CN102430371A - Urea-formaldehyde resin microcapsule material with capsule core half-filled structure and preparation method thereof - Google Patents
Urea-formaldehyde resin microcapsule material with capsule core half-filled structure and preparation method thereof Download PDFInfo
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- CN102430371A CN102430371A CN2011102443918A CN201110244391A CN102430371A CN 102430371 A CN102430371 A CN 102430371A CN 2011102443918 A CN2011102443918 A CN 2011102443918A CN 201110244391 A CN201110244391 A CN 201110244391A CN 102430371 A CN102430371 A CN 102430371A
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Abstract
The invention discloses a urea-formaldehyde resin microcapsule with a capsule core half-filled structure and a preparation method thereof. The urea-formaldehyde resin microcapsule is prepared by the following steps of: performing ultrasonic treatment on two liquids of different volatilities to serve as core materials; synthesizing powdery microcapsule with excellent dispersibility through polymerization reaction of urea and formaldehyde; and then releasing the core material serving as a volatile component in the prepared microcapsule under the condition of 60 DEG C and maintaining the non-volatile component in the microcapsule to obtain the half-filled microcapsule with a stable structure. The microcapsule prepared by the method can have a half-filled cavity with different cavity ratios by controlling the proportion of the mixed core material. The preparation method has the advantages of readily available raw materials and simple process; and the microcapsule has high structural strength and high stability.
Description
Technical field
The present invention relates to a kind of urea-formaldehyde resin microcapsule material and preparation method thereof, especially a kind of have capsule-core and partly be full of urea-formaldehyde resin microcapsule material of structure and preparation method thereof.
Technical background
Microcapsules are that the natural or synthetic macromolecule filming material of a kind of usefulness coats dispersed solids material, drop or gas fully, make it become the fine particle with nucleocapsid structure, so that it has special function.After U.S. NCR Corp. utilized microcapsules technology to process first generation NCR, microcapsules technology obtained extensive use in medicine, spices and essence, anticorrosion, textile, pigment, liquid crystal display, agricultural chemicals and military field.Along with the continuous progress of microcapsules technology, the application of microcapsules is also constantly expanded.
In recent years, along with the application of microcapsules in the composite selfreparing, the feasible Research Significance that can be applicable to the polymer matrix composites microcapsules of synthesizing is more outstanding.Especially in the damping material field; Because the unique nucleocapsid structure of microcapsules; When microcapsules are used for resin matrix as filler, can wait the damping capacity (plastics science and technology 2010,38 (8)) of regulating composite through the viscosity that changes the microcapsules core materials, the size of microcapsules particle diameter.As far as microcapsules/resin compounded damping material; The resonance potential of liquid (or gas) cavity must produce great influence to the damping capacity of material in the microcapsules; If can prepare a kind of microcapsules that capsule-core partly is full of structure that have; Through regulating the size of microcapsules internal cavity, be expected to obtain the excellent microcapsules/resin composite materials of damping capacity.Yet traditional method for preparing microcapsules can only be prepared and be full of the perhaps microcapsules of hollow fully; As Chinese patent 200910098979.X disclose a kind of with silica dioxide granule, silane coupler be feedstock production the parcel silica dioxide granule microcapsules; In hydrofluoric acid solution, inner silicon dioxide granule is removed then, obtained the microcapsules of multi-cavity chamber.BP WO 96/15814 discloses and has utilized protein aqueous solution to spray in the gas, makes the method for aqueous solvent evaporation obtain being used to strengthen the hollow microcapsule of ultrasonic imaging.For how preparing a kind of microcapsules that capsule-core partly is full of structure that have, relevant report is not arranged also at present.
Summary of the invention:
The object of the present invention is to provide and a kind ofly have capsule-core and partly be full of structure Preparation of Urea-formaldehyde Microcapsule method.This method technology is simple relatively, controllable process.The microcapsules that make have the stable structure that partly is full of.
The present invention realizes through following technical proposals: at first choose two kinds of water-fast liquid that volatility differs greatly as core, under ultrasonication, two kinds of liquid cores are mixed in certain proportion.In the process of preparation urea-formaldehyde resin microcapsule, will mix the core coating through polycondensation reaction, the less urea-formaldehyde resin microcapsule of particle diameter distribution of system through condition formaldehyde such as control stir speed (S.S.), emulsifier content, reaction temperature and urea.With the microcapsules of the mixing core that obtains at a certain temperature, make and mix volatile components tetrachloro-ethylene volatilization in the core, partly be full of the microcapsules of structure.What can obtain simultaneously different cavity ratios through the ratio of control internal mix core partly is full of the structure microcapsules.A kind of preparation method with the microcapsules that partly are full of structure is characterized in that comprising following process:
(1) preparation of mixing core
Two kinds of organic phase solutions of a certain proportion of different volatility are mixed under 50 ℃, behind supersonic oscillations 30min, obtain the organic phase solution of homogeneous stability, sealing is preserved subsequent use.
(2) preparation of microcapsules
Under the room temperature; Add in reactor that a certain amount of (0.2～0.35wt%) the aqueous solution that contains surfactant stirs down to wherein adding certain amount of urea and accounting for sodium chloride, ammonium chloride and the resorcinol of urea quality 10%～15% water as the preparation microcapsules.With NaOH or HCl solution the pH value of solution is transferred to high degree of agitation limit, 3.5. limit and drip the mixing oil phase core material that accounts for water volume 10%-30% (this oil phase is water insoluble and do not dissolve each other) with Lauxite wall material.Adding formalin behind the emulsification 30min under certain stir speed (S.S.).Slowly be warming up to 50-60 ℃, finish reaction behind isothermal reaction 3～4h, cooling, suction filtration, be drying to obtain free-pouring microscapsule powder.
(3) partly be full of the preparation of microcapsules
With the Powdered microcapsules that obtain behind 60 ℃ of condition held 120h, obtain rock-steady structure partly to be full of the microcapsules scheme specific as follows:
Having invented a kind of inside is the stable urea-formaldehyde resin microcapsule material that partly is full of cavity structure.
Aforesaid urea-formaldehyde resin microcapsule preparation methods may further comprise the steps:
Further, two kinds of different cores mix to obtain the microcapsules of different cavity size in varing proportions described in the step 1, and mixed volume is 0～4 than ratio scope.
Further, two kinds of liquid cores carry out the homogeneous phase mixing through sonicated described in the step 1.
Further, two kinds of liquid cores all do not dissolve each other in water described in the step 1, and can dissolve each other between the two and be homogeneous phase solution.
Further, said two kinds of liquid cores, the relative volatility of two kinds of liquid cores is greater than 100.
Further, the core of said high volatility is a kind of in the following core: tetrachloro-ethylene, carbon tetrachloride or acetone, low volatility be a kind of in the following core: olive oil, atoleine or hexadecane.
Further; Further comprising the steps of described in the step 2: under the room temperature through urea and prepared formaldehyde Lauxite; In reactor, add the aqueous solution that contains the surfactant that accounts for urea quality 12%～20%; Stir down to wherein adding urea and the ammonium chloride and the resorcinol that account for urea quality 10%～15%,, the pH value of solution is transferred to 2.5～4.5 as water; Add the mixing core that accounts for water volume 10%～30%, add after the emulsification and contain the formalin that accounts for urea quality 80%～100% formaldehyde.
Further, said surfactant is an anionic surfactant.
Further, said anionic surfactant is polyvinyl-maleic anhydride or neopelex.
The invention has the advantages that and to obtain the microcapsules of various cavitys through regulating the ratio of two kinds of liquid cores than structure.Preparation simultaneously partly to be full of microcapsules cyst wall intensity high, be not out of shape because of the part volatilization of capsule-core, its structure and core volatilize, and difference is not little before; Its structure is as shown in Figure 2, shows among the figure, after the core volatilization; Microcapsules are not out of shape, and can well disperse.Core is not an atoleine owing to volatilize, and it partly is full of cavity structure stable existence for a long time, and after after a while, core no longer discharges.Partly be full of structure by what the thermogravimetic analysis (TGA) before and after the microcapsules core volatilization had also proved microcapsules, as shown in Figure 5, these microcapsules that partly are full of structure can improve the damping capacity of material.
Description of drawings:
Fig. 1 partly is full of structural representation for microcapsules;
Fig. 2 is the sem photograph that partly is full of structure microcapsules pattern;
Fig. 3 is that capsule-core prepares the weight-loss curve of different microcapsules under 60 ℃ for the mixed solution with tetrachloro-ethylene, olive oil, tetrachloro-ethylene and olive oil.
Fig. 4 respectively with tetrachloro-ethylene, olive oil be core preparation microcapsules with mix microcapsules that core prepares, partly be full of the thermogravimetic analysis (TGA) figure of the microcapsules of structure;
Fig. 5 is respectively the damping capacity correlation curve that is full of tetrachloro-ethylene core microcapsules and half filled with liquid paraffin core microcapsules entirely.
The specific embodiment:
(1) 10g tetrachloro-ethylene and 5.5g olive oil are mixed stirring down at 50 ℃, and ultrasonication 30min, the homogeneous phase organic solution that obtains mixing.
(2) under the room temperature, in the 250ml four-hole bottle, adding 15ml concentration is the polyvinyl-maleic anhydride aqueous solution of 2.5wt%, under the stirring condition, to wherein adding 2.5g urea, 0.25g ammonium chloride and 0.25g resorcinol.With hydrochloric acid or sodium hydrate aqueous solution the pH value of solution is adjusted to 3.5.The adjusting speed of agitator is 600rpm, to wherein slowly dripping prepared mixing core in (1), emulsification 30min.Begin reaction after adding the 6.4g mass fraction and be 37% formalin, slowly be warming up to 50-60 ℃, stop reaction behind the 3h, cooling, suction filtration spend deionised water, and drying obtains free-pouring microscapsule powder under the room temperature.Get dried microcapsules and place measuring cup, in 60 ℃ of baking ovens, heat-treat, its weightless situation is investigated in the calculated mass loss, measures the result and is shown in Fig. 3.
Among the embodiment 1, change the 5.5g olive oil that adds into adding 6g atoleine, all the other are with embodiment 1.
Among the embodiment 1, the initial pH value of reactant liquor is adjusted to 4.5, all the other are with embodiment 1.
Among the embodiment 1, the initial pH value of reactant liquor is adjusted to 2.5, all the other are with embodiment 1.
Among the embodiment 1, change the amount that adds the polyvinyl-maleic anhydride aqueous solution in the reactant liquor into 5ml, all the other are with embodiment 1.
Embodiment 6
Among the embodiment 1, change the amount that adds the polyvinyl-maleic anhydride aqueous solution in the reactant liquor into 25ml, all the other are with embodiment 1.
Embodiment 7
Among the embodiment 1, be that the polyvinyl-maleic anhydride aqueous solution of 2.5wt% changes into and adds the 0.1g sodium dodecyl benzenylsulfonate with adding 15ml concentration, all the other are with embodiment 1.
The standard specimen preparation
Under the room temperature, get a certain amount of epoxy resin and place beaker to stir with the modified amine epoxy curing agent that accounts for epoxy resin-base 30%～40%.Build and solidify 12h in the self-control grinding tool under 70 ℃, obtain being used to test the standard batten of DMA.
Comparative Examples 1
Under the room temperature, in the 250ml four-hole bottle, adding 15ml concentration is the polyvinyl-maleic anhydride aqueous solution of 2.5wt%, under the stirring condition, to wherein adding 2.5g urea, 0.25g ammonium chloride and 0.25g resorcinol.With hydrochloric acid or sodium hydrate aqueous solution the pH value of solution is adjusted to 3.5.The adjusting speed of agitator is 600rpm, to wherein slowly dripping the 20g tetrachloro-ethylene as core, emulsification 30min.Begin reaction after adding 6.4g formalin, slowly be warming up to 50-60 ℃, stop reaction behind the 3h, cooling, suction filtration spend deionised water, and drying obtains free-pouring microscapsule powder under the room temperature.Get dried microcapsules and place measuring cup, in 60 ℃ of baking ovens, heat-treat, its weightless situation is investigated in the calculated mass loss, measures the result and is shown in Fig. 3.
Comparative Examples 2
In the Comparative Examples 1, change core into adding 11g olive oil, all the other are with Comparative Examples 1.
The weight-loss curve of embodiment 1, Comparative Examples 1 or Comparative Examples 2 is measured the result and is shown in Fig. 3.
The weightless assay determination result of embodiment 1, Comparative Examples 1 or Comparative Examples 2 is shown in Fig. 4.Can find through contrast, be the liquid of two kinds of different volatility owing to mix core, after release after a while, calculates through weightlessness, obtained partly being full of the microcapsules of structure.
The damping capacity correlation curve of embodiment 1, embodiment 2, embodiment 7, Comparative Examples 1 and standard specimen is measured the result and is shown in Fig. 5.
Being merely the preferred embodiment of invention in sum, is not to be used for limiting practical range of the present invention.Be that all equivalences of doing according to the content of claim of the present invention change and modification, all should be technological category of the present invention.
Claims (10)
1. have capsule-core and partly be full of the urea-formaldehyde resin microcapsule material of structure, it is characterized in that, these microcapsules are inner to be the stable cavity structure that partly is full of.
2. a urea-formaldehyde resin microcapsule preparation methods as claimed in claim 1 is characterized in that,
Step 1 is chosen the liquid core of two kinds of different volatility, makes it fully be mixed into homogeneous phase;
Step 2 adds the described mixing core of step 1 through in urea and the prepared formaldehyde Lauxite wall material process, is warming up to 50～60 ℃, and insulation reaction 3～4h finishes to react, and cooling, suction filtration, is drying to obtain the microcapsule wall material powder.
3. preparation method as claimed in claim 2 is characterized in that, two kinds of different cores mix to obtain the microcapsules of different cavity size in varing proportions described in the step 1, and mixed volume is 0～4 than ratio scope.
4. preparation method as claimed in claim 2 is characterized in that, two kinds of liquid cores described in the step 1 carry out homogeneous phase through sonicated to be mixed.
5. preparation method as claimed in claim 2 is characterized in that, two kinds of liquid cores all do not dissolve each other in water described in the step 1, and can dissolve each other between the two and be homogeneous phase solution.
6. like arbitrary preparation method in the claim 2～5, it is characterized in that, said two kinds of liquid cores, the relative volatility of two kinds of liquid cores is greater than 100.
7. like arbitrary preparation method in the claim 6; It is characterized in that; The core of said high volatility is a kind of in the following core: tetrachloro-ethylene, carbon tetrachloride or acetone, low volatility be a kind of in the following core: olive oil, atoleine or hexadecane.
8. preparation method as claimed in claim 2; It is characterized in that; Further comprising the steps of described in the step 2: as under the room temperature, in reactor, to add the aqueous solution that contains the surfactant that accounts for urea quality 12%～20%, stir down to wherein adding urea and the ammonium chloride and the resorcinol that account for urea quality 10%～15% through urea and prepared formaldehyde Lauxite; As water; The pH value of solution is transferred to 2.5～4.5, add the mixing core that accounts for water volume 10%～30%, add after the emulsification and contain the formalin that accounts for urea quality 80%～100% formaldehyde.
9. preparation method as claimed in claim 8 is characterized in that, said surfactant is an anionic surfactant.
10. like preparation method as claimed in claim 9, it is characterized in that said anionic surfactant is polyvinyl-maleic anhydride or neopelex.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108813761A (en) * | 2018-05-14 | 2018-11-16 | 江苏瑞斯达安全防护用品有限公司 | PVC slip-proof glove and its production technology with open cells structure |
| CN115000516A (en) * | 2022-06-17 | 2022-09-02 | 吉林大学 | Ammonium polyphosphate @ polyurea-formaldehyde microcapsule structured flame retardant material and synthesis method thereof |
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| CN101113322A (en) * | 2006-07-24 | 2008-01-30 | 中国科学院化学研究所 | Method for preparation of monodisperse phase-change microcapsule |
| CN101274248A (en) * | 2007-12-28 | 2008-10-01 | 哈尔滨工业大学 | Surface treating method of microcapsule for polymer based composite self-repair |
| CN101362067A (en) * | 2007-08-06 | 2009-02-11 | 天津科技大学 | Microcapsule preparation method |
| US20100071882A1 (en) * | 2008-09-25 | 2010-03-25 | Eternal Chemical Co., Ltd. | Natural microtubule encapsulated phase-change materials and preparation thereof |
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- 2011-08-25 CN CN2011102443918A patent/CN102430371A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113322A (en) * | 2006-07-24 | 2008-01-30 | 中国科学院化学研究所 | Method for preparation of monodisperse phase-change microcapsule |
| CN101362067A (en) * | 2007-08-06 | 2009-02-11 | 天津科技大学 | Microcapsule preparation method |
| CN101274248A (en) * | 2007-12-28 | 2008-10-01 | 哈尔滨工业大学 | Surface treating method of microcapsule for polymer based composite self-repair |
| US20100071882A1 (en) * | 2008-09-25 | 2010-03-25 | Eternal Chemical Co., Ltd. | Natural microtubule encapsulated phase-change materials and preparation thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108813761A (en) * | 2018-05-14 | 2018-11-16 | 江苏瑞斯达安全防护用品有限公司 | PVC slip-proof glove and its production technology with open cells structure |
| CN115000516A (en) * | 2022-06-17 | 2022-09-02 | 吉林大学 | Ammonium polyphosphate @ polyurea-formaldehyde microcapsule structured flame retardant material and synthesis method thereof |
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Application publication date: 20120502 |