CN106317409A - Preparing method of polyorganosiloxane microsphere - Google Patents
Preparing method of polyorganosiloxane microsphere Download PDFInfo
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- CN106317409A CN106317409A CN201610717438.0A CN201610717438A CN106317409A CN 106317409 A CN106317409 A CN 106317409A CN 201610717438 A CN201610717438 A CN 201610717438A CN 106317409 A CN106317409 A CN 106317409A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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Abstract
The invention provides a preparing method of polyorganosiloxane microsphere, comprising the steps of adding the acid catalyst into the deionized water with the conductivity of 5-60us/cm, and within 0-50 degree centigrade, adding siloxane monomer while stirring for hydrolytic equilibrium to get silanol solution, and then adding base catalyst for condensation under the conditions of normal temperature and stirring; washing the final obtained centrifugal reaction liquid to be neutral and dried and to obtain the polysiloxane microsphere. By adopting the preparing method,1- 1-10Mum polysiloxane microsphere can be prepared; and the method is simple in process, easy for operation, and no need of surface active agent and nitrogen protection device, which has a low requirement for equipment. Besides, the post-treatment technology is extremely simple, no need to use organic solvent, green environmental protection, environmentally friendly, and conducive to large scale production.
Description
Technical field
The present invention relates to LED, coating, leather, ink, cosmetic technical field, more particularly to a kind of poly-silicon
The preparation method of oxygen alkane microsphere.
Background technology
The research and development of polysiloxanes microsphere are the focuses of organosilicon research in recent years.Polysiloxanes microsphere is that a class is held concurrently
There is machine performance and the polymer microsphere of inorganic performance, its have high-wearing feature, high rigidity, high-melting-point, lubricious, nontoxic, tasteless,
The advantage such as transparent, is widely used in rubber plastic industry, cosmetics, coating, pigment, optical articles.
Japan Patent (JP 2000302878) provides a kind of basic hydrolysis condensation one-step method and prepares hydrophobic silicon resin microsphere,
Method is simple, but does not proposes how to control particle diameter.Patent (JP 20032973) is then to use hydrolysis-condensation two-step method to be prepared for
Polysiloxanes microsphere, the method has been abandoned and has been hydrolyzed on two-phase interface and the conventional method of polycondensation simultaneously, will hydrolyze and contracting
Gather and separately carry out, make reaction easily controllable, substantially increase production efficiency, but do not propose how to control particle diameter.Patent
It is 0.5-10 μm that CN1205345 prepares particle diameter, simultaneously the silicones microsphere of particle diameter narrow distribution, but with the addition of the moon in the reaction
The additives such as ion interface activating agent, polymer stabilizer, post processing simultaneously uses again injection, and operation is complicated.Patent
The high efficiency silicones microsphere of preparing of CN103214674A, but reaction need to be entered under the protection of high-temperature high-pressure reaction kettle and nitrogen
OK, reaction condition is the harshest.The silicones that CN 104744700A employing hydrolysis-condensation two-step method prepares uniform particle sizes is micro-
Ball, method is simple, but the microspherulite diameter preparing gained is 1.5-5 μm, and kind is less, and needs to make during the later stage processes
Use substantial amounts of organic solvent.Polymer microballoon prepared by CN 103030752A, including the silicones microsphere kernel containing vinyl and
Being attached to the polymer that the acrylic ester monomer of core surface is formed, under the effect of initiator, olefinic polymerization forms microsphere.
Summary of the invention
In view of this, it is desirable to provide the preparation method of the polysiloxanes microsphere of a kind of controllable grain size, the method has
Standby step is simple, environmental protection, it is easy to the advantages such as operation, and the particle diameter preparing the polysiloxanes microsphere of gained is 1-10 μm, with
Time particle diameter narrow distribution, granule is more uniform, can meet the demand of different product.
The preparation method that the present invention provides comprises the following steps:
1) acid catalyst is added to the deionized water that electrical conductivity is 5-60us/cm, at 0-50 DEG C, in the case of stirring
Adding siloxanyl monomers hydrolysising balance and obtain silanol solution, wherein deionized water is 1: 10-with the mol ratio of siloxanyl monomers
100；
2) in step 1) the silanol solution of gained adds base catalyst, it is condensed under conditions of room temperature, stirring；
3) by step 2) the reactant liquor centrifugal water that obtains is washed till neutrality, is dried to obtain polysiloxanes microsphere.
Polysiloxanes microspherulite diameter provided by the present invention is 1-10 μm.
Particularly, the present invention is to be come by mol ratio and the deionization electrical conductivity of water of deionized water with siloxanyl monomers
Control the size of particle diameter, be embodied in: deionized water is 1/32-1/27 with the mol ratio of siloxanyl monomers, and deionized water
Electrical conductivity when being 22-52us/cm, the polysiloxanes microspherulite diameter obtained is 8-10 micron order；Deionized water and siloxanes list
The mol ratio of body is 1/63-1/37, and when deionization electrical conductivity of water is 5-14us/cm, the polysiloxanes microspherulite diameter obtained
For 2-6 micron order；Deionized water is 1/83-1/77 with the mol ratio of siloxanyl monomers, and deionization electrical conductivity of water is 5-
During 7us/cm, the polysiloxanes microspherulite diameter obtained is 1 micron order.
Siloxanyl monomers of the present invention is MTMS, ethyl trimethoxy silane, phenyl trimethoxy
Base silane, aminopropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-methacryloxypropyl trimethoxy
One or more in the trimethoxy silanes such as silane.
Described acid catalyst is one or more in hydrochloric acid, acetic acid, phosphoric acid, sulphuric acid etc., the acid catalysis of addition
Agent is (0.018-0.18) with the mol ratio of deionized water: 1.
Described base catalyst is ammonia, one or more in sodium hydroxide, potassium hydroxide, calcium hydroxide, adds
The base catalyst entered is (1.8 × 10 with the mol ratio of deionized water-8-1.8×10-7)∶1。
Particularly, the feed postition of described siloxanyl monomers is selected from being directly added into, and half dropping half is directly added into, dropping
In one.
Particularly, step 1) response time be 0.5～10 hour, mixing speed is 200-1000rpm, preferably 200-
600rpm。
Particularly, step 2) response time be 2-72 hour, mixing speed is 0-600rpm, preferably 0-200rpm.
The present invention provide preparation method to obtain polysiloxanes microsphere that particle diameter is 1-10 μm, compared with prior art,
The present invention is that the deionized water by regulation reaction system obtains not with the mol ratio of raw material and the conductivity of deionized water
Polysiloxanes microsphere with particle diameter.The preparation method that the present invention provides, on the premise of ensureing narrow diameter distribution, has relatively simultaneously
High product yield, and technique is simple, it is easy to operation, it is not necessary to add surfactant, it is not necessary to nitrogen protection device, equipment is wanted
Asking relatively low, aftertreatment technology is extremely simple, it is not necessary to use organic solvent, and environmental protection is environmentally friendly, is conducive to extensive raw
Produce.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the embodiment of the present invention 1.
Fig. 2 is the SEM figure of the embodiment of the present invention 2.
Fig. 3 is the SEM figure of the embodiment of the present invention 3.
Fig. 4 is the SEM figure of the embodiment of the present invention 4.
Fig. 5 is the SEM figure of the embodiment of the present invention 5.
Fig. 6 is the SEM figure of the embodiment of the present invention 6.
Detailed description of the invention
Below by embodiment, present aspect done concrete description, it is necessary to it is pointed out here that be that following example are served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in this field
Nonessential improvement and adjustment can be made according to the present invention.
Embodiment 1
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 5us/cm
1404g, adds hydrochloric acid 1.5g, is warming up to 50 DEG C, adds MTMS 132.6g under the speed of agitator of 200rpm,
Balancing response 0.5 hour, is subsequently adding ammonia 4.5g, 40rmp and reacts 8h.Centrifugal water is washed till neutrality, 150 DEG C of bakings in drying baker
Dry obtain silicones microsphere.Microsphere particle size is about 1 μm, and productivity is 92.8%, and SEM is as shown in Figure 1.
Embodiment 2
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 7us/cm
1404g, adds acetic acid 1.2g, is warming up to 30 DEG C, adds MTMS 176.8g under the speed of agitator of 300rpm,
Balancing response 1 hour, is subsequently adding potassium hydroxide aqueous solution 7.5g and stirs, and 25rmp reacts 10 hours.During centrifugal water is washed till
Property, in drying baker, 150 DEG C of drying obtain silicones microsphere.Microsphere particle size is about 2 μm, and productivity is 94.5%, SEM such as Fig. 2
Shown in.
Embodiment 3
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 9us/cm
1404g, adds hydrochloric acid and the mixture 0.5g of acetic acid, and temperature is 40 DEG C, adds ethyl front three under the speed of agitator of 500rpm
TMOS 212.2g, balancing response 2 hours, it is subsequently adding sodium hydrate aqueous solution 5.4g and stirs, 10rmp reacts
20hr.Centrifugal water is washed till neutrality, and in drying baker, 150 DEG C of drying obtain silicones microsphere.Microsphere particle size is about 4 μm, productivity
Being 94.7%, SEM is as shown in Figure 3.
Embodiment 4
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 10us/cm
1404g, adds phosphoric acid 0.9g, is cooled to 20 DEG C, drips ethyl trimethoxy silane 265.2g under the speed of agitator of 600rpm,
Balancing response 3 hours, is subsequently adding ammonia 6g and stirs, and stands 24h.Centrifugal water is washed till neutrality, 150 DEG C of bakings in drying baker
Dry obtain silicones microsphere.Microsphere particle size is about 6 μm, and productivity is 93.5%, and SEM is as shown in Figure 4.
Embodiment 5
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 25us/cm
1404g, adds hydrochloric acid and the mixture 0.5g of acetic acid, is cooled to 10 DEG C, drips phenyl base three under the speed of agitator of 400rpm
Methoxy silane 353.6g, balancing response 3 hours, it is subsequently adding ammonia 5g and stirs, 5rmp reacts 26hr.Centrifugal water is washed till
Neutrality, in drying baker, 150 DEG C of drying obtain silicones microsphere.Microsphere particle size is 8 μm, and productivity is 94.7%, SEM such as Fig. 5 institute
Show.
Embodiment 6
In the 2L four-hole boiling flask equipped with stirring, thermometer and reflux condensing tube, adding electrical conductivity is the water of 50us/cm
1404g, adds phosphoric acid 0.9g, is cooled to 15 DEG C, drips phenyltrimethoxysila,e 353.6g under the speed of agitator of 300rpm,
Balancing response 3 hours, the mixture 6.5g being subsequently adding ammonia and sodium hydrate aqueous solution stirs, and stands 24h.Centrifugal water
Being washed till neutrality, in drying baker, 150 DEG C of drying obtain silicones microsphere.Microsphere particle size is 10 μm, and productivity is 91.9%, and SEM is such as
Shown in Fig. 6.
Claims (9)
1. the preparation method of a polysiloxanes microsphere, it is characterised in that include for following steps:
1) acid catalyst is added to the deionized water that electrical conductivity is 5-60us/cm, at 0-50 DEG C, add in the case of stirring
Siloxanyl monomers hydrolysising balance obtains silanol solution, and wherein deionized water is 1 with the mol ratio of siloxanyl monomers: (10-100)；
2) in step 1) the silanol solution of gained adds base catalyst, it is condensed under conditions of room temperature, stirring；
3) by step 2) the reactant liquor centrifugal water that obtains is washed till neutrality, is dried to obtain polysiloxanes microsphere.
2. preparation method as claimed in claim 1, it is characterised in that described polysiloxanes microspherulite diameter is 1-10 μm.
3. preparation method as claimed in claim 1, it is characterised in that by the mol ratio of deionized water and siloxanyl monomers with
And deionization electrical conductivity of water controls the size of particle diameter, it is embodied in: deionized water with the mol ratio of siloxanyl monomers is
1/32-1/27, and when deionization electrical conductivity of water is 22-52us/cm, the polysiloxanes microspherulite diameter obtained is 8-10 micron
Level；Deionized water is 1/63-1/37 with the mol ratio of siloxanyl monomers, and when deionization electrical conductivity of water is 5-14us/cm,
To polysiloxanes microspherulite diameter be 2-6 micron order；Deionized water is 1/83-1/77 with the mol ratio of siloxanyl monomers, and goes
When ion electrical conductivity of water is 5-7us/cm, the polysiloxanes microspherulite diameter obtained is 1 micron order.
4. the preparation method as described in claim 1 or 3, it is characterised in that described siloxanyl monomers is methyl trimethoxy epoxide
Silane, ethyl trimethoxy silane, phenyltrimethoxysila,e, aminopropyl trimethoxysilane, γ-mercapto propyl trimethoxy silicon
One or more in the trimethoxy silanes such as alkane, γ-methacryloxypropyl trimethoxy silane.
5. preparation method as claimed in claim 1, it is characterised in that described acid catalyst is hydrochloric acid, acetic acid, phosphoric acid, sulfur
One or more in acid etc., the acid catalyst of addition and the mol ratio of deionized water are (0.018-0.18): 1.
6. preparation method as claimed in claim 1, it is characterised in that the feed postition of described siloxanyl monomers is selected from directly adding
Entering, half dropping half is directly added into, the one in dropping.
7. preparation method as claimed in claim 1, it is characterised in that described step 1) response time be 0.5～10 hour,
Mixing speed is 200-1000rpm.
8. preparation method as claimed in claim 1, it is characterised in that described base catalyst is ammonia, sodium hydroxide, hydrogen-oxygen
Change in potassium, calcium hydroxide one or more, the base catalyst of addition and the mol ratio of deionized water are (1.8 × 10-8-
1.8×10-7)∶1。
9. preparation method as claimed in claim 1, it is characterised in that described step 2) response time be 2-72 hour, stir
Mixing speed is 0-600rpm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978069A (en) * | 2017-04-19 | 2017-07-25 | 苏州圣咏电子科技有限公司 | The preparation method of antifouling hydrophobic coating and the manufacturing process of antifouling hydrophobic film |
| CN107573507A (en) * | 2017-09-29 | 2018-01-12 | 贵州正业工程技术投资有限公司 | A kind of preparation method of big particle diameter polysiloxanes microballoon |
| CN109608680A (en) * | 2019-01-18 | 2019-04-12 | 贵州大学 | A kind of preparation method of micro-nano multistage polysilsesquioxane core-shell material |
| CN111286028A (en) * | 2020-02-17 | 2020-06-16 | 湖州五爻硅基材料研究院有限公司 | Preparation method of spherical poly-alkyl siloxane |
| CN111320754A (en) * | 2020-04-17 | 2020-06-23 | 湖州五爻硅基材料研究院有限公司 | Preparation method of spherical polysiloxane |
| CN111801369A (en) * | 2018-12-28 | 2020-10-20 | 浙江三时纪新材科技有限公司 | Polysiloxane powder without pungent smell during heating and preparation method thereof |
| CN111848206A (en) * | 2020-07-20 | 2020-10-30 | 贵州正业龙腾新材料开发有限公司 | Preparation method of monodisperse micron-sized hollow ceramic microspheres |
| CN112080147A (en) * | 2020-09-18 | 2020-12-15 | 宁波工程学院 | Preparation method of sulfydryl organic silicon nanospheres and sulfydryl-alkene polymer flame-retardant system thereof |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112811429A (en) * | 2020-12-31 | 2021-05-18 | 浙江三时纪新材科技有限公司 | Preparation method of silicon dioxide light diffusant and light diffusant obtained by preparation method |
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| CN1311266A (en) * | 2000-01-13 | 2001-09-05 | Ge东芝硅氧烷株式会社 | Ball shaped granular of polyorganosiloxane, and its prepn. method |
| CN104744700A (en) * | 2015-03-09 | 2015-07-01 | 华南理工大学 | Preparation method of mono-dispersion polysiloxane microspheres with controllable particle size |
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Patent Citations (2)
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| CN104744700A (en) * | 2015-03-09 | 2015-07-01 | 华南理工大学 | Preparation method of mono-dispersion polysiloxane microspheres with controllable particle size |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978069A (en) * | 2017-04-19 | 2017-07-25 | 苏州圣咏电子科技有限公司 | The preparation method of antifouling hydrophobic coating and the manufacturing process of antifouling hydrophobic film |
| CN107573507A (en) * | 2017-09-29 | 2018-01-12 | 贵州正业工程技术投资有限公司 | A kind of preparation method of big particle diameter polysiloxanes microballoon |
| CN111801369A (en) * | 2018-12-28 | 2020-10-20 | 浙江三时纪新材科技有限公司 | Polysiloxane powder without pungent smell during heating and preparation method thereof |
| CN111801369B (en) * | 2018-12-28 | 2021-05-18 | 浙江三时纪新材科技有限公司 | Polysiloxane powder without pungent smell during heating and preparation method thereof |
| CN109608680A (en) * | 2019-01-18 | 2019-04-12 | 贵州大学 | A kind of preparation method of micro-nano multistage polysilsesquioxane core-shell material |
| CN111286028A (en) * | 2020-02-17 | 2020-06-16 | 湖州五爻硅基材料研究院有限公司 | Preparation method of spherical poly-alkyl siloxane |
| CN111320754A (en) * | 2020-04-17 | 2020-06-23 | 湖州五爻硅基材料研究院有限公司 | Preparation method of spherical polysiloxane |
| CN111320754B (en) * | 2020-04-17 | 2021-06-25 | 浙江三时纪新材科技有限公司 | Preparation method of spherical polysiloxane |
| CN111848206A (en) * | 2020-07-20 | 2020-10-30 | 贵州正业龙腾新材料开发有限公司 | Preparation method of monodisperse micron-sized hollow ceramic microspheres |
| CN112080147A (en) * | 2020-09-18 | 2020-12-15 | 宁波工程学院 | Preparation method of sulfydryl organic silicon nanospheres and sulfydryl-alkene polymer flame-retardant system thereof |
| CN112080147B (en) * | 2020-09-18 | 2023-03-31 | 宁波工程学院 | Preparation method of sulfydryl organic silicon nanospheres and sulfydryl-alkene polymer flame-retardant system thereof |
| CN112221474A (en) * | 2020-09-23 | 2021-01-15 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112221474B (en) * | 2020-09-23 | 2023-04-07 | 重庆天外天生物技术有限公司 | Bilirubin adsorbent with high mechanical strength and good biocompatibility and preparation method thereof |
| CN112811429A (en) * | 2020-12-31 | 2021-05-18 | 浙江三时纪新材科技有限公司 | Preparation method of silicon dioxide light diffusant and light diffusant obtained by preparation method |
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