CN104226213B - A kind of manufacture method containing cinnamic many shells liquid crystal microcapsule - Google Patents
A kind of manufacture method containing cinnamic many shells liquid crystal microcapsule Download PDFInfo
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- CN104226213B CN104226213B CN201410514834.4A CN201410514834A CN104226213B CN 104226213 B CN104226213 B CN 104226213B CN 201410514834 A CN201410514834 A CN 201410514834A CN 104226213 B CN104226213 B CN 104226213B
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Abstract
The present invention relates to a kind of method of manufacturing many shells liquid crystal microcapsule containing cinnamic different types of softgel shell material and different types of polymerization interact. It is characterized in that having by polymerization and forming the polystyrene that outermost layer intensity is higher in this softgel shell. Another feature is the uniqueness of structure; in order effectively to protect the distinctive optical color of liquid crystal to adopt the capsule form of many shell protections; its architectural feature is that the first shell is that two kinds of hydrophilic colloids with different electric charges do wall material; the second shell is the polymer of organic compound monomer; the high polymer alloy transition zone of having constructed one deck interpenetrating networks between first and second shell, intensity significantly improves. That has effectively protected liquid crystal is not subject to environment acid and alkali corrosion, has improved resistance, mechanical pressure-bearing property, and application security is high, can, really effectively for as printing-ink, bear the pressure of printing. And effectively protect the distinctive optical color of liquid crystal.
Description
Technical field
The present invention relates to a kind of different types of softgel shell material and different types of polymerization interacts and manufactures many shellsThe method of liquid crystal microcapsule
Background technology
In order to prevent that Cucumber (gas, liquid, solid) is oxidized, variable color, corrosion and loss of stability, will take correspondingTechnological means is protected. Adopt filmogen to be wrapped up in it, include and wherein form different tiny capsules, interior bag thing is coreMaterial, external coating is shell material, the method for this kind of tiny capsules technology of preparing is a high-end skill of being shown great attention to this centuryArt, purposes is very extensive.
The quality that is protection medicine at field of medicaments at present adopts capsule technique, but the particle diameter of medicine class capsule is larger. ButThe application of industry and high-end technology field is very few, in fact in the urgent need to. As developer, function long-acting sustained-release agent, anticorrisive agent etc. are allNeed to be taked microcapsules technology to implement protection.
Field of medicaments adopts high temperature spray-drying technology more at present, although technique is simple, high temperature evaporation, can destroy activityMaterial, cyst wall breaks, and compactness is poor, and protectiveness is poor.
The core of manufacturing at present capsule mostly is pressed powder and high concentration liquid, become capsule opaque. Relate to liquid crystalSeldom. Most coated capsules that form of individual layer that adopt, shaky, dangerous at present, but because it is final products, therefore do not haveThere is relation. But applying it in industry is intermediate products, it will be subject to the effect of various power, can be damaged, thus infeasible, do not reachThe protection such as colour developing and the slowly-releasing object of expection.
Liquid crystal makes it have unique optical characteristics due to special molecular structure and in the arrangement conformation in space, and presentsGo out distinctive optical color. At present little about the relevant report of liquid crystal applications, only limit to liquid crystal display at applied technical fieldDevice, and temperature display meter, reason is that liquid crystal can be subject to can changing in solvent, soda acid, pressure and collision in surrounding mediumWith this distinctive optical characteristics that disappears. Also it applies difficult reason on ink just for this. Therefore the document of this respect is little. CauseVery special for the form of liquid crystal, be the 4th state of the non-solid non-gas of non-liquid, between fluid and solid, so to its coated difficultyLarger, conventional individual layer is coated, and cyst wall is solid not, soft and soggy, easily adhesion. Under collision and extruding, all can break, as: printing is oneExert pressure to press ink shift process, therefore capsule shaky be must break undoubtedly. The present invention has overcome application number in 2013The cigarette of a CN103233397A reversible temperature-sensitive is by its capsule particle size in the preparation of wrapping paper to 5-1000 μ m, and it is than China inkLayer is all high, cannot realize the shortcoming of printing; Clad is one deck, capsule easily break and its capsule shell in add clay, siliconThe material such as hydrochlorate, aluminium, causes the optical color of liquid crystal the shortcoming such as cannot represent.
The CN102675958A clad that the present invention has overcome application in 2012 is one deck, the shortcoming that capsule easily breaks. ThisIt is but that double walled capsule internal layer is that grease is difficult to gather that invention has overcome the liquid crystal of the CN1062744A employing of application in 1992Close bonding not firm shortcoming between ground floor shell and second layer shell.
The present invention is special in effectively coated technical method of liquid crystal capsule, increase cyst wall intensity and soft firm conjugation,And be multilayer softgel shell, ensured the security and stability of application, therefore can apply in gravure and serigraphy.
Summary of the invention
The present invention be directed to special the 4th form product of one of material, have the feature of fluidised form and crystalline state concurrently, have dynamicallyThe little molecule liquid crystal of molecular combinations conformation, is prepared into microemulsion, carries out variety classes material and variety classes polymerization is mutualThe polymerization of blending property, is characterized by many shell structurres of having constructed microcapsules uniquenesses. Form many shells microcapsules. Based on liquid crystal moleculeThe gravitation of two terminal polar groups, is difficult for disperseing, and dissolves therefore introduce the 3rd component. Adopt natural electronegative Arab treeGlue and positively charged gelatin, interacted and progressively deposited to capsule-core around by attracting each other of positive and negative charge, makes elder generationThe gelatin that the gum arabic of enclosing and rear absorption are got on is double-deck multiple state of aggregation and is coated on the surface of capsule-core, and it is right to have realizedIt is coated that liquid crystal carries out the first shell. Before the second shell is coated, centre is constructed and has been formed swelling grafting transition zone, adopts naturalGelatin, gum arabic respectively accounts for 50%. This layer is by various radical reactions and grafting, and in bulk polymerization, formation passes closing of network mutuallyGold structure sheaf. The last radical polymerization of styrene monomer, formation the second shell of carrying out under the effect of emulsifying agent, initator.Form microcapsules tiny evenly, solid, not inter-adhesive, good stability, safe, liquid crystal is protected therein, and it is peculiarBirefringence optics characteristic and color be protected, avoided that PH in the coated applied environment causing changes, solventUnder the effects such as burn into light, stress, lose its distinctive optical signature and color.
The present invention for the technical scheme that realizes above-mentioned technical goal and take is:
The manufacture method of many shells liquid crystal microcapsule of A, a kind of mutual polymerization is characterised in that following reactions steps and process flowJourney. In reactor, first add the electronegative hydrophilic colloid aqueous solution, under high-speed stirred, add liquid crystal solution, form micro emulsionLiquid, and then under specific temperature-time, then adding the positively charged hydrophilic colloid aqueous solution, two kinds of different electric charges are done mutuallyWith, form multiple coacervate, then cooling gradually, reduces mixing speed, under certain hour stability, then by curing agent and promoterEffect will answer coacervate and be converted into undissolved cross-linked structure the first shell.
B, then add colloidal solution and form the swelling grafting transition zone on the first shell surface, that is to say ground floor and the second layerBetween swelling grafting transition zone. Because the first shell is at the post bake that completes below freezing, epidermis consolidation is smooth, is difficult to adhere toOther foreign peoples's materials, are difficult to carry out the coated polymerization of second layer shell. Therefore heating makes first shell epidermis is swelling to be clamminess, then addsColloid of the same race is just easy on swelling epidermis, adhere to and then realize the fusion grafting of molecule, here except physical action,Also has ionization, the effect of hydroxyl and other group. The grafting transition zone of preparation is conducive to the coated of the second shell like this. LeadThe organic compound that causes grafting strand and the second shell forms inierpeneirating network structure in follow-up polymerization, quite high polymer alloyLayer, so layer intensity is very large.
C, then under the protection of emulsifying agent, further realize the radical polymerization of styrene monomer, form the second shell.The microcapsule product that forms 2-20 μ m left and right after cleaning separation, product has fully shown the distinctive optical characteristics of liquid crystal and lookColor.
This manufacturing system is one and condenses again and form small parcel shell from the effect of emulsion process positive and negative charge, then and then hands overConnection, then realizes the radical polymerization of the styrene monomer of secondary emulsion by the swelling grafting layer of middle interpenetrating networks, formThe class emulsion polymerization systems of many shells tiny capsules. Its appearance has drawn together emulsion and solution, ion and free radical, interpenetrating networks and nucleocapsid are poly-The multiple excellent characteristics closing.
This its core of manufacturing system material therefor is little molecule cholesteryl liquid crystal, and this kind of liquid crystal is a kind of non-solid, non-liquid, non-Gas form, is the 4th state outside tri-state, has characteristic liquid and crystalline state concurrently, present fluidised form and solid-state between form. PossessThe peculiar birefringent characteristic of optical anisotropy crystal, is subject to temperature, and the impact of light and angle is sent out its various optical propertiesLight changes, and presents different color. But do any or any combination in core cholesteryl liquid crystal. Liquid crystal is slichem-79Mixture with BDH2281. or cholesterine cinnamate, cholesteryl nonanoate, cholesteryl benzoate, benzoic acid acetic acid esters.
In this manufacture method, the first shell shell material is gum arabic and gelatin, is natural environmental protection colloid. Centre is constructedSwelling grafting transition zone be also gum arabic and gelatin, the second shell material is distyryl compound monomer. Mounting medium isWater. therefore production process is harmless, Product Green, safety. In this manufacture method, the emulsifying agent of formation the second shell polymerization used isEnuatrol, neopelex, lauryl sodium sulfate.
In this manufacture method, the initator of formation the second shell polymerization used is potassium peroxydisulfate, ammonium persulfate, peroxidatingDibenzoyl.
The curing agent that makes coacervate form cross-linked structure in this manufacture method is formaldehyde, sulfuryl ethyl sulfonate, Alpha-hydroxyOne in sulfuryl, pyridine salt, hardening accelerator is 1,3,5-trihydroxybenzene, hybar X, uracil, sodium hydrogen tartrate whereinKind.
Material usage from capsule-core to multilayer softgel shell in manufacturing technology of the present invention:
Capsule-core
Liquid crystal and acetone, butanone ratio are to account for 4.25% of total system weight at 1: 1
The first shell
Concentration be the Arabic gum aqueous solution of 15-20% account for total system weight 1.59%.
Concentration be the aqueous gelatin solution of 15-20% account for total system weight 1.59%.
With the HAc tune system PH=4 of concentration 50%, (do not participate in reaction, ignore).
Carry out system dilution with distilled water, distilled water accounts for 74.4% of total system weight
The curing agents such as the formaldehyde of 37% concentration or sulfuryl ethyl sulfonate, account for 0.637% of total system weight
Hardening accelerator 1,3,5-trihydroxybenzene or the hybar X etc. of 1% concentration account for 0.03% of total system weight.
With the NaHCo of concentration 10%3Tune system PH=8 left and right, (do not participate in reaction, ignore).
Swelling grafting transition zone in the middle of first and second shell
Colloidal solution by 15-20% concentration forms, and gum arabic/gelatin is: 50%/50%. accounts for total system weight1%
Emulsifying agent enuatrol accounts for 0.03% of total system weight.
The solvent of dissolved emulsifier is distilled water, accounts for 5.3% of total system weight
The second shell
Add emulsifying agent (enuatrol or the neopelex etc.) aqueous solution to form emulsion protection, total system weight0.021％
Add initator (potassium peroxydisulfate or ammonium persulfate or dibenzoyl peroxide etc.), account for total system weight0.053％
Add monomer styrene, account for 0.9% of total system weight
The solvent that dissolves above-mentioned three kinds of auxiliary agents is distilled water, accounts for 10% of total system weight
In the core of liquid crystal, introduce a solvent composition, formed and in microemulsion, introduced the 3rd component butanone or thirdKetone, they play the effect of dissolving liquid crystal, make it to become liquid crystal solution. And contribute to the diffusion of liquid crystal with mobile.
The technique particularity that forms the first shell step in manufacture method is: stir from liquid crystal and start the high rotating speed disperseing1400-2200 rev/min, is progressively down to 100-500 rev/min, and effect is to stablize established ground floor clad, makes it not collideNon-caked. When temperature is down to encystation from starting 40 DEG C-70 DEG C of dispersed liquid crystal below 0 DEG C of point, effect is to form physics to shrink and obtainObtain solid rete.
Constructing in the step of intermediate swellings grafting layer, mixing speed is 200-700 rev/min, and temperature is from adding 50%/50%The 35-50 DEG C of the colloidal solution of gelatin/gum arabic, is adjusted to the 50-70 DEG C while putting into emulsifying agent, and effect is to accelerate emulsification to divideLoose.
In the step of formation the second shell, the second shell mixing speed remains on 200-700 rev/min, and temperature is from adding breastThe 50-70 of agent DEG C is transferred to the 60-90 DEG C of polyaddition monomer monomer. and effect is to promote polymerization. Reaction time is 2-3.5 hour,Wherein monomer adds the dropping mode that adopts.
The pH value of manufacturing system is by from starting the PH=2-of dispersed liquid crystal form microemulsion in gum arabic gelatin time4, effect is the dispersion that acidity is conducive to system, the PH=8-12 while being adjusted to last encystation, and effect is that alkalescence is conducive to softgel shellStable.
Beneficial effect of the present invention:
Importantly, by under first step high-speed stirred, form and be full of the colloid of negative electrical charge and the microemulsion of liquid crystal solution,Just because of the protection of electric charge makes formed microemulsion very even, trickle, so that afterwards from small glue-line inclusion enclave to micro-glueThe formation of capsule is can both particle diameter even, tiny, can reach 2-20 μ m.
Just because of the adding of curing agent and hardening accelerator, make system in reaction, form the cross-linked structure of ground floor,And at the first shell surface construction the swelling grafting layer of one deck, after polymerization, form the alloy structure layer of interpenetrating networks, lastUnder the protective effect of emulsifying agent, formed the second shell, the microcapsules of formation are stable, solid, safety, do not reveal. Can reach expectionProtection object.
Above-mentioned condition ensures just, so that the microcapsules that obtain can fully show the distinctive optical birefringence spy of liquid crystalLevy and color.
Brief description of the drawings
Fig. 1 is depth-of-field microscope photo and the Stereo microscope photo of product of the present invention.
Detailed description of the invention:
Embodiment 1.
The Arabic gum aqueous solution 15ml that is first 20% by concentration adds reaction bulb, adds liquid crystal under high-speed stirred againSolution (20g Liquid crystal pour 20ml acetone), accelerates to be stirred to 2200 revs/min. At 70 DEG C, form microemulsion, stablize after 5 minutes, addEnter concentration and be 15% aqueous gelatin solution 15ml. With the HAc tune system PH=4 of concentration 50%, stir speed (S.S.) is down to 500 revs/min,Stablize 5 minutes, adding distil water (40 DEG C) 200ml dilution, now mixing speed is down to 200 revs/min, the outer positive and negative charge of system coreEffect produces multiple cohesion, stablizes 10 minutes, then adds the distilled water 500ml of 35 DEG C and dilute, and system temperature is 35 DEG C, 10 minutesLeft and right, is then cooled to solution system-5 DEG C, and adds 37% curing agent formaldehyde 20ml, the equal benzene three of 3ml hardening acceleratorPhenol, with the NaHCo of concentration 10%3Tune system PH=8 left and right, reacts 60 minutes, will stir 600 revs/min of modulation, then be warming up to 40DEG C, add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml, form swelling grafting transition zone, 55 DEG C time, addEnter to contain the 60ml aqueous solution of 0.5 gram of emulsifying agent (enuatrol), form emulsion protection, 65 DEG C time, drip and there is 0.3 gram of initatorPotassium peroxydisulfate, the emulsifying agent enuatrol of 0.2 gram, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 200-300 revs/min. 80 DEG C of reactions finish for 3.5 hours. Room temperature was placed after 24 hours, and distilled water cleans, and separated. Obtaining particle diameter is 2-20 μ mMicrocapsules. Product has fully shown optical signature and the color of liquid crystal.
Embodiment 2.
The Arabic gum aqueous solution 18ml that is first 15% by concentration adds reaction bulb to stir. Then incite somebody to action (20g liquid crystal+20ml butanone) solution inject, stir be down to 1400 revs/min, under temperature 60 C, form microemulsion, stablize about 10 minutes, addEntering concentration is the gelatin solution 15ml of 20% concentration. With the HAc tune PH=3.5 of concentration 50%, stirring reduction of speed rate is 500 revs/min,Stablize 5-10 minute, add the distilled water 170ml dilution of (50 DEG C), now mixing speed is down to 300 revs/min, the outsourcing of system coreWrap up in layer charge effect and form multiple cohesion, stablize 5 minutes, then add the distilled water 4500ml of 30 DEG C to dilute, temperature is 30-40DEG C, about 10 minutes, afterwards system is cooled to below freezing-5 DEG C, and adds curing agent and enter sulfuryl ethyl sulfonate 20ml, hardChange promoter hybar X 3ml, stir 40 minutes, with the NaHCo of concentration 10%3Tune system PH=8 left and right. To stir modulation100 revs/min, react 50 minutes. Be warming up to again 30 DEG C, add 20% (gum arabic 50%/gelatin 50%) colloidal solution10ml, forms swelling grafting transition zone, adds the aqueous solution of the 50ml that contains 0.3 gram of neopelex, shape 45 DEG C timeBecome emulsion protection, 60 DEG C time, add and there is 0.3 gram of ammonium persulfate, 0.2 gram of neopelex, 9ml styrene monomerThe 100ml aqueous solution, mixing speed remains on 200-300 rev/min. React end in 3.5 hours. Room temperature was placed after 24 hours, distillationWater cleans, and separates. Obtaining particle diameter is the microcapsules of 2-20 μ m. Product has fully shown optical signature and the color of liquid crystal.
Embodiment 3.
The Arabic gum aqueous solution 15ml that is first 20% by concentration adds reaction bulb, adds liquid crystal under high-speed stirred againSolution (20g Liquid crystal pour 20ml acetone), accelerates to be stirred to 1700 revs/min. At 50 DEG C, form microemulsion, stablize after 5 minutes, addEnter concentration and be 15% aqueous gelatin solution 18ml. Adjust system PH=4 with the HAc of concentration 50%, stir speed (S.S.) be down to 1000 turn/Point, stablize 5 minutes, adding distil water (40 DEG C) 200ml dilution, now mixing speed is down to 200 revs/min, and system core surface is justNegative electrical charge effect produces multiple cohesion, stablizes 10 minutes, then adds the distilled water 500ml of 35 DEG C and dilute, and system temperature is 35 DEG C,About 10 minutes, then solution system is cooled to-5 DEG C, and adds 37% curing agent Alpha-hydroxy sulfuryl 20ml, 3ml sclerosisPromoter uracil,, with the NaHCo of concentration 10%3Tune system PH=8 left and right, reacts 45 minutes, stirring modulation 600 is turned/Point, then be warming up to 45 DEG C, and add colloidal solution 10ml, form swelling grafting transition zone, 50 DEG C time, add and contain 0.5 gram of emulsifying agentThe 60ml aqueous solution of lauryl sodium sulfate, forms emulsion protection, adds and have 0.3 gram of initiator potassium persulfate, 0.2 75 DEG C timeGram lauryl sodium sulfate, the 100ml miscible fluid of the styrene monomer of 9ml, mixing speed remains on 200 revs/min. Reaction 3.5Hour finish. Room temperature was placed after 24 hours, and distilled water cleans, and separated. Obtaining particle diameter is the microcapsules of 2-20 μ m. Product fully showsOptical signature and the color of liquid crystal.
Embodiment 4.
The Arabic gum aqueous solution 15ml that is first 20% by concentration adds reaction bulb, adds liquid crystal under high-speed stirred againSolution (20g Liquid crystal pour 20ml acetone), accelerates to be stirred to 1800 revs/min. At 50 DEG C, form microemulsion, stablize after 5 minutes, addEnter concentration and be 15% aqueous gelatin solution 15ml. Adjust system PH=4 with the HAc of concentration 50%, stir speed (S.S.) be down to 1000 turn/Point, stablize 5 minutes, adding distil water (40 DEG C) 200ml dilution, now mixing speed is down to 250 revs/min, and system core is outer positive and negativeCharge effect produces multiple cohesion, stablizes 10 minutes, then adds the distilled water 450ml of 35 DEG C and dilute, and system temperature is 35 DEG C, and 10About minute, then solution system is cooled to-2 DEG C, and adds 37% curing agent pyridiniujm 20ml, 3ml hardening acceleratorSodium hydrogen tartrate, with the NaHCo of concentration 10%3Tune system PH=8 left and right, reacts 65 minutes, will stir 450 revs/min of modulation, thenBe warming up to 45 DEG C, add 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml, form swelling grafting transition zone,60 DEG C time, add the 60ml aqueous solution that contains 0.5ml emulsification enuatrol, form emulsion protection, 70 DEG C time, add to there is 0.3 gram and drawSend out agent potassium peroxydisulfate, 0.2 gram of enuatrol, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 300 revs/min.React end in 3 hours. Room temperature was placed after 24 hours, and distilled water cleans, and separated. Obtaining particle diameter is the microcapsules of 2-20 μ m. Product fillsDivide the optical signature and the color that have shown liquid crystal.
Embodiment 5.
The Arabic gum aqueous solution 15ml that is first 20% by concentration adds reaction bulb, adds liquid crystal under high-speed stirred againSolution (20g Liquid crystal pour 20ml acetone), accelerates to be stirred to 1700 revs/min. At 50 DEG C, form microemulsion, stablize after 5 minutes, addEnter concentration and be 15% aqueous gelatin solution 18ml. Adjust system PH=4 with the HAc of concentration 50%, stir speed (S.S.) be down to 1000 turn/Point, stablize 5 minutes, adding distil water (40 DEG C) 185ml dilution, now mixing speed is down to 200 revs/min, and system core is outer positive and negativeCharge effect produces multiple cohesion, stablizes 10 minutes, then adds the distilled water 515ml of 35 DEG C and dilute, and system temperature is 35 DEG C, and 10About minute, then solution system is cooled to-5 DEG C, and adds 37% curing agent Alpha-hydroxy sulfone 20ml, the 3ml promotion of hardeningAgent uracil, with the NaHCo of concentration 10%3Tune system PH=8 left and right, reacts 35 minutes, will stir 600 revs/min of modulation, then riseTemperature, to 40 DEG C, adds 20% (gum arabic 50%/gelatin 50%) colloidal solution 10ml, forms swelling grafting transitionLayer, adds the 60ml aqueous solution that contains 0.5 gram of emulsifying agent (enuatrol) 55 DEG C time, form emulsion protection, 70 DEG C time, adds and has0.2 gram of enuatrol of 0.3 gram of initator dibenzoyl peroxide, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed is protectedBe held in 200-300 rev/min. React end in 3.5 hours. Room temperature was placed after 24 hours, and distilled water cleans, and separated. Obtaining particle diameter is 2-The microcapsules of 20 μ m. Product has fully shown optical signature and the color of liquid crystal. About minute, then that solution system is coolingTo-5 DEG C, and add 37% curing agent formaldehyde 20ml, 3ml hardening accelerator 1,3,5-trihydroxybenzene, with the NaHCo of concentration 10%3AdjustSystem PH=8 left and right, reacts 45 minutes, will stir 600 revs/min of modulation, then be warming up to 45 DEG C, adds 20% (gum arabic50%/gelatin 50%) colloidal solution 10ml, form swelling grafting transition zone, 65 DEG C time, add and contain 0.5 gram of emulsifying agent dodecaneThe 60ml aqueous solution of base benzene sulfonic acid sodium salt, forms emulsion protection, and 70 DEG C time, add and there is 0.3 gram of initator dibenzoyl peroxide,0.2 gram of neopelex, the 100ml aqueous solution of the styrene monomer of 9ml, mixing speed remains on 200-300 and turns/Point. React end in 3.5 hours. Room temperature was placed after 24 hours, and distilled water cleans, and separated. Obtaining particle diameter is the microcapsules of 2-20 μ m. ProduceProduct have fully shown optical signature and the color of liquid crystal.
Product photo, as accompanying drawing, can find out that from accompanying drawing above-mentioned many shells liquid crystal distinctive birefringence optics characteristic and color are subject toTo protection, the PH variation in the coated applied environment causing, the lower mistake of the effect such as burn into light, stress of solvent are avoidedRemove its distinctive optical signature and color. (seeing accompanying drawing 1)
Claims (12)
1. a manufacture method for the many shells liquid crystal microcapsule that contains polystyrene, its feature comprises the following steps: (1) forms capsuleCore and the first shell: in reactor, first add the electronegative gum arabic hydrophilic colloid aqueous solution, then in high-speed stirringMix down the liquid crystal solution adding with butanone or acetone solution, form microemulsion, then at 40-60 DEG C, after 3-15 minute,Add again the positively charged gelatin hydrophilic colloid aqueous solution, two kinds of different charge interactions, shape on the capsule-core forming at liquid crystalBecome multiple coacervate; Then cooling gradually, reduces mixing speed, under 20-50 minute stable state, then by curing agent and promoterEffect will be answered coacervate and will be converted into undissolved cross-linked structure the first shell, and (2) form swelling grafting transition zone: at heating 35-At 50 DEG C, adding concentration is 15-25%, and consumption is that the colloidal solution of 50% gelatin/50% gum arabic forms the first shell tableThe swelling grafting transition zone of face, because the first shell smooth surface of compacting is difficult to adhere to other materials, but heating rear surface is swellingBe clamminess, add and just adhere to easily surface after a small amount of gelatin/gum arabic and form grafting through reaction, this will be to the second shellThe coated positive role that plays of layer material, causes the organic compound of grafting strand and the second shell to form in follow-up polymerizationInierpeneirating network structure, is equivalent to high polymer alloy; (3) form the second shell: be warming up to again afterwards 35-60 DEG C, add quantitativeEmulsifier solution, under the protection of emulsifying agent, when system is warming up to 60-90 DEG C, will contain initator, emulsifying agent, styrene listThe solution of body splashes into system, reacts and within 2-3.5 hour, has realized styrene monomer radical polymerization, forms the second shell; (4) cleanAfter separation, obtain the microcapsule product of 2-20 μ m.
2. liquid crystal microcapsule manufacture method as claimed in claim 1, is characterized in that,
(1), in formation capsule-core and the first shell step, rotating speed, by the high rotating speed 1400-2200 rev/min that makes dispersed liquid crystal, acts onIt is the more tiny dispersion of microemulsion that makes formation; Progressively be down to 100-500 rev/min, effect is to stablize established the first shell, makesDo not collide non-caked; Temperature is down to below 0 DEG C from 40 DEG C-70 DEG C of starting dispersed liquid crystal, and effect is to form physics contraction to obtainObtain solid rete;
(2), forming in the step of swelling grafting transition zone, mixing speed is 200-700 rev/min, temperature from add 50% gelatin/35-50 DEG C when the colloidal solution of 50% gum arabic, is adjusted to the 50-70 DEG C while putting into emulsifying agent, and effect is to accelerate emulsificationDisperse;
(3) in the step of formation the second shell, the second shell mixing speed remains on as 200-700 rev/min, is transferred to polyadditionThe 60-90 DEG C of monomer, effect is to promote polymerization, and the reaction time is 2-3.5 hour, and wherein monomer adds the dropping mode that adopts.
3. liquid crystal microcapsule manufacture method as claimed in claim 1, is characterized in that, regulates the pH of manufacturing system in reactorValue, will be capsule-core from starting to form liquid crystal, the pH=2-4 when microemulsion that gelatin-gum arabic is clad disperses, effectThe dispersion that acidity is conducive to system, the pH=8-12 while being adjusted to last encystation, effect is that alkalescence is conducive to the stable of softgel shell.
4. the liquid crystal microcapsule of shell more than, is characterized in that, many shells liquid crystal microcapsule comprises capsule-core, the first shell, swelling graftingTransition zone and the second shell; The first shell and swelling grafting layer comprise the material being made up of pure natural substance, and the second shell comprisesThe material being made up of polymerisable organic compound, in the first shell, the material of pure natural substance composition is to utilize Arabic treeThe different hydrophilic colloid aqueous solution of electric charge of glue, gelatin, forms the clad of liquid crystal surfactant fast, with formaldehyde, pyridine salt itsMiddle one is done curing agent, with 1,3,5-trihydroxybenzene, hybar X, uracil, sodium hydrogen tartrate wherein one do hardening accelerator and carry outQuick cross-linking forms; The second shell is polymer, and it is made up of polymerisable organic compound styrene, and the second shell is usedInitator is potassium peroxydisulfate or ammonium persulfate or dibenzoyl peroxide, and the emulsifying agent wherein using is enuatrol, dodecylBenzene sulfonic acid sodium salt or lauryl sodium sulfate one wherein; Between first and second shell, also constructed with 50% gelatin/50% gum arabic forms swelling grafting transition zone in heating process; Capsule-core layer is the liquid crystal with butanone or acetone solution,Increase microemulsion with butanone or acetone solution and spread and mobile effect, above-mentioned capsule is small evenly, and particle diameter is 2 μ m-20 μ m.
5. liquid crystal microcapsule as claimed in claim 4, is characterized in that, capsule-core is little molecule cholesteryl liquid crystal, this cholestericLiquid crystal is the combination of single kind liquid crystal or several liquid crystal.
6. liquid crystal microcapsule as claimed in claim 4, is characterized in that, capsule-core liquid crystal used is with 50% butanone or 50% the thirdKetone dissolves, thereby increases microemulsion diffusion and mobile effect, and the capsule-core solution of liquid crystal and butanone or acetone accounts for total system weight4.25% of amount.
7. liquid crystal microcapsule as claimed in claim 4, is characterized in that, the hydrophilic solution that the first housing uses for concentration isThe Arabic gum aqueous solution of 15-20%, accounts for 1.59% of system gross weight, and aqueous gelatin solution concentration is 15-20%, accounts for system1.59% of gross weight, accounts for the 10-20% of this layer of total solid content.
8. liquid crystal microcapsule as claimed in claim 4, is characterized in that,, accounts for as sclerosis crosslinking agent taking concentration as 37% formaldehyde0.637% of total system weight; The hardening accelerator 1,3,5-trihydroxybenzene of 1% concentration or hybar X account for total system weight0.03%; For the distilled water of diluted system, account for 74.4% of total system weight.
9. liquid crystal microcapsule as claimed in claim 4, is characterized in that, the swelling grafting transition in first and second shellLayer, it is to be formed by 15-20% colloidal solution, and described colloidal solution is 50% gelatin/50% gum arabic, and both account for always altogether1% of system weight, the 80-95% of this layer of solid content, emulsifying agent enuatrol accounts for 0.03% of total system weight, dissolved emulsifierSolvent be distilled water, account for 5.3% of total system weight.
10. liquid crystal microcapsule as claimed in claim 4, is characterized in that, the second shell contains emulsifying agent enuatrol or 12Sodium alkyl benzene sulfonate, accounts for 0.021% of total system weight.
11. liquid crystal microcapsules as claimed in claim 4, is characterized in that, the initiator potassium persulfate of styrene monomer or mistakeAmmonium sulfate or dibenzoyl peroxide a kind of 0.053% of total system weight that accounts for wherein.
12. liquid crystal microcapsules as claimed in claim 4, is characterized in that, styrene monomer accounts for 0.9% of total system weight,Be distilled water for the solvent that dissolves initator, emulsifying agent and monomer, account for 10% of total system weight.
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| CN109317064B (en) * | 2018-09-30 | 2020-07-07 | 江南大学 | Preparation method of carbon black-doped liquid crystal microcapsule |
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