formula polymerization methods, above-mentioned organosilane monomer miniemulsion dropped in the reactor, and polymerization reaction take place under catalyst action, temperature of reaction 30-90 ℃, the reaction times is 3-10 hour, can make organic silican polymer emulsion.
Compare with the preparation method of organic silican polymer emulsion in the prior art, the present invention has the following advantages:
Method steps used in the present invention is less, and is simple to operate, and the method cost is lower, the transformation efficiency height, and the prepared emulsion of the inventive method is stable very good, and normal temperature is placed layering or breakdown of emulsion was not taken place more than 1 year.
The organosilicon polymer miniemulsion of the present invention preparation has excellent comprehensive performances, can be widely used in the low surface energyization, makeup of polymer surfaces, many fields such as lubricated.
Describe the present invention below in conjunction with embodiment.Scope of the present invention is not exceeded with embodiment, but is limited by the scope of claim.
Embodiment
Embodiment one
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
A) preparation of organosilane monomer miniemulsion
With 0.15g Sodium dodecylbenzene sulfonate and 0.4 gram Witco 1298 Soft Acid 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the 25g octamethylcyclotetrasiloxane with dropping funnel under the whipped state, drip to finish back continuation stirring 1 hour, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Ultrasonic time is 10 minutes.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.
The proportioning of above-mentioned each material is as follows:
A Sodium dodecylbenzene sulfonate 0.15g
B Witco 1298 Soft Acid 0.4g
C water 125g
D octamethylcyclotetrasiloxane 25g
As stated above, obtain the organosilane monomer miniemulsion that mean diameter is 216 nanometers.
B) polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 80 ℃, and the reaction timing begins.React after 6 hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 216 nanometers, the transformation efficiency of organosilane monomer is 92.3%.
Embodiment 2
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
A) preparation of organosilane monomer miniemulsion
With 0.1125g Sodium dodecylbenzene sulfonate and 0.3 gram Witco 1298 Soft Acid 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mix monomer of 22.5g octamethylcyclotetrasiloxane and 2.5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane with dropping funnel under the whipped state, drip to finish the back and continue to stir 1.5 hours, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Ultrasonic time is 8 minutes.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.
The material proportioning is:
A Sodium dodecylbenzene sulfonate 0.1125g
B Witco 1298 Soft Acid 0.3g
C water 125g
D octamethylcyclotetrasiloxane 22.5g
E tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 2.5g
Obtaining mean diameter is the organosilane monomer miniemulsion of 236 nanometers.
B) polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 60 ℃, and the reaction timing begins.React after 9 hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 230 nanometers, the transformation efficiency of organosilane monomer is 85.6%.
Embodiment 3
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
A) preparation of organosilane monomer miniemulsion
With 0.15g Sodium dodecylbenzene sulfonate and 0.2 gram vitriol oil 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mixture of 20g octamethylcyclotetrasiloxane, 5g tetramethyl-tetrahydrochysene cyclotetrasiloxane and 0.274g hexamethyldisiloxane under the whipped state with dropping funnel, drip and finish back continuation stirring 2 hours, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Ultrasonic time is 15 minutes.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.
Each material proportioning is:
A Sodium dodecylbenzene sulfonate 0.15g
B vitriol oil 0.2g
C water 125g
D octamethylcyclotetrasiloxane 20g
E tetramethyl-tetrahydrochysene cyclotetrasiloxane 5g
F hexamethyldisiloxane 0.274g
Obtaining mean diameter is the organosilane monomer miniemulsion of 218 nanometers.
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 50 ℃, and the reaction timing begins.React after 8 hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 215 nanometers, the transformation efficiency of organosilane monomer is 82.0%.
Embodiment 4
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 0.9912g dodecylbenzyl brometo de amonio and 0.037 gram sodium hydroxide 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.Whipped state (1000 rev/mins) slowly drips the 25g octamethylcyclotetrasiloxane with dropping funnel, drips to finish back continuation stirring 2 hours, makes the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 5 minutes.
The proportioning of above-mentioned each material is:
A dodecylbenzyl brometo de amonio 0.9912g
B sodium hydroxide 0.037g
C water 125g
D octamethylcyclotetrasiloxane 25g
Obtaining mean diameter is the organosilane monomer miniemulsion of 330 nanometers.
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 50 ℃, and the reaction timing begins.React after 7 hours cooling and with in the dilute hydrochloric acid and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 328 nanometers, the transformation efficiency of organosilane monomer is 79.4%.
Embodiment 5
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 0.3g Sodium dodecylbenzene sulfonate and 0.3 gram concentrated hydrochloric acid 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mixture of 25g octamethylcyclotetrasiloxane and 0.1g tetramethyl-dihydro sily oxide with dropping funnel under the whipped state, drip to finish the back and continue to stir 1 hour, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 15 minutes.
Proportioning:
A Sodium dodecylbenzene sulfonate 0.3g
B concentrated hydrochloric acid 0.3g
C water 125g
D octamethylcyclotetrasiloxane 25g
E tetramethyl-dihydro sily oxide 0.1g
Obtaining mean diameter is the organosilane monomer miniemulsion of 193 nanometers
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 70 ℃, and the reaction timing begins.React after ten hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 190 nanometers, the transformation efficiency of organosilane monomer is 91.1%.
Embodiment 6
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 2.5g Sodium dodecylbenzene sulfonate and 0.4 gram Witco 1298 Soft Acid 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mixture of 12.5g octamethylcyclotetrasiloxane and 0.4g tetramethyl divinyl disiloxane with dropping funnel under the whipped state, drip to finish the back and continue to stir 1 hour, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 15 minutes.
Proportioning:
A Sodium dodecylbenzene sulfonate 2.5g
B Witco 1298 Soft Acid 0.4g
C water 125g
D octamethylcyclotetrasiloxane 12.5g
E tetramethyl divinyl disiloxane 0.4g
Obtaining mean diameter is the organosilane monomer miniemulsion of 160 nanometers
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 40 ℃, and the reaction timing begins.React after ten hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 158 nanometers, the transformation efficiency of organosilane monomer is 75%.
Embodiment 7
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 5g Sodium dodecylbenzene sulfonate and 2.5 gram Witco 1298 Soft Acid 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the 37.5g octamethylcyclotetrasiloxane with dropping funnel under the whipped state, drip to finish back continuation stirring 1 hour, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 10 minutes.
Proportioning:
A Sodium dodecylbenzene sulfonate 5g
B Witco 1298 Soft Acid 2.5g
C water 125g
D octamethylcyclotetrasiloxane 37.5g
Obtaining mean diameter is the organosilane monomer miniemulsion of 135 nanometers
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 50 ℃, and the reaction timing begins.React after eight hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 130 nanometers, the transformation efficiency of organosilane monomer is 96.4%.
Embodiment 8
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 2.5g Sodium dodecylbenzene sulfonate and 0.5 gram vitriol oil 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip 12.5g octamethylcyclotetrasiloxane and 12.5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane with dropping funnel under the whipped state, drip to finish back continuation stirring 1 hour, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 8 minutes.
Proportioning:
A Sodium dodecylbenzene sulfonate 2.5g
B vitriol oil 0.5g
C water 125g
D octamethylcyclotetrasiloxane 12.5g
E tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 12.5g
Obtaining mean diameter is the organosilane monomer miniemulsion of 170 nanometers
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 60 ℃, and the reaction timing begins.React after six hours cooling and with in the sodium hydroxide and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 188 nanometers, the transformation efficiency of organosilane monomer is 93.1%.
Embodiment 9
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 3g dodecylbenzyl brometo de amonio and 0.1 gram potassium hydroxide 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mix monomer of 25g octamethylcyclotetrasiloxane and 0.1g hexamethyldisiloxane with dropping funnel under the whipped state, drip to finish the back and continue to stir 3 hours, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 15 minutes.
The proportioning of above-mentioned each material is:
A dodecylbenzyl brometo de amonio 3g
B potassium hydroxide 0.1g
C water 125g
D octamethylcyclotetrasiloxane 25g
E hexamethyldisiloxane 0.1g
Obtaining mean diameter is the organosilane monomer miniemulsion of 240 nanometers.
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 70 ℃, and the reaction timing begins.React after 7 hours cooling and with in the dilute hydrochloric acid and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 237 nanometers, the transformation efficiency of organosilane monomer is 79.4%.
Embodiment 10
The method according to this invention prepares organic silican polymer emulsion, may further comprise the steps:
The first step: the preparation of organosilane monomer miniemulsion
With 4g dodecylbenzyl brometo de amonio and 0.05 gram calcium hydroxide 125g water dissolution, after treating fully to dissolve, join and be equipped with in agitator, prolong, the dropping funnel there-necked flask earlier.(1000 rev/mins) slowly drip the mixture of 12.5g octamethylcyclotetrasiloxane, 12.5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane and 0.2g hexamethyldisiloxane under the whipped state with dropping funnel, drip and finish back continuation stirring 2 hours, make the organosilane monomer pre-emulsion.
Above-mentioned organosilane monomer pre-emulsion is transferred in the beaker, inserts the ultrasonic wave rod therein, open ultrasonic generator.Mix bath with frozen water in the ultrasonic procedure and take away the heat that produces in the ultrasonic procedure.Ultrasonic time is 10 minutes.
The proportioning of above-mentioned each material is:
A dodecylbenzyl brometo de amonio 4g
B calcium hydroxide 0.05g
C water 125g
D octamethylcyclotetrasiloxane 12.5g
E tetramethyl-tetrem thiazolinyl cyclotetrasiloxane 12.5g
F hexamethyldisiloxane 0.2g
Obtaining mean diameter is the organosilane monomer miniemulsion of 210 nanometers.
Second step: the polymerization of organosilane monomer miniemulsion
Above-mentioned organosilane monomer miniemulsion is joined in the four-hole boiling flask that has agitator, condenser, thermometer, nitrogen conduit, and logical nitrogen also is warmed up to 65 ℃, and the reaction timing begins.React after 6 hours cooling and with in the dilute hydrochloric acid and emulsion neutral stopped reaction extremely.
Through above-mentioned steps, obtain the organic silican polymer emulsion that median size is 206 nanometers, the transformation efficiency of organosilane monomer is 86.3%.
Claims (9)
1, a kind of manufacture method of organic silican polymer emulsion may further comprise the steps:
A) preparation of siloxanyl monomers miniemulsion: with the catalyst dissolution of the emulsifying agent of 0.05-5 part quality and 0.05-5 part quality in the water of 100 parts of quality, under agitation drip the siloxanyl monomers of 10-40 part quality, drip the back and continue to stir 0.5-3 hour, form monomer pre-emulsion; Monomer pre-emulsion is placed under the ultrasonic wave effect 1-15 minute, to monomer droplet be the 100-500 nanometer, make the siloxanyl monomers miniemulsion;
B) polymerization of siloxanyl monomers miniemulsion: with steps A) resulting siloxanyl monomers miniemulsion input reactor carries out polyreaction, and temperature of reaction 30-90 ℃, reacted 3-10 hour, make organic silican polymer emulsion.
2, the manufacture method of organic silican polymer emulsion according to claim 1 is characterized in that: described siloxanyl monomers is octamethylcyclotetrasiloxane (D
4), tetramethyl-tetrem thiazolinyl cyclotetrasiloxane (D
4 V), tetramethyl-tetrahydrochysene cyclotetrasiloxane (D
4 H), hexamethyldisiloxane (MM), tetramethyl divinyl disiloxane (M
2 V) or tetramethyl-dihydro sily oxide (M
2 H), or their mixture.
3, the manufacture method of organic silican polymer emulsion according to claim 1 is characterized in that: described emulsifying agent is cationic surfactant or aniorfic surfactant.
4, the manufacture method of organic silican polymer emulsion according to claim 3 is characterized in that: described cats product is N-alkyl monoethanolamine salt, N-alkyl diethanolamine salt and polyethylene polyamines salt, alkyl quaternary amine salt, two alkyl quaternary amine salt, pyridinium salt, imidazoline type cats product or morpholine type cats product.
5, the manufacture method of organic silican polymer emulsion according to claim 3 is characterized in that: described anion surfactant is C
12-C
18Sodium alkyl sulfate, C
12-C
18Sodium alkyl benzene sulfonate, polyxyethylated alkylphenol vitriol or Succinic Acid modification polyxyethylated alkylphenol anion surfactant.
6, the manufacture method of organic silican polymer emulsion according to claim 1 is characterized in that: described catalyzer is an acidic catalyst or basic catalyst.
7, the manufacture method of organic silican polymer emulsion according to claim 6 is characterized in that: described an acidic catalyst is sulfuric acid, hydrochloric acid, Phenylsulfonic acid.
8, the manufacture method of organic silican polymer emulsion according to claim 6 is characterized in that: described basic catalyst is sodium hydroxide, potassium hydroxide or calcium hydroxide.
9, the manufacture method of organic silican polymer emulsion according to claim 1 is characterized in that: the mode of described ultrasonic wave effect, in pre-emulsion, inserting the ultrasonic wave rod, open ultrasonic generator.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143929B (en) * | 2007-09-06 | 2010-12-15 | 湖北德邦化工新材料有限公司 | High stable water chain alkyl silane emulsion and preparation method thereof |
| CN101649545B (en) * | 2008-08-13 | 2011-06-29 | 浙江康丝丽家居科技有限公司 | Process for producing mosquito repelling silk quilt |
| CN103936998A (en) * | 2014-03-31 | 2014-07-23 | 南京工业大学 | Preparation method of organic silicon microemulsion |
| CN103951826A (en) * | 2014-03-27 | 2014-07-30 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN105111932A (en) * | 2015-08-26 | 2015-12-02 | 武汉知睿达新材料有限公司 | Production method of reactive organosilicon waterproofing agent |
| CN106832300A (en) * | 2017-01-19 | 2017-06-13 | 广州市斯洛柯高分子聚合物有限公司 | A kind of silicone elastomer emulsions and preparation method thereof |
| CN107746461A (en) * | 2017-10-31 | 2018-03-02 | 广州中国科学院工业技术研究院 | Cross-linking organosilicon miniemulsion and preparation method thereof, application |
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| CN110951079A (en) * | 2019-12-25 | 2020-04-03 | 广东省稀有金属研究所 | Alkali-resistant hydrogen-containing silicone oil microemulsion and preparation method thereof |
| CN110982425A (en) * | 2019-11-29 | 2020-04-10 | 湖北新四海化工股份有限公司 | Environment-friendly self-crosslinking ceramic antifouling agent and preparation method thereof |
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2006
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143929B (en) * | 2007-09-06 | 2010-12-15 | 湖北德邦化工新材料有限公司 | High stable water chain alkyl silane emulsion and preparation method thereof |
| CN101649545B (en) * | 2008-08-13 | 2011-06-29 | 浙江康丝丽家居科技有限公司 | Process for producing mosquito repelling silk quilt |
| CN103951826A (en) * | 2014-03-27 | 2014-07-30 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN103951826B (en) * | 2014-03-27 | 2017-02-15 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN103936998A (en) * | 2014-03-31 | 2014-07-23 | 南京工业大学 | Preparation method of organic silicon microemulsion |
| CN105111932A (en) * | 2015-08-26 | 2015-12-02 | 武汉知睿达新材料有限公司 | Production method of reactive organosilicon waterproofing agent |
| CN106832300A (en) * | 2017-01-19 | 2017-06-13 | 广州市斯洛柯高分子聚合物有限公司 | A kind of silicone elastomer emulsions and preparation method thereof |
| CN107746461A (en) * | 2017-10-31 | 2018-03-02 | 广州中国科学院工业技术研究院 | Cross-linking organosilicon miniemulsion and preparation method thereof, application |
| CN107746461B (en) * | 2017-10-31 | 2020-12-01 | 广州中国科学院工业技术研究院 | Cross-linking type organic silicon miniemulsion and preparation method and application thereof |
| CN110423349A (en) * | 2019-08-23 | 2019-11-08 | 上海应用技术大学 | A kind of stable non-ionic silicone lotion and preparation method thereof |
| CN110423349B (en) * | 2019-08-23 | 2021-12-07 | 上海应用技术大学 | Stable nonionic organosilicon emulsion and preparation method thereof |
| CN110982425A (en) * | 2019-11-29 | 2020-04-10 | 湖北新四海化工股份有限公司 | Environment-friendly self-crosslinking ceramic antifouling agent and preparation method thereof |
| CN110951079A (en) * | 2019-12-25 | 2020-04-03 | 广东省稀有金属研究所 | Alkali-resistant hydrogen-containing silicone oil microemulsion and preparation method thereof |
| CN115404117A (en) * | 2021-05-26 | 2022-11-29 | 中国石油天然气股份有限公司 | Isolation working fluid and preparation method thereof |
| CN115404117B (en) * | 2021-05-26 | 2023-09-26 | 中国石油天然气股份有限公司 | Isolation working solution and preparation method thereof |
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