CN103301789A - Preparation method of microcapsule for self-repair material with phenolic resin as wall material - Google Patents
Preparation method of microcapsule for self-repair material with phenolic resin as wall material Download PDFInfo
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- CN103301789A CN103301789A CN2013102249067A CN201310224906A CN103301789A CN 103301789 A CN103301789 A CN 103301789A CN 2013102249067 A CN2013102249067 A CN 2013102249067A CN 201310224906 A CN201310224906 A CN 201310224906A CN 103301789 A CN103301789 A CN 103301789A
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Abstract
The invention relates to the technical field of a self-repair material, and provides a microcapsule for a self-repair material with phenolic resin as a wall material. The wall material of the microcapsule is cross-linked and solidified phenolic resin; a core material is dicyclopentadiene. The invention also provides a preparation method of the microcapsule for the self-repair material with phenolic resin as the wall material. The preparation method comprises the following steps of: preparing thermosetting resin to obtain reaction liquid; preparing core material emulsion; mixing the core material emulsion with the reaction liquid at 60-65 DEG C to obtain mixing solution; adjusting the pH value of the mixing solution to 2.5-1; heating to 70-80 DEG C; reacting for 1.5-2hours; heating to 85-90 DEG C; reacting for 1.5-2 hours, so as to obtain microcapsule sediments; and filtering and drying at 40-60 DEG C, so as to obtain the microcapsule for the self-repair material with phenolic resin as the wall material.
Description
Technical field
The invention belongs to the self-repair material technical field, be specifically related to a kind of microcapsules that are used for self-repair material take phenolic resins as the wall material and preparation method thereof.
Background technology
Phenolic resins is industrial widely used a kind of polymer, and it has remarkable adhesiveness, good heat resistance, unique anti-ablation ability and good anti-flammability, and synthesis technique is simple, cheap.Phenolic resins is a large class synthetic resin that forms by phenol and aldehyde polycondensation, phenol commonly used has: phenol, cresols, mixture cresol, nonyl phenol, octyl phenol, xylenol, anacardol, aralkyl phenol, bisphenol-A etc., aldehyde commonly used has: formaldehyde, paraformaldehyde, furfural, acetaldehyde etc., and wherein the most frequently used with the synthetic phenolic resins (PF) of phenol (Phenol) and formaldehyde (Formaldehyde).
The synthetic reaction of phenolic resins is in two steps: the first step is addition reaction, is that formaldehyde and phenol effect generate a methylol and hydroxymethyl-phenol; Second step is condensation and polycondensation reaction, is hydroxymethylphenol and phenol, or the progressively chain propagation reaction between the hydroxymethylphenol.The Acidity of Aikalinity of the chemical constitution that the structure of the PF polymer that finally obtains and character depend mainly on raw material, phenol/aldehyde mol ratio (P/F) and reaction medium.It is divided into two kinds of thermoplastic resin (Novolak) and thermosetting resins (Resole) usually.The Novolak formation condition generally is: pH＜3, P/F〉1, reaction temperature〉60 ℃; And the formation condition of Resole is: pH〉7, P/F＜1, reaction temperature〉60 ℃.Novolak and Resole are solvable fusible, just have good mechanical property, electrical insulation capability, chemical stability and heat endurance after only having crosslinking curing, but Novolak can not solidify voluntarily, needs to add catalyst and formaldehyde, and Resole can heat or directly solidify in acid medium.According to the difference of state of cure, usually Resole is divided into first rank, second rank and the third rank.First rank Resole dissolves in the alkaline aqueous solution, ethanol, acetone etc.; Second rank Resole can only be dissolved in or even be partially soluble in ethanol or the acetone, is insoluble to alkaline aqueous solution; The third rank are crosslinking curing fully, is not dissolved in any solvent, does not also melt.Usually will claim two step method through the route of Novolak novolak resin, claim one-step method through the route of Resole.
Phenolic resins rarely has report as the wall material of microcapsules, but phenolic resins is synthetic simple, cheap, and the wall material that is used as microcapsules is widely used pollopas, melamine resin and polyureas and should has more advantage than at present.Existing report shows, phenolic resins is good microcapsule wall material, microcapsule preparation process take it as the wall material is also also uncomplicated, the tiny microcapsules (average grain diameter only has 7.5 μ m) that prepared the phenolic aldehyde encapsulated red phosphorus such as document one [plastics industry, 39(2011) 89-92] by situ aggregation method.Document two [Chinese invention patent, publication number CN101249409B, 2008] has prepared ultrafine microencapsulated (particle diameter hundreds of nanometer is to several microns) of phenolic aldehyde coating amine hardener by situ aggregation method, can make amine ooze out cured epoxy under 120 ℃.Document three [Chinese invention patent, publication number CN100496698C, 2006] makes first the microcapsules that the Resole phenolic aldehyde coats alkane then take thermosetting phenolic resin (first rank Resole) as raw material by the coacervation that is separated, and heating is solidified phenolic aldehyde wall material again.Document four [Chinese invention patent, publication number CN102618223A, 2012] is also take thermosetting phenolic resin as raw material, but the employing situ aggregation method has prepared the microcapsules of phenolic aldehyde coating alkane.
Do not see up to now the relevant report that is used for the microcapsules of self-repair material take phenolic resins as the wall material.Possible reason is that self-repair material epoxy resin commonly used is done renovation agent, and phenolic resins and epoxy curing agent each other, perhaps this is so that the microcapsules difficult of novolak resin coating epoxy.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of prior art, and a kind of microcapsules that are used for self-repair material take phenolic resins as the wall material and preparation method thereof are provided.
The present invention is achieved in that provides a kind of microcapsules that are used for self-repair material take phenolic resins as the wall material, and its wall material is the phenolic resins of crosslinking curing, and core is bicyclopentadiene.
The embodiment of the invention also provides a kind of preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material, and it comprises the steps:
Produce first rank thermosetting resin: the pH value to 8 of adjusting phenol and aldehyde mixed aqueous solution～10, be warming up to 60～65 ℃, stir, be warming up to again 70～90 ℃ of reactions, get reactant liquor, wherein, the mol ratio of phenol and aldehyde is 1:1～3 in described phenol and the aldehyde mixed aqueous solution;
Produce the core emulsion: 40～120% bicyclopentadiene, polyacrylic acid and the water of getting described phenol and aldehyde phenol in aqueous solution and aldehyde quality summation mix, be warming up to 50～80 ℃, stir, get the core emulsion, wherein, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:0.5～2:3～14;
Under 60～65 ℃, described core emulsion is mixed with described reactant liquor, get mixed liquor, regulate described pH of mixed value to 2.5～1, be warming up to 70～80 ℃, reacted 1.5～2 hours, be warming up to again 85～90 ℃, reacted 1.5～2 hours, and got the microcapsules precipitation, suction filtration, 40～60 ℃ of dryings obtain the described microcapsules that are used for self-repair material take phenolic resins as the wall material.
The microcapsules that are used for self-repair material take phenolic resins as the wall material provided by the invention, size is large, and form is regular, and wall thickness is even, and is sticking glutinous, easily disperses, and cyst wall is fine and close, hard and crisp, easily triggered by stress and broken, is particularly suitable for the self-repair material use.Further, because the phenolic resins behind the curing cross-linked is hard and crisp, be especially suitable for use as the wall material of the self-repairing microcapsule of mechanics triggering.
Description of drawings
Fig. 1 is the optical microscope photograph that is used for the microcapsules of self-repair material take phenolic resins as the wall material of the embodiment of the invention 1 preparation;
Fig. 2 is the stereoscan photograph that is used for the microcapsules of self-repair material take phenolic resins as the wall material of the embodiment of the invention 1 preparation;
Fig. 3 is the optical microscope photograph that is used for the microcapsules of self-repair material take phenolic resins as the wall material of the embodiment of the invention 2 preparations;
Fig. 4 is the stereoscan photograph that is used for the microcapsules of self-repair material take phenolic resins as the wall material of the embodiment of the invention 2 preparations.
The specific embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of microcapsules that are used for self-repair material take phenolic resins as the wall material, and its wall material is the phenolic resins of crosslinking curing, and core is bicyclopentadiene (DCPD).
Wherein, described microcapsules are of a size of 30～1000 μ m.
The embodiment of the invention also provides a kind of preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material, comprises the steps:
S01: produce first rank thermosetting resin: the pH value to 8 of adjusting phenol and aldehyde mixed aqueous solution～10, be warming up to 60～65 ℃, stir, be warming up to again 70～90 ℃ of reactions, get reactant liquor, wherein, the mol ratio of phenol and aldehyde is 1:1～3 in described phenol and the aldehyde mixed aqueous solution;
S02: produce the core emulsion: 40～120% bicyclopentadiene, polyacrylic acid and the water of getting described phenol and aldehyde phenol in aqueous solution and aldehyde molal weight summation mix, be warming up to 50～80 ℃, stir, get the core emulsion, wherein, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:(0.5～2): (3～14);
S03: under 60～65 ℃, described core emulsion is mixed with described reactant liquor, get mixed liquor, regulate described pH of mixed value to 2.5～1, be warming up to 70～80 ℃, reacted 1.5～2 hours, be warming up to again 85～90 ℃, reacted 1.5～2 hours, and got the microcapsules precipitation, suction filtration, 40～60 ℃ of dryings obtain the described microcapsules that are used for self-repair material take phenolic resins as the wall material.
Particularly, among the step S01, described phenol is at least a in phenol, cresols, the mixture cresol, is preferably phenol; Described aldehyde is at least a in formaldehyde, paraformaldehyde, furfural, the acetaldehyde, is preferably formaldehyde; Described phenol/aldehyde mol ratio is 1:(1.2～2.0), preferred 1:1.5; Described adjusting phenol and aldehyde pH value of water solution are selected the 5wt%NaOH aqueous solution.
Among the step S02, described polyacrylic acid is the key that successfully obtains phenolic aldehyde bag epoxy microcapsule.
Step S03 specifically comprises the steps:
S031: mix: regulate the temperature to 60 of described core emulsion～65 ℃, and regulate stir speed (S.S.) to 280～550 rpm, with described reactant liquor, namely Resole solution all is added in the described core emulsion;
S032: acid adjustment second processed rank Resole cyst wall: add pH value conditioning agent in the reactant liquor of S031 and core emulsion, regulate pH value to 2.5～1, temperature and stir speed (S.S.) in the maintenance S031 step are constant;
S033: heat up to solidify system the third rank Resole cyst wall: keep in the S032 step stir speed (S.S.) constant, temperature is transferred to 70～80 ℃ first, and insulation reaction 1.5～2 hours, temperature is risen to 85～90 ℃ again, insulation reaction 1.5～2 hours gets the spherical microcapsules precipitation of rufous, and gained sediment vacuum filters, 40～60 ℃ of dryings get target product.Wherein, described pH value is regulated the aqueous hydrochloric acid solution of selecting 2wt%.
The preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material provided by the invention, can avoid the Microcapsules Size of background technology Literature one and two preparations too small, and being not suitable for the defective that self-repair material uses, the phenolic aldehyde that can prepare large particle diameter (30～1000 μ m) coats the DCPD microcapsules.
Below illustrate the above-mentioned preparation that is used for the microcapsules of self-repair material take phenolic resins as the wall material by specific embodiment.
Embodiment one:
Difference weighing 5g phenol (P) and 6.5g formaldehyde (F), place 500mL that the there-necked flask of condenser pipe reflux is housed, add the 5wt%NaOH aqueous solution and regulate pH value to 9, first 65 ℃ of lower stirrings 10 minutes, then be warming up to 70 ℃ and insulation reaction 2 hours, and obtained rufous first rank Resole solution.
Be equipped with in the 500mL there-necked flask of agitator, thermometer at another, add 7g dicyclopentadiene (DCPD) as core, 7g polyacrylic acid (pH=6～7) as emulsifying agent and 50g distilled water as continuous phase, be heated to 70 ℃, stirred 20 minutes with 1000 rpms rates of rotation, get the DCPD white emulsion.Regulate DCPD emulsion temperature to 65 ℃, reducing stir speed (S.S.) is 500 rpms, and first rank Resole solution all is added drop-wise in the DCPD emulsion with per 4 seconds one speed, after mixing, slowly drip 2% hydrochloric acid solution, regulate pH value to 1, then be warming up to 70 ℃, insulation reaction 2 hours, rise to 90 ℃, insulation reaction 2 hours stops to stir again, cooling gets the spherical microcapsules of rufous in the reactant liquor bottom.
With the product vacuum filter, clear water washing, 40～60 ℃ of dryings are after 4 hours, the microcapsules that are used for self-repair material take phenolic resins as the wall material that obtain are carried out optics and scanning electron microscopy is observed, Fig. 1 is the optical microphotograph picture, Fig. 2 is the ESEM picture.As shown in the figure, capsule grain diameter is 60～300 μ m, and wall thickness is about 3 μ m.
Embodiment two:
Difference weighing 5g phenol (P) and 7.5g formaldehyde (F), place 500mL that the there-necked flask of condenser pipe reflux is housed, add the 5wt%NaOH aqueous solution and regulate pH value to 10, first 65 ℃ of lower stirrings 10 minutes, then be warming up to 80 ℃ and insulation reaction 1.5 hours, and obtained rufous first rank Resole solution.
Be equipped with in the 500mL there-necked flask of agitator, thermometer at another, add 14g dicyclopentadiene (DCPD) as core, 20g polyacrylic acid (pH=6～7) as emulsifying agent and 100g distilled water as continuous phase, be heated to 70 ℃, stirred 20 minutes with 1000 rpms rates of rotation, get the DCPD white emulsion.Regulate DCPD emulsion temperature to 65 ℃, reducing stir speed (S.S.) is 300 rpms, directly all joins first rank Resole solution in the DCPD emulsion, after mixing, slowly drip 2% hydrochloric acid solution, regulate pH value to 2, then be warming up to 75 ℃, insulation reaction 2 hours, rise to 90 ℃, insulation reaction 2 hours stops to stir again, cooling gets the spherical microcapsules of rufous in the reactant liquor bottom.
With the product vacuum filter, clear water washing, 40～60 ℃ of dryings are after 4 hours, the microcapsules that are used for self-repair material take phenolic resins as the wall material that obtain are carried out optics and scanning electron microscopy is observed, Fig. 3 is the optical microphotograph picture, Fig. 4 is the ESEM picture.As can be seen from the figure, Microcapsules Size is 400～1000 μ m, and wall thickness is about 3 μ m.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. microcapsules that are used for self-repair material take phenolic resins as the wall material is characterized in that, the wall material of described microcapsules is the phenolic resins of crosslinking curing, and core is bicyclopentadiene.
2. the microcapsules that are used for self-repair material take phenolic resins as the wall material as claimed in claim 1 is characterized in that, described microcapsules are of a size of 30～1000 μ m.
3. preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material, it comprises the steps:
Produce first rank thermosetting resin: the pH value to 8 of adjusting phenol and aldehyde mixed aqueous solution～10, be warming up to 60～65 ℃, stir, be warming up to again 70～90 ℃ of reactions, get reactant liquor, wherein, the mol ratio of phenol and aldehyde is 1:1～3 in described phenol and the aldehyde mixed aqueous solution;
Produce the core emulsion: 40～120% bicyclopentadiene, polyacrylic acid and the water of getting described phenol and aldehyde phenol in aqueous solution and aldehyde quality summation mix, be warming up to 50～80 ℃, stir, get the core emulsion, wherein, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:0.5～2:3～14;
Under 60～65 ℃, described core emulsion is mixed with described reactant liquor, get mixed liquor, regulate described pH of mixed value to 2.5～1, be warming up to 70～80 ℃, reacted 1.5～2 hours, be warming up to again 85～90 ℃, reacted 1.5～2 hours, and got the microcapsules precipitation, suction filtration, 40～60 ℃ of dryings obtain the described microcapsules that are used for self-repair material take phenolic resins as the wall material.
4. the preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material as claimed in claim 3, it is characterized in that, described phenol is at least a in phenol, cresols, the mixture cresol, and described aldehyde is at least a in formaldehyde, paraformaldehyde, furfural, the acetaldehyde.
5. such as claim 3 or the 4 described preparation methods that are used for the microcapsules of self-repair material take phenolic resins as the wall material, it is characterized in that, described phenol is phenol, and described aldehyde is formaldehyde.
6. the preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material as claimed in claim 3 is characterized in that, the mol ratio of described phenol and aldehyde phenol in aqueous solution and aldehyde is 1:1.2～2.0.
7. such as claim 3 or the 6 described preparation methods that are used for the microcapsules of self-repair material take phenolic resins as the wall material, it is characterized in that, the mol ratio of described phenol and aldehyde phenol in aqueous solution and aldehyde is 1:1.5.
8. the preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material as claimed in claim 3 is characterized in that, the pH value to 8 of described adjusting phenol and the aldehyde aqueous solution～10 select the 5wt%NaOH aqueous solution to regulate.
9. the preparation method who is used for the microcapsules of self-repair material take phenolic resins as the wall material as claimed in claim 3, it is characterized in that, described described reactant liquor all is added in the described core emulsion, regulates the aqueous hydrochloric acid solution adjusting that 2wt% is selected in pH value to 2.5～1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310224906.7A CN103301789B (en) | 2013-06-07 | 2013-06-07 | A kind of taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material |
| PCT/CN2013/080951 WO2014194561A1 (en) | 2013-06-07 | 2013-08-07 | Preparation method for microcapsule for self-repairing material with phenolic resin as wall material |
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| CN201310224906.7A CN103301789B (en) | 2013-06-07 | 2013-06-07 | A kind of taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material |
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| CN103301789A true CN103301789A (en) | 2013-09-18 |
| CN103301789B CN103301789B (en) | 2016-05-25 |
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| WO (1) | WO2014194561A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103599739A (en) * | 2013-11-25 | 2014-02-26 | 深圳大学 | Method for preparing epoxy microcapsules by taking phenolic resin as wall material |
| CN104801248A (en) * | 2015-04-23 | 2015-07-29 | 北京宇田相变储能科技有限公司 | Water-soluble inorganic salt microcapsule and preparation method thereof |
| CN104944833A (en) * | 2015-03-31 | 2015-09-30 | 深圳大学 | Microcapsule for self-repair concrete and preparation method of self-repair concrete |
| CN105032313A (en) * | 2015-07-23 | 2015-11-11 | 北京宇田相变储能科技有限公司 | Water soluble salt microcapsule wrapped by polybenzoxazine resin and preparation method thereof |
| CN105080441A (en) * | 2015-07-28 | 2015-11-25 | 西北工业大学 | Preparation method of microcapsules coated with liquid alkene |
| CN107224945A (en) * | 2017-06-26 | 2017-10-03 | 西北工业大学 | It is a kind of using phenolic resin be wall material solids as emulsifying agent dicyclopentadiene microcapsule and preparation method |
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| CN111298729A (en) * | 2018-12-11 | 2020-06-19 | 中国船舶重工集团公司第七二五研究所 | Self-repairing microcapsule and preparation and application methods thereof |
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| CN103599739A (en) * | 2013-11-25 | 2014-02-26 | 深圳大学 | Method for preparing epoxy microcapsules by taking phenolic resin as wall material |
| WO2015074341A1 (en) * | 2013-11-25 | 2015-05-28 | 深圳大学 | Method for preparing epoxy microcapsule by using phenolic resin as wall material |
| CN103599739B (en) * | 2013-11-25 | 2015-10-21 | 深圳大学 | A kind of take phenolic resins as the preparation method of the epoxy microcapsule of wall material |
| CN104944833A (en) * | 2015-03-31 | 2015-09-30 | 深圳大学 | Microcapsule for self-repair concrete and preparation method of self-repair concrete |
| CN104801248A (en) * | 2015-04-23 | 2015-07-29 | 北京宇田相变储能科技有限公司 | Water-soluble inorganic salt microcapsule and preparation method thereof |
| CN104801248B (en) * | 2015-04-23 | 2016-06-01 | 北京宇田相变储能科技有限公司 | Water-soluble inorganic salt microcapsule and preparation method |
| CN105032313A (en) * | 2015-07-23 | 2015-11-11 | 北京宇田相变储能科技有限公司 | Water soluble salt microcapsule wrapped by polybenzoxazine resin and preparation method thereof |
| CN105080441A (en) * | 2015-07-28 | 2015-11-25 | 西北工业大学 | Preparation method of microcapsules coated with liquid alkene |
| CN105080441B (en) * | 2015-07-28 | 2017-10-13 | 西北工业大学 | A kind of preparation method for coating liquid olefinic microcapsules |
| CN107224945A (en) * | 2017-06-26 | 2017-10-03 | 西北工业大学 | It is a kind of using phenolic resin be wall material solids as emulsifying agent dicyclopentadiene microcapsule and preparation method |
| CN109453499A (en) * | 2018-10-27 | 2019-03-12 | 汇昇（厦门）运动器材有限公司 | A kind of basketball and its manufacturing process |
| CN109453499B (en) * | 2018-10-27 | 2021-03-23 | 汇昇（厦门）运动器材有限公司 | Basketball and manufacturing process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103301789B (en) | 2016-05-25 |
| WO2014194561A1 (en) | 2014-12-11 |
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