CN106633117B - A method of continuously and organosilicon micron ball is prepared without discharge - Google Patents
A method of continuously and organosilicon micron ball is prepared without discharge Download PDFInfo
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- CN106633117B CN106633117B CN201610877240.9A CN201610877240A CN106633117B CN 106633117 B CN106633117 B CN 106633117B CN 201610877240 A CN201610877240 A CN 201610877240A CN 106633117 B CN106633117 B CN 106633117B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention provides a kind of continuously and without the method that discharge prepares organosilicon micron ball, and described method includes following steps：1）Raw material components carry out pre-emulsification in pre-emulsification device；The raw material components include the polysiloxanes containing si-h bond, the polysiloxanes containing unsaturated carbon-carbon bond, the catalyst containing platinum group metal, cure retarder, water and emulsifier；2）Solution emulsifies in emulsifier unit after pre-emulsification；3）Heated device is heating and curing；4）It is filtered through continuous filter unit；5）The solid elastomers micron ball drying device obtained after filtering dries to form finished product；6）Water after filtering containing emulsifier enters in pre-emulsification device after apparatus for supercooling is cooling to be recycled.It is prepared while the method for the present invention is the advantages that keeping existing heat-resisting, the easy dispersion of organosilicon photo-diffusion particle, low-refraction using continuity method production technology, accomplishes cycling use of water while significantly improving production capacity, efficiency, saves emulsifier, without discharge, clean manufacturing.
Description
Technical field
The present invention relates to a kind of methods for preparing organic silicon sphere type particle, more particularly to one kind is continuous and is prepared with without discharge
The method of machine silicon micron ball.
Background technique
It can deflect when light passes through the interface of the transparency material with different refractivity, generate refraction, scattering etc.
Phenomenon enables light to spread, and point light source becomes area source.The more big then light deflection angle of refractive index is bigger, diffusion effect
Rate is higher.Light is also more by the more more then deflection number of times of number of different refractivity material interface, and diffuser efficiency is also
It is higher.
Positive spherical shaped transparent micro-size particles can be used as light diffusion particle and use in widely industry known to professional person.
The solid positive organic silicon particle of ball-type of micron order has the spies such as heat resistance height, good dispersion, the low, high transparency of refractive index
Point since applying initially as light diffusion particle, has gradually replaced the polymethyl methacrylate that the transparency is good but heat resistance is bad
(PMMA) though micron ball and the heat-resisting good but undesirable calcium carbonate of the transparency, barium sulfate micro-size particles and become the market mainstream.
Its high transparency presented, haze significant advantage by LED illumination industry and LCD backlight mould group light diffusing sheet etc.
Industry will be widely welcomed.
However current organosilicon micron ball is entirely to have production efficiency low, equipment using interval, the preparation of discontinuous hair
The big equal prominent drawback of occupied space, more each workshop section's equipment, container as involved in batch process need frequent clean, generate a large amount of
Waste water needs to discharge, and pollutes environment.
Summary of the invention
The purpose of the present invention is in view of the drawbacks of the prior art, provide a kind of preparation method of organosilicon micron ball, energy
Realize that organosilicon micron ball is continuously produced without discharge, enough to solve that there is life using interval, the preparation of discontinuous hair in the prior art
Low efficiency is produced, equipment occupation space is big to wait prominent drawback, and more each workshop section's equipment as involved in batch process, container need frequent
Cleaning, generates a large amount of waste water and needs to discharge, pollute the defect of environment.
To solve the above-mentioned problems and other problems, the present invention is achieved through the following technical solutions.
A method of continuously and organosilicon micron ball being prepared without discharge, described method includes following steps：
1) raw material components carry out pre-emulsification in pre-emulsification device；The raw material components include the poly- silicon oxygen containing si-h bond
Alkane, the polysiloxanes containing unsaturated carbon-carbon bond, the catalyst containing platinum group metal, cure retarder, water and emulsifier；
2) solution emulsifies in emulsifier unit after pre-emulsification；
3) heated device is heating and curing；
4) it is filtered through continuous filter unit；
The solid elastomers micron ball drying device obtained after filtering dries to form finished product；
Water after filtering containing emulsifier enters in pre-emulsification device after apparatus for supercooling is cooling to be recycled.
Preferably, before pre-emulsification, each raw material component first carries out premixing another rise into pre- in pre-mixing apparatus respectively
Emulsifier unit；Polysiloxanes and cure retarder containing si-h bond premix in the first pre-mixing apparatus, contain unsaturated carbon
The polysiloxanes of carbon key and catalyst containing platinum group metal premix in the second pre-mixing apparatus, and water and emulsifier are premixed in third
It is premixed in device.
Preferably, after the mixed liquor of first pre-mixing apparatus and the second pre-mixing apparatus enters static mixer mixing again
Into pre-emulsification device.
Preferably, pre-emulsification refer to using sawtooth pattern dispersion impeller and the stirring slurry with shearing function at high speed, will
Liquid polysiloxane cuts into 1~100 μm of liquid particle and is emulsified agent package, is evenly dispersed in water as polysiloxanes
Aqueous dispersion.Zigzag dispersion impeller more than 50 meter per second of preferred linear velocity.
Preferably, the emulsifier unit is selected from high-speed revolution shearing mulser, high pressure spray emitting mulser, colloid mill and surpasses
One of sound emulsifier and resonant wedge whistle formula mulser.In view of needing primary disengaging just to need to gather liquid in aqueous dispersion
Siloxanes average grain diameter cuts into average grain diameter in 0.1-10 micron range from 1-100 microns of range, here the preferred U.S.
The Sonolator of Sonic company production, device model：Model BT series SonolatorTM。
Preferably, emulsification is that the range by liquid polysiloxane average grain diameter in aqueous dispersion from 1~100 micron continues to cut
Average grain diameter is cut into 0.1~10 micron range.The aqueous silicon dispersions of small particle are more stable, are not easy demulsification layering.
It is highly preferred that booster pump is additionally provided between emulsifier unit and pre-emulsification device, to pre-emulsification mixed liquor is suitable
Benefit is squeezed into emulsifier unit.
Preferably, it is heating and curing and refers to and lead to the aqueous dispersion containing 0.1~10 micron of liquid polysiloxane spheroidal particle
Heating device is crossed to heat up and be solidified into elastomer silicone under the catalyst containing platinum group metal.It is preferred that in heating rapidly
Outer uniform microwave heating equipment.
Preferably, the heater is in heat exchange type heating device, infrared heating device or microwave heating equipment
It is a kind of.
Preferably, the continuous filter unit is selected from rotary drum continuous filter, rotating disc type continuous filter, centrifugal filtration
One of machine, continuous band vacuum filter or continuous horizontal type filter.In view of production efficiency and elastomer silicone
Water as few as possible and emulsifier remain in micron ball, here preferred continuous band vacuum filter.
Preferably, one of cooling device in open cooling tower, sealed cooling tower, heat exchanger or refrigerator is stated
Kind.In view of cooling efficiency, it is cooling after water temperature the factors such as accurately control, preferably can accurately set cooling water temperature, stream here
Measure the combination of the refrigerator and closed heat exchanger of flow velocity.
Preferably, drying unit be selected from tray dryer, conveyorized drier, rotary-drum drier, vertical drier,
Mechanical agitation type drier, roundabout drier, fluidized bed type drier, pneumatic dryer, oscillatory type drier and spraying
One of formula drier.It is preferred that pneumatic dryer.By the drying of pneumatic dryer high temperature air-flow, will effectively have
Moisture removal in machine silicone elastomer micron ball much filtrate.
Preferably, the organosilicon micron ball includes following raw material components and parts by weight：
100~110 parts by weight of liquid silicone composition
0.01~5 parts by weight of cure retarder
0.01~20 parts by weight of surfactant
The liquid silicone composition includes the polysiloxanes containing si-h bond and gathering containing unsaturated carbon-carbon bond
Siloxanes；
The raw material components further include the catalyst of the platinum group metal of effective catalytic amount.
Wherein the mass ratio of the polysiloxanes containing unsaturated carbon-carbon bond and the polysiloxanes containing si-h bond is 100：1
~10.It is highly preferred that the mass ratio of polysiloxanes and the polysiloxanes containing si-h bond containing unsaturated carbon-carbon bond is
100：1~5.
Preferably, at least containing there are three si-h bonds in the polysiloxanes containing si-h bond；Contain unsaturated carbon-carbon bond
Polysiloxanes at least contains there are three unsaturated carbon-carbon bond.
Liquid silicone composition includes two kinds of polysiloxanes that cross-linking reaction can be carried out under catalyst in the present invention.
The structural formula of polysiloxanes is shown below in the present invention：
R, R ' is the substituted or unsubstituted monovalent hydrocarbon or hydrogen being connected on Si atom comprising 1~30 carbon atom.Institute
State R and R ' it can be identical or not identical.
Preferably, the monovalent hydrocarbon is selected from alkyl, aryl, aralkyl, alkenyl, naphthenic base and arbitrarily in the above base
Be bonded in group carbon atom all or part of hydrogen atom replaced by halogen atom or/and other substituent groups after the group that is formed,
Other described substituent groups are acryloxy, methacryloxy, epoxy group, glycidoxy or carboxyl.More specifically,
The alkyl is methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, 14
Alkyl, pentadecyl, cetyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, 22
Alkyl, tricosyl or tetracosyl or melissyl.The aryl is phenyl, tolyl or naphthalene.The aralkyl
For benzyl or phenethyl.The alkenyl is vinyl, allyl, acrylic, cyclobutenyl, pentenyl or hexenyl.The cycloalkanes
Base is cyclopenta, cyclohexyl or suberyl.
Polysiloxanes containing unsaturated carbon-carbon bond and the polysiloxanes containing si-h bond can have any straight chain, ring-type
And branched structure, the preferred linear chain structure of the present invention.
For commercial value, it is further preferable that at least 60% mole of whole R ' groups are methyl.
Polysiloxanes abbreviation vinyl silicone oil containing vinyl, vinyl can be located at the two of polysiloxane molecule chain
End, one end, on side chain etc., all vinyl are all directly connected to silicon (Si).
Polysiloxanes abbreviation containing hydrogen silicone oil containing silicon hydrogen-based, hydrogen bond can be located at the both ends of polysiloxane molecule chain, one
On end, side chain etc., all hydrogen-baseds are all directly connected to silicon (Si).
Vinyl silicone oil reacts as shown below under platinum metal catalysts catalysis with containing hydrogen silicone oil：
Preferably, viscosity of the polysiloxanes at 25 DEG C is no more than 100000mm in the liquid silicone composition2/s。
Because when viscosity is more than 100000mm2When/s, small particle cannot be prepared by following methods and with the particle of narrow ditribution.When viscous
Degree is no more than 500mm2When/s, it is 10 that the micron ball for being typically prepared acquisition, which tests the range of the partial size obtained by laser particle analyzer,
Micron or less.Viscosity number can be measured by rotational viscometer.Preferably, viscosity of the polysiloxanes at 25 DEG C does not surpass
Cross 1000mm2/s.Viscosity of the polysiloxanes at 25 DEG C is no more than 500mm2/s。
Preferably, the degree of polymerization of polysiloxanes is 5~5000 in the organosilicon micron ball.
Catalyst includes the modified chloroplatinic acid of platinum group metal simple substance, platinum chloride, the chloride of platinum, chloroplatinate, alcohol, chlorine platinum
Acid and the complex of alkene load on platinum group metal simple substance, rhodium and olefin complex, chloro three (triphenylphosphine) on carrier
Rhodium, the complex of platinum and the polysiloxanes containing vinyl and platinum chloride, chloroplatinic acid and chloroplatinate and the silicon containing vinyl
The complex of oxygen alkane.
Preferably, the platinum group metal simple substance includes platinum, rhodium and palladium.The chloride of the platinum includes H2PtCl4·kH2O、
H2PtCl6·kH2O、NaHPtCl6·kH2O、KHPtCl6·kH2O、Na2PtCl6·kH2O、K2PtCl4·kH2O、PtCl4·
kH2O、PtCl2And Na2HPtCl4·kH2O, wherein the integer that k is 0~6.It is highly preferred that k is 0 or 6.
Preferably, the carrier is aluminium oxide, silica or carbon.
Preferably, the additional amount of platinum metal catalysts is can effectively amount required for catalyzing addition reaction of silicon with hydrogen be
It is quasi-.Preferably, the additional amount relative to liquid silicone composition total amount as the platinum group metal of catalyst, the catalyst
Additional amount is 0.1~500ppm.It is highly preferred that the additional amount of the catalyst is 0.5~200ppm.It is highly preferred that described urge
The additional amount of agent is 1~30ppm.In view of platinum catalyst required for the present invention should have it is colourless, transparent, do not dissolve in
Water, it is efficient the features such as, preferred widely used platinum (0)-divinyl tetramethyl disiloxane complex in the market also referred to as blocks
Family name's catalyst (Karstedt Catalyst).
Preferably, the cure retarder is selected from 01 derivatives, yne compounds, gathering containing alkenyl with triple carbon-carbon bonds
Siloxanes, amide compound, using one of ester of maleic acid synthesis or a variety of.
The 01 derivatives with triple carbon-carbon bonds be 3- methyl-1-butine-3- alcohol, methylpentynol, 3,
5- dimethyl -1- hexin -3- alcohol, 3-Phenyl-1-butyn-3-ol or 1- acetylene -1- cyclohexanol.Yne compounds are 3- methyl-
Pirylene or 3,5- dimethyl -3- hexene -1- alkynes.The polysiloxanes containing alkenyl is tetramethyl tetravinyl ring four
Four hexenyl cyclotetrasiloxane of siloxanes or tetramethyl.The amide compound is N, N- diallyl formamide, N, N- diene
Propyl benzamide, N, N, N ', N '-tetraallyl phthalic amide, N, N, N ', N '-tetraallyl terephthalamide or
N, N, N ', N '-tetraallyl isophtalamide.The maleic acid ester type compound is ethyl maleate, maleic acid monoene
The mono- 2- ethylhexyl of propyl ester, maleic acid or diallyl maleate.
It is highly preferred that the cure retarder is more vinyl polysiloxanes, structure is as follows：
(CH2=CH)3-SiO-(Si(CH3) (CH=CH2)O)n- Si- (CH=CH2)3, n be 0~20 integer；
Or (CH2=CH)3-SiO-(Si-(CH3) (CH=CH2)O)8- Si (CH=CH2)3,
Or CH2=CH-Si (CH3)2-O-(Si(CH3) (CH=CH2)O)8-Si(CH3)2- CH=CH2,
Or (CH3)3SiO-(Si-(CH3) (CH=CH2)O)8-Si(CH3)3。
More vinyl polysiloxanes are not soluble in water, volatility is small, tasteless and polysiloxanes compatibility is good, does not influence
The cure retarder of lightness.
Preferably, the raw material components further include the surfactant no more than 20 parts by weight.
Preferably, the surfactant is nonionic surfactant, cationic surfactant, anionic surface are lived
Property one of agent or amphoteric surfactant or a variety of.
Nonionic surfactant includes polyethylene oxide alkyl ethers, polyethylene glycol oxide polypropylene oxide alkyl ether, polyoxy
Change vinyl alkyl phenyl ether, cithrol, sorbitan fatty acid esters, polyoxyethylene sorbitan
Aliphatic ester, polyoxyethylene sorbitan aliphatic ester, fatty acid glyceride, polyoxyethylene glycerol aliphatic ester gather sweet
Oil and fat acid esters, methyl glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyethylene glycol oxide hydrogen
Change Castor Oil Fatty Acid ester, polyoxyethylene, polyoxyethylene fatty acid amides, polyethylene oxide modified organic group
Polysiloxanes and polyethylene glycol oxide polypropylene oxide-modification organopolysiloxane.Anionic surfactant includes alkyl
Sulfate, polyethylene oxide alkyl ethers sulfate, polyethylene glycol oxide alkyl phenyl ether sulfate, N- acyl taurine salt, alkyl
Benzene sulfonate, polyethylene glycol oxide alkyl phenyl ether sulfonate, alpha-alkene sulfonate, alkylnaphthalene sulfonate, two sulphur of alkyl diphenyl ether
Hydrochlorate, dialkyl sulfosuccinates, monoalkyl sulfosuccinate, polyethylene oxide alkyl ethers sulfosuccinate, fat
Hydrochlorate, polyethylene oxide alkyl ethers acetate, N- acyl amino hydrochlorate, N- acylalaninies salt, alkenyl succinate, alkyl phosphorus
Hydrochlorate and polyethylene oxide alkyl ethers phosphate.Amphoteric surfactant includes alkyldimethylamine oxide, carboxybetaine, alkane
Base amido propyl dimethyl hydroxyl glycine betaine, alkyl hydroxy sulfobetaines.
Above-mentioned surfactant can be used alone or two or more are applied in combination, it is contemplated that non-ionic surface active
Agent not adversely affects substantially to platinum group metal catalyzed system, it is preferable to use nonionic surfactant.
Preferably, the dosage of surfactant is no more than the 20wt% of liquid silicone composition.Dosage is excessively brought into non-
Organosilicon impurity component is too many, and if less than 0.01%, it is extremely difficult to be emulsified into micron ball for dosage.
It is highly preferred that the dosage of the surfactant is 0.1~10wt% of liquid silicone composition weight.
Heretofore described continuous production is each raw material component to be at the uniform velocity added in proportion by metering pump, and pass through static state
Mixer is uniformly mixed, into pre-emulsification device pre-emulsification, enter back into emulsifier unit fritter reach required for after micron grain size, lead to
Crossing heating makes liquid polysiloxane particle be solidified into solid elastomers micron ball, refilters realization solid and liquid separation, solid elastomers
Micron ball enters drying unit and is converted into finished product, and the water containing emulsifier recirculates utilization after supercooling.Water, emulsifier are mixed
It closes water, emulsification dosage that holding vessel takes away according to actual elastic body micron ball to be supplemented, formula is maintained to be basically unchanged.
The method of the present invention is same the advantages that keeping existing heat-resisting, the easy dispersion of organosilicon photo-diffusion particle, low-refraction
It is prepared by Shi Caiyong continuity method production technology, accomplish while significantly improving production capacity, efficiency cycling use of water, save emulsifier,
Without discharge, clean manufacturing.
Detailed description of the invention
Fig. 1 is the process and schematic device of the method for the present invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
In the embodiment of the present invention more vinyl polysiloxane cure retarders purchased from U.S. Gelest company (Gelest,
Inc.11East Steel Rd.Morrisville, PA 19067, USA
A kind of method for preparing organosilicon micron ball is disclosed in the present embodiment, described method includes following steps：
1) raw material components carry out pre-emulsification in pre-emulsification device；The raw material components include the poly- silicon oxygen containing si-h bond
Alkane, the polysiloxanes containing unsaturated carbon-carbon bond, the catalyst containing platinum group metal, cure retarder, water and emulsifier；
2) solution emulsifies in emulsifier unit after pre-emulsification；Emulsifier unit is selected from the production of U.S. Sonic company
Sonolator, device model：Model BT series SonolatorTM；
3) heated device is heating and curing；Heater selects microwave heating equipment；
4) it is filtered through continuous filter unit；Continuous filter unit selects continuous band vacuum filter；
The solid elastomers micron ball drying device obtained after filtering dries to form finished product；Drying unit is dry for air-flowing type
Dry device；
Water after filtering containing emulsifier enters in pre-emulsification device after apparatus for supercooling is cooling to be recycled.Cooling dress
Set the combination for selecting refrigerator and closed heat exchanger.
The preparation method used in the present embodiment is specific as follows and as shown in Figure 1.
Heretofore described continuous production is each raw material component to be at the uniform velocity added in proportion by metering pump, and pass through static state
Mixer is uniformly mixed, into pre-emulsification device pre-emulsification, enter back into emulsifier unit fritter reach required for after micron grain size, lead to
Crossing heating makes liquid polysiloxane particle be solidified into solid elastomers micron ball, refilters realization solid and liquid separation, solid elastomers
Micron ball enters drying unit and is converted into finished product, and the water containing emulsifier recirculates utilization after supercooling.Water, emulsifier are mixed
It closes water, emulsification dosage that holding vessel takes away according to actual elastic body micron ball to be supplemented, formula is maintained to be basically unchanged.
Embodiment 1
The type and content of each raw material component is as follows in the present embodiment：
100 parts by weight viscosity 450cSt, the vinyl silicone oil of contents of ethylene 1.4%；
The platinum-vinyl siloxane composition catalyst of 0.4 parts by weight platinum content 3000ppm；
The containing hydrogen silicone oil of 2.5 parts by weight hydrogen contents 1%；
0.03 parts by weight structure：(CH2=CH)3-SiO-(Si-(CH3) (CH=CH2)O)8- Si (CH=CH2)3Solidification
Delayed-action activator；
The isomeric alcohol polyethenoxy ether of 5 parts by weight HLB values 13；The deionized water of 200 parts by weight.
In the present embodiment preparation method:
The condition of being heating and curing is：Reach 80-85 DEG C by emulsion temperature after heating device, silicone liquid particle moment is solid
It is melted into elastomer particle；
Drying condition is：Pneumatic drier, 150 DEG C of inlet air temperature, 110 DEG C of leaving air temps, elastomer particle is in drying machine
9 seconds middle disengaging interval times prepared 4.5 microns of average grain diameter of elastomer particle；
Cooling condition is：80-85 DEG C of the water containing emulsifier is cooled to 20-25 DEG C to ensure in pre-emulsification and emulsification
Period polyorganosiloxane fluid mixture viscosity increases slow.
Embodiment 2
The type and content of each raw material component is as follows in the present embodiment：
100 parts by weight viscosity 500cSt, the vinyl silicone oil of contents of ethylene 0.8%；
The platinum-vinyl siloxane composition catalyst of 0.3 parts by weight platinum content 3000ppm；
The containing hydrogen silicone oil of 1.9 parts by weight hydrogen contents 0.75%；
0.02 parts by weight structure：CH2=CH-Si (CH3)2-O-(Si(CH3) (CH=CH2)O)8-Si(CH3)2- CH=CH2
Cure retarder；
The secondary alcohol polyoxyethylene ether of 4 parts by weight HLB values 11.
In the present embodiment preparation method:
The condition of being heating and curing is：Reach 60-65 DEG C by emulsion temperature after heating device, silicone liquid particle moment is solid
It is melted into elastomer particle；
Drying condition is：Pneumatic drier, 200 DEG C of inlet air temperature, 140 DEG C of leaving air temps, gel particles are in drying machine
Disengaging interval time 8 seconds, prepares 5.0 microns of average grain diameter of elastomer particle；
Cooling condition is：60-65 DEG C of the water containing emulsifier is cooled to 10-15 DEG C to ensure in pre-emulsification and emulsification
Period polyorganosiloxane fluid mixture viscosity increases slow.
Embodiment 3
The type and content of each raw material component is as follows in the present embodiment：
100 parts by weight viscosity 250cSt, the vinyl silicone oil of contents of ethylene 0.6%；
The platinum-vinyl siloxane composition catalyst of 0.45 parts by weight platinum content 3000ppm；
The containing hydrogen silicone oil of 1.7 parts by weight hydrogen contents 1.0%；
0.01 parts by weight structure is (CH3)3SiO-(Si-(CH3) (CH=CH2)O)8-Si(CH3)3Cure retarder；
The branched chain isomer tridecanol polyoxyethylene ether of 6 parts by weight HLB values 12；
In the present embodiment preparation method:
The condition of being heating and curing is：Reach 70-75 DEG C by emulsion temperature after heating device, silicone liquid particle moment is solid
It is melted into elastomer particle；
Drying condition is：Pneumatic drier, 250 DEG C of inlet air temperature, 170 DEG C of leaving air temps, gel particles are in drying machine
Disengaging interval time 10 seconds, prepares 3.5 microns of average grain diameter of elastomer particle；
Cooling condition is：70-75 DEG C of the water containing emulsifier is cooled to 1-5 DEG C to ensure in pre-emulsification and emulsified phase
Between polyorganosiloxane fluid mixture viscosity increase it is slow.
Embodiment 4
The type and content of each raw material component is as follows in the present embodiment：
100 parts by weight viscosity 200cSt, contents of ethylene 1.2% is vinyl silicone oil；
The platinum-vinyl siloxane composition catalyst of 0.5 parts by weight platinum content 3000ppm；
The containing hydrogen silicone oil of 2.5 parts by weight hydrogen contents 1.0%；
0.01 parts by weight structure is (CH2=CH)3-SiO-(Si-(CH3) (CH=CH2)O)8- Si (CH=CH2)3Solidification
Delayed-action activator；
The isomerous tridecanol polyoxyethylene ether of 5.5 parts by weight HLB values 13；
In the present embodiment preparation method:
Be heating and curing condition：Reach 85-90 DEG C by emulsion temperature after heating device, silicone liquid particle instantaneous solidification
Elastomer-forming particle；
Drying condition：Pneumatic drier, 300 DEG C of inlet air temperature, 180 DEG C of leaving air temps, gel particles in drying machine into
3.0 microns of average grain diameter of elastomer particle is prepared in interval time 9 seconds out；
Cooling condition：85-90 DEG C of the water containing emulsifier is cooled to 1-5 DEG C to ensure during pre-emulsification and emulsification
Polyorganosiloxane fluid mixture viscosity increases slow.
Elastomer silicone micron ball application example：
1. polystyrene is added with 1.5% additive amount (weight) in 4.5 microns of elastomer silicone balls made of example 1
In be uniformly mixed by extruder or mixer, then be fabricated to the light diffusing sheet of thickness 1mm, after tested light transmittance 68%, mist degree
80%；
2. polycarbonate is added with 2.0% additive amount (weight) in 5.0 microns of elastomer silicone balls made of example 2
In be uniformly mixed by extruder or mixer, then be fabricated to the light diffusing sheet of thickness 1mm, after tested light transmittance 85%, mist degree
93%；
3. 3.0 microns of elastomer silicone balls made of example 4 are added in polypropylene with 1.0% additive amount (weight)
It is uniformly mixed by extruder or mixer, then is fabricated to the light diffusing sheet of thickness 1mm, after tested light transmittance 63%, mist degree
91%.
The method of the present invention is same the advantages that keeping existing heat-resisting, the easy dispersion of organosilicon photo-diffusion particle, low-refraction
It is prepared by Shi Caiyong continuity method production technology, accomplish while significantly improving production capacity, efficiency cycling use of water, save emulsifier,
Without discharge, clean manufacturing.
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that under the premise of not departing from the method for the present invention, can also be made for those skilled in the art
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are equivalent embodiment of the invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations made by above-described embodiment, still fall within the range of technical solution of the present invention
It is interior.
Claims (7)
1. method that is a kind of continuous and preparing organosilicon micron ball without discharge, which is characterized in that described method includes following steps：
1) raw material components carry out pre-emulsification in pre-emulsification device；The raw material components include the polysiloxanes containing si-h bond,
Polysiloxanes containing unsaturated carbon-carbon bond, the catalyst containing platinum group metal, cure retarder, water and emulsifier；
2) solution emulsifies in emulsifier unit after pre-emulsification；
3) heated device is heating and curing；
4) it is filtered through continuous filter unit；
The solid elastomers micron ball drying device obtained after filtering dries to form finished product；
Water after filtering containing emulsifier enters in pre-emulsification device after apparatus for supercooling is cooling to be recycled；
Before pre-emulsification, each raw material component first carries out premixing another rise into pre-emulsification device in pre-mixing apparatus respectively；Contain
The polysiloxanes and cure retarder for having si-h bond premix in the first pre-mixing apparatus, the poly- silicon oxygen containing unsaturated carbon-carbon bond
Alkane and catalyst containing platinum group metal premix in the second pre-mixing apparatus, and water and emulsifier premix in third pre-mixing apparatus；
Pre-emulsification is entered back into after the mixed liquor of first pre-mixing apparatus and the second pre-mixing apparatus enters static mixer mixing
Device；
Pre-emulsification refer to using sawtooth pattern dispersion impeller and the stirring slurry with shearing function at high speed, by liquid polysiloxane
It cuts into 1~100 μm of liquid particle and is emulsified agent package, is evenly dispersed in water as polysiloxanes aqueous dispersion；
The cure retarder is selected from 01 derivatives, yne compounds, the polysiloxanes containing alkenyl, amide with triple carbon-carbon bonds
One of compound, the ester synthesized using maleic acid are a variety of.
2. method as described in claim 1, which is characterized in that the emulsifier unit is selected from high-speed revolution shearing mulser, high pressure
One of ejection-type mulser, colloid mill and ultraemulsifier and resonant wedge whistle formula mulser.
3. method as described in claim 1, which is characterized in that emulsification be by liquid polysiloxane average grain diameter in aqueous dispersion from
1~100 micron of range continues to cut into average grain diameter in 0.1~10 micron range.
4. method as described in claim 1, which is characterized in that being heating and curing, refer to will be containing the poly- silicon oxygen of 0.1~10 micron of liquid
The aqueous dispersion of alkane spheroidal particle is heated up by heating device and is solidified under the catalyst containing platinum group metal organic
Silicone elastomer.
5. method as described in claim 1, which is characterized in that the heater is selected from heat exchange type heating device, infrared heating
One of device or microwave heating equipment.
6. method as described in claim 1, which is characterized in that the continuous filter unit is selected from rotary drum continuous filter, turns
One of disk like continuous filter machine, filter centrifugal, continuous band vacuum filter or continuous horizontal type filter.
7. method as described in claim 1, which is characterized in that the cooling device is selected from open cooling tower, closed cooling
One of tower, heat exchanger or refrigerator.
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| CN106543455B (en) * | 2016-11-03 | 2020-05-19 | 涌奇材料技术（上海）有限公司 | Method for continuously preparing organic silicon micro-spheres without emission |
| CN111500067B (en) * | 2020-05-29 | 2022-02-25 | 长兴特殊材料（珠海）有限公司 | Porous organosilicon elastic microsphere and preparation method thereof |
| CN111978916A (en) * | 2020-09-02 | 2020-11-24 | 安晟技术(广东)有限公司 | Anti-sedimentation fluorescent glue and preparation method thereof |
| CN115232475A (en) * | 2022-06-30 | 2022-10-25 | 江苏涌新材料科技有限公司 | Refractive index adjustable organic spherical micro-nano particle and preparation method thereof |
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| US4248751A (en) * | 1979-08-31 | 1981-02-03 | Dow Corning Corporation | Process for producing a silicone elastomer emulsion and use thereof |
| JPS62257939A (en) * | 1986-05-02 | 1987-11-10 | Shin Etsu Chem Co Ltd | Production of spherical fine powder of silicone elastomer |
| CN1323103C (en) * | 2005-04-28 | 2007-06-27 | 陈俊光 | Ball-shaped organic silicon bubber products and its preparation process |
| KR20120102781A (en) * | 2009-12-23 | 2012-09-18 | 블루스타 실리콘즈 프랑스 에스에이에스 | Hydrosilylation reaction inhibitors, and use thereof in a coating method |
| CN103242801B (en) * | 2013-05-14 | 2015-03-11 | 汕头市骏码凯撒有限公司 | Single-component high-refractivity LED (light-emitting diode) packaging adhesive and preparation method thereof |
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