CN104744701A - Method for synthesizing polysiloxane miniemulsion by utilizing microlatex seeds under single emulgator - Google Patents
Method for synthesizing polysiloxane miniemulsion by utilizing microlatex seeds under single emulgator Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of polysiloxane emulsion, and discloses a method for synthesizing polysiloxane miniemulsion by utilizing microlatex seeds under a single emulgator as well as the polysiloxane miniemulsion and application of the polysiloxane miniemulsion. The method comprises the following specific steps of dissolving the emulgator in water, adding an organosilicone monomer, mixing mechanically for pre-emulsification, adding a super basic catalyst after heating, and mixing at a constant temperature to obtain the organic siloxane microlatex seed emulsion; dropwise adding the organosilicone monomer in the organic siloxane microlatex seed emulsion semi-intermittently while mixing at the constant temperature, mixing continuously at the constant temperature for reaction after the dropwise adding, cooling, and neutralizing to obtain the polysiloxane miniemulsion. According to the method, long-chain alkyl-di-polyoxyethylene quaternary ammonium salt is used as the single cationic emulsifier, the polysiloxane microlatex is used as seeds, the same monomer is added semi-intermittently, the polysiloxane miniemulsion which is small in grain size, narrow in distribution and good in stability is prepared without relying on other homogenizing means, and the polysiloxane miniemulsion can be widely applied to the fields of textiles, coatings and household chemicals.
Description
Technical field
The invention belongs to polysiloxane emulsion preparing technical field, particularly under a kind of single emulsifier, utilize fine latex seed to synthesize the method for polysiloxane miniemulsion and polysiloxane miniemulsion thereof and application.
Background technology
The chemical structure of polysiloxane be the-Si-O-that forms of Si, O inorganic elements as main chain ,-CH
3deng organic group as side base, this chemical structure makes polysiloxane have organic and character that is inorganic polymer two aspect, as high-low temperature resistant, snappiness, ventilation property, release property and lower surface tension, thus polysiloxane is made to be widely used in weaving, rubber, building, electronic apparatus and cosmetic field.Based on the consideration of the aspects such as environmentally friendly property and saving type production, emulsion-type polysiloxane, has captured current most market.
The preparation method of emulsion-type polysiloxane has mechanical emulsion process and emulsion polymerization two kinds of modes, and the most conventional is emulsion polymerization.Emulsion polymerization overcomes the defect of mass polymerization in machinery emulsification method and the drawback of difficult emulsification and poor stability, be that the raw materials such as organosilane monomer, emulsifying agent, catalyzer and water are made organic silicon emulsion by letex polymerization under certain conditions, therefore there is the advantages such as short, good emulsion stability simple to equipment requirements, easy to operate, consuming time.Emulsion, miniemulsion and fine latex liquid is divided into successively according to the grain size size of polysiloxane emulsion.And the grain size of traditional emulsion is comparatively large, stability is not good enough; Meanwhile, need by a large amount of emulsifying agents to maintain the unstable of low particle size emulsion in the preparation process of fine latex liquid.And the good stability of traditional miniemulsion, size is little, makes it have wide range of applications; But its traditional preparation process needs to make monomer emulsion evenly pre-emulsified by the means of homogenizing in the external world, makes miniemulsion synthesis technique complexity loaded down with trivial details.
In addition, letex polymerization can be divided into anions and canons ring-opening polymerization again according to synthesis emulsifier used, respectively corresponding positive and negative ionic emulsifying agent.Anionic ring-opening polymerization under cationic emulsifier exists is few compared with cation ring-opening polymerization side reaction, is studied widely, and cationic emulsifier is wherein the most important thing of research.Now the most frequently used complex emulsifier is undertaken composite by cationic emulsifier and nonionic emulsifying agent, and by being spaced of nonionic emulsifying agent and cationic emulsifier, make the interval between adjacent charge become large, reactive force reduces; But also making interfacial film thickness increase while increasing stability of emulsion, there is sacrificial polymeric speed in compound emulsifying agent, level of response is slowed down, the drawback of length consuming time, the oil loving positively charged ion of the hydrophilic height of novel height and the compatible New-type emulsifier of non-ionic emulsifier are probed into, extremely urgent.
At present, the preparation method of traditional polysiloxane miniemulsion is under the compound emulsifying agent and co-stabilizer existence of proper ratio, obtain monomer miniemulsion through ultrasonic wave, the pre-emulsification means such as high-pressure homogeneous, then carry out polymerization and obtain, and be the disposable interval synthesis method fed intake.The composite of multiple auxiliary agent is needed in the method, and pre-emulsified preparation, corresponding technique becomes loaded down with trivial details thereupon.So, probe into new synthesis technique and expand being applied to as the research emphasis of people in polysiloxane miniemulsion of novel cation emulsifying agent.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention utilizes fine latex seed to synthesize the method for polysiloxane miniemulsion under being to provide a kind of single emulsifier, the method is with polysiloxane fine latex for seed, and the same monomer synthesis that adds of Semi-batch Process obtains polysiloxane miniemulsion; And the method is using the two polyoxyethylene quaternary ammonium salt of chain alkyl as emulsifying agent, not by the external world the loaded down with trivial details means that homogenize prerequisite under synthesis obtain the little and polysiloxane miniemulsion of narrowly distributing, good stability of particle diameter.
Another object of the present invention is the polysiloxane miniemulsion providing aforesaid method to prepare.
Still a further object of the present invention is to provide the application of above-mentioned polysiloxane miniemulsion in weaving, coating and daily chemical products field.
Object of the present invention is realized by following proposal:
Utilize fine latex seed to synthesize a method for polysiloxane miniemulsion under single emulsifier, comprise following concrete steps:
(1) preparation of polysiloxane fine latex seed: emulsifying agent is soluble in water, adds organosilane monomer, and mechanical stirring pre-emulsification, adds alkali catalyst after heating, and constant temperature stirs, and obtains organo-siloxane fine latex seed emulsion;
(2) under constant temperature stirs, in the organo-siloxane fine latex seed emulsion of step (1), the dropping organosilane monomer of semi-batch, is added dropwise to complete rear continuation constant temperature stirring reaction, cooling, and neutralization, obtains polysiloxane miniemulsion.
Emulsifying agent described in step (1) is the two polyoxyethylene quaternary ammonium salt of chain alkyl, and its structural formula is as follows:
Wherein, C
nh
2n+1for the chain alkyl of C12 ~ C18, R is the chain alkyl of C1 ~ C22, benzyl, styroyl, hydrocinnamyl, benzene sec.-propyl, benzene isobutyl-, the benzene tertiary butyl or benzene normal-butyl, and x+y=10 ~ 20, X is Cl or Br.
Described emulsifying agent is preferably octadecyl bi-polyoxyethylene benzyl ammonium chloride, dodecyl double focusing oxyethylene group Benzylphosphonium Bromide ammonium or hexadecyl double focusing oxyethylene group benzyl ammonium chloride, x+y=10 ~ 20 in structure.
Organosilane monomer general structure described in above-mentioned preparation method is as follows:
Wherein, n is the integer of 3 ~ 10; R
1, R
2identical or different, the alkyl being respectively hydrogen, the alkyl of C1 ~ C16, thiazolinyl, cycloalkyl group, aryl or being substituted.
Preferably, described organosilane monomer is hexamethyl cyclotrisiloxane (D
3), octamethylcyclotetrasiloxane (D
4), decamethylcyclopentaandoxane (D
5), t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), tetramethyl-tetrahydrochysene cyclotetrasiloxane (D
4 h), tetramethyl tetraphenyl cyclotetrasiloxane, 1,3,5,7-tetramethyl-four (3,3,3-trifluoro propyl) cyclotetrasiloxane and 1,3, at least one in 5,7-tetramethyl-four (3-cyanogen propyl group) cyclotetrasiloxane, is more preferably octamethylcyclotetrasiloxane (D
4).
In step (1), emulsifying agent used, water and organosilane monomer mass ratio are (2.4 ~ 8.4): (67.6 ~ 236.6): (3 ~ 36).
In step (1), the amount of organosilane monomer used and the mol ratio of step (1) and step (2) organosilane monomer total amount used are 1:9 ~ 2:3.
In step (1), the amount of alkali catalyst used is catalytic amount, is preferably 0.6:36 ~ 2.1:36 with the mass ratio of organosilane monomer.
Described alkali catalyst is preferably at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and ammonium hydroxide.
Pre-emulsification described in step (1) is preferably and stirs 5 ~ 25min under 600 ~ 1500r/min stirs shearing rate.Described pre-emulsification adopts mechanical stirring to carry out shear and homogenize.
The speed dripped described in step (2) is preferably 0.225 ~ 1.35g/min.
The time of continuing constant temperature stirring reaction in step (2) is preferably 0.5 ~ 4h.
Neutralization described in step (2) refers to neutralize with this area conventional acid solution.
It is 300 ~ 550r/min that step (1) and the constant temperature described in step (2) stir preferred rotating speed, and temperature is 70 ~ 90 DEG C.The time that constant temperature described in step (1) stirs is preferably 10 ~ 30min.
Described in step (2), cooled temperature is preferably 30 ~ 50 DEG C.
Above-mentioned preparation method's reaction times is short, and the polysiloxane miniemulsion obtained has the features such as particle diameter little and narrowly distributing, good stability, emulsifier are few, can be widely used in weaving, coating and daily chemical products field.
Mechanism of the present invention is:
The present invention is with polysiloxane fine latex for seed, and the same monomer synthesis that adds of Semi-batch Process obtains polysiloxane miniemulsion; And utilize the two polyoxyethylene quaternary ammonium salt of chain alkyl as single cationic emulsifier, not by the external world the loaded down with trivial details means that homogenize prerequisite under synthesize the little and polysiloxane miniemulsion of narrowly distributing, good stability of particle diameter.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) adopt the continuous dosing method of semi-batch, eliminate and to homogenize means by external worlds such as such as high-pressure homogeneous, ultrasonic homogeneous, only need simple mechanical stirring.Simplify miniemulsion preparation technology, save production cost;
(2) under the existence of organosilicon fine latex seed, the size distribution of seeding polymerization organosilicon miniemulsion is more homogeneous, expands its range of application in weaving, coating and daily chemical products;
(3) the two polyoxyethylene quaternary ammonium salt of chain alkyl has the dual property of nonionic and cationic emulsifier concurrently, under the prerequisite ensureing stability and speed of reaction, the use of single novel cation emulsifying agent, avoid composite loaded down with trivial details of nonionic emulsifying agent, Simplified flowsheet step, more reduces production cost;
(4) the two polyoxyethylene quaternary ammonium salt of chain alkyl has low critical micell value, and efficient surfactivity makes it when ring-opening polymerization, and the consumption of emulsifying agent is few, and product performance are excellent;
(5) without the interpolation of co-stabilizer in the preparation process of miniemulsion, the postprocessing working procedures of corresponding product is more succinct;
(6) the miniemulsion good stability prepared by the present invention, emulsifier is few, the little and narrowly distributing of emulsion particle size, and the required reaction times is short, and the efficiency of prepared polysiloxane miniemulsion is higher.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=15) 2.4g and add 67.6g deionized water, mechanical stirring, to dissolving completely, adds 3g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 600r/min mechanical shearing homogeneous 25min, adding 1.25g massfraction after emulsification completes is 40% potassium hydroxide solution, under rotating speed is 450r/min condition, be warming up to 70 DEG C, reaction 20min, obtained polysiloxane fine latex seed.
(2) in the polysiloxane fine latex seed of above-mentioned (1), 27g D is dropwise dripped with 0.225g/min
4, keeping rotating speed to be 450r/min and temperature of reaction is under 70 DEG C of conditions, is added dropwise to complete rear continuation reaction 1h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 77.42nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.137.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min under 5000r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 2
(1) get dodecyl double focusing oxyethylene group Benzylphosphonium Bromide ammonium (in structure oxyethylene group x+y=15) 3.6g and add 101.4g deionized water, mechanical stirring, to dissolving completely, adds 4g octamethylcyclotetrasiloxane (D
4), then carry out pre-emulsification by 1000r/min mechanical shearing homogeneous 10min, adding 1.875g massfraction after emulsification completes is 40% sodium hydroxide solution, under rotating speed is 500r/min condition, be warming up to 80 DEG C, reaction 30min, obtained polysiloxane fine latex seed.
(2) in polysiloxane fine latex seed, 36g D is dropwise dripped with 0.45g/min
4, keeping rotating speed to be 500r/min and temperature of reaction is under 80 DEG C of conditions, is added dropwise to complete rear continuation reaction 2h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 77.52nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.272.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 40min clock under 5800r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 3
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=15) 4.8g and add 135.2g deionized water, mechanical stirring, to dissolving completely, adds 6g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 1200r/min mechanical shearing homogeneous 20min, adding 3g massfraction after emulsification completes is 20% potassium hydroxide solution, under rotating speed is 350r/min condition, be warming up to 85 DEG C, reaction 20min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 54g D is dropwise dripped with 0.9g/min
4, keeping rotating speed to be 350r/min and temperature of reaction is under 85 DEG C of conditions, is added dropwise to complete rear continuation reaction 4h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 87.16nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.311.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 6000r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 4
(1) get hexadecyl double focusing oxyethylene group benzyl ammonium chloride (in structure oxyethylene group x+y=15) 8.4g and add 236.6g deionized water, mechanical stirring, to dissolving completely, adds 10.5g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 1200r/min mechanical shearing homogeneous 10min, adding 7g massfraction after emulsification completes is 30% potassium hydroxide solution, under rotating speed is 300r/min condition, be warming up to 90 DEG C, reaction 30min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 94.5g D is dropwise dripped with 1.35g/min
4, keeping rotating speed to be 350r/min and temperature of reaction is under 90 DEG C of conditions, is added dropwise to complete rear continuation reaction 4h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 78.04nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.137.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 5500r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 5
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=20) 6g and add 169g deionized water, mechanical stirring, to dissolving completely, adds 7.5g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 1500r/min mechanical shearing homogeneous 5min, adding 3.75g massfraction after emulsification completes is 40% potassium hydroxide solution, under rotating speed is 550r/min condition, be warming up to 80 DEG C, reaction 10min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 67.5g D is dropwise dripped with 0.225g/min
4, keeping rotating speed to be 550r/min and temperature of reaction is under 70 DEG C of conditions, is added dropwise to complete rear continuation reaction 0.5h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 72.28nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.119.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 6000r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 6
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=15) 4.8g and add 135.2g deionized water, mechanical stirring, to dissolving completely, adds 12g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 1000r/min mechanical shearing homogeneous 15min, adding 3g massfraction after emulsification completes is 40% potassium hydroxide solution, under rotating speed is 450r/min condition, be warming up to 80 DEG C, reaction 15min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 48g D is dropwise dripped with 0.225g/min
4, keeping rotating speed to be 450r/min and temperature of reaction is under 80 DEG C of conditions, is added dropwise to complete rear continuation reaction 1h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 89.15nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.2.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 5500r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 7
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=15) 4.8g and add 135.2g deionized water, mechanical stirring, to dissolving completely, adds 18g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 1000r/min mechanical shearing homogeneous 15min, adding 2.5g massfraction after emulsification completes is 40% potassium hydroxide solution, under rotating speed is 400r/min condition, be warming up to 80 DEG C, reaction 10min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 42g D is dropwise dripped with 0.225g/min
4, keeping rotating speed to be 400r/min and temperature of reaction is under 80 DEG C of conditions, is added dropwise to complete rear continuation reaction 2h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 91.02nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.329.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 5000r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Embodiment 8
(1) get octadecyl bi-polyoxyethylene benzyl ammonium chloride (in structure oxyethylene group x+y=10) 7.2g and add 202.8g deionized water, mechanical stirring, to dissolving completely, adds 36g octamethylcyclotetrasiloxane (D
4), it is made to mix by stirring, then pre-emulsification is carried out by 900r/min mechanical shearing homogeneous 15min, adding 4g massfraction after emulsification completes is 30% potassium hydroxide solution, under rotating speed is 400r/min condition, be warming up to 80 DEG C, reaction 10min, obtained polysiloxane fine latex seed.
(2) in above-mentioned polysiloxane fine latex seed, 54g D is dropwise dripped with 0.225g/min
4, keeping rotating speed to be 400r/min and temperature of reaction is under 80 DEG C of conditions, is added dropwise to complete rear continuation reaction 1h, is neutralized to pH=7, obtains polysiloxane miniemulsion after cooling with acid.
(3) be 96.97nm (Z-Average) with the miniemulsion particle diameter that dynamic light scattering method records, size distribution coefficient (PDI) is 0.358.Get 5mL polysiloxane emulsion and put into centrifuge tube, there is not layering in centrifugal 30min clock under 5000r/min, and made emulsion is at room temperature placed and also do not occurred layering in 150 days, shows that gained emulsion intercalation method is good.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. utilize fine latex seed to synthesize a method for polysiloxane miniemulsion under single emulsifier, it is characterized in that comprising following concrete steps:
(1) preparation of polysiloxane fine latex seed: emulsifying agent is soluble in water, adds organosilane monomer, and mechanical stirring pre-emulsification, adds alkali catalyst after heating, and constant temperature stirs, and obtains organo-siloxane fine latex seed emulsion;
(2) under constant temperature stirs, in the organo-siloxane fine latex seed emulsion of step (1), the dropping organosilane monomer of semi-batch, is added dropwise to complete rear continuation constant temperature stirring reaction, cooling, and neutralization, obtains polysiloxane miniemulsion.
2. utilize fine latex seed to synthesize the method for polysiloxane miniemulsion under single emulsifier according to claim 1, it is characterized in that: the emulsifying agent described in step (1) is the two polyoxyethylene quaternary ammonium salt of chain alkyl, and its structural formula is as follows:
Wherein, C
nh
2n+1for the chain alkyl of C12 ~ C18, R is the chain alkyl of C1 ~ C22, benzyl, styroyl, hydrocinnamyl, benzene sec.-propyl, benzene isobutyl-, the benzene tertiary butyl or benzene normal-butyl, and x+y=10 ~ 20, X is Cl or Br.
3. under single emulsifier according to claim 1, utilize fine latex seed to synthesize the method for polysiloxane miniemulsion, it is characterized in that: the emulsifying agent described in step (1) is octadecyl bi-polyoxyethylene benzyl ammonium chloride, dodecyl double focusing oxyethylene group Benzylphosphonium Bromide ammonium or hexadecyl double focusing oxyethylene group benzyl ammonium chloride, x+y=10 ~ 20 in structure.
4. utilize fine latex seed to synthesize the method for polysiloxane miniemulsion under single emulsifier according to claim 1, it is characterized in that: described organosilane monomer general structure is as follows:
Wherein, n is the integer of 3 ~ 10; R
1, R
2identical or different, the alkyl being respectively hydrogen, the alkyl of C1 ~ C16, thiazolinyl, cycloalkyl group, aryl or being substituted.
5. under single emulsifier according to claim 1, utilize fine latex seed to synthesize the method for polysiloxane miniemulsion, it is characterized in that: described organosilane monomer is hexamethyl cyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, t etram-ethyltetravinylcyclotetrasiloxane, tetramethyl-tetrahydrochysene cyclotetrasiloxane, tetramethyl tetraphenyl cyclotetrasiloxane, 1,3,5,7-tetramethyl-four (3,3,3-trifluoro propyl) cyclotetrasiloxane and 1,3, at least one in 5,7-tetramethyl-four (3-cyanogen propyl group) cyclotetrasiloxane.
6. utilize fine latex seed to synthesize the method for polysiloxane miniemulsion under single emulsifier according to claim 1, it is characterized in that: in step (1), emulsifying agent used, water and organosilane monomer mass ratio are (2.4 ~ 8.4): (67.6 ~ 236.6): (3 ~ 36); In step (1), the amount of organosilane monomer used and the mol ratio of step (1) and step (2) organosilane monomer total amount used are 1:9 ~ 2:3.
7. utilize fine latex seed to synthesize the method for polysiloxane miniemulsion under single emulsifier according to claim 1, it is characterized in that: described alkali catalyst is at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and ammonium hydroxide.
8. utilize fine latex seed to synthesize the method for polysiloxane miniemulsion under single emulsifier according to claim 1, it is characterized in that: the pre-emulsification described in step (1) refers to stir 5 ~ 25min under 600 ~ 1500r/min stirs shearing rate; The speed dripped described in step (2) is 0.225 ~ 1.35g/min; The time of continuing constant temperature stirring reaction in step (2) is 0.5 ~ 4h; The rotating speed that step (1) and the constant temperature described in step (2) stir is 300 ~ 550r/min, and temperature is 70 ~ 90 DEG C; The time that constant temperature described in step (1) stirs is 10 ~ 30min.
9. a polysiloxane miniemulsion, the method utilizing fine latex seed to synthesize polysiloxane miniemulsion under it is characterized in that the single emulsifier according to any one of claim 1 ~ 8 prepares.
10. the application of polysiloxane miniemulsion according to claim 9 in weaving, coating and daily chemical products field.
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| CN107759806A (en) * | 2017-11-09 | 2018-03-06 | 陈晨特 | A kind of moisturizing lubricating type polysiloxanes Pickering emulsions and preparation method thereof |
| CN107951747A (en) * | 2017-11-14 | 2018-04-24 | 湖南博隽生物医药有限公司 | A kind of polyglutamic acid modified organic silicon Pickering moisturizing emulsions and preparation method thereof |
| CN112552442A (en) * | 2020-11-23 | 2021-03-26 | 浙江理工大学 | Organic silicon modified polymer/pigment composite latex and preparation method thereof |
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| CN103772708A (en) * | 2013-12-30 | 2014-05-07 | 上海发凯化工有限公司 | Glycosyl modified polysiloxane organic silicone softener and preparation method thereof |
| 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 |
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| CN107759806A (en) * | 2017-11-09 | 2018-03-06 | 陈晨特 | A kind of moisturizing lubricating type polysiloxanes Pickering emulsions and preparation method thereof |
| CN107739440A (en) * | 2017-11-14 | 2018-02-27 | 唐山三友硅业有限责任公司 | The method that emulsion polymerization prepares silicone release |
| CN107951747A (en) * | 2017-11-14 | 2018-04-24 | 湖南博隽生物医药有限公司 | A kind of polyglutamic acid modified organic silicon Pickering moisturizing emulsions and preparation method thereof |
| CN112552442A (en) * | 2020-11-23 | 2021-03-26 | 浙江理工大学 | Organic silicon modified polymer/pigment composite latex and preparation method thereof |
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