CN103301789B - A kind of taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material - Google Patents
A kind of taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material Download PDFInfo
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- CN103301789B CN103301789B CN201310224906.7A CN201310224906A CN103301789B CN 103301789 B CN103301789 B CN 103301789B CN 201310224906 A CN201310224906 A CN 201310224906A CN 103301789 B CN103301789 B CN 103301789B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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Abstract
The present invention relates to self-repair material technical field, provide a kind of taking phenolic resins as wall material is for the microcapsules of self-repair material, the phenolic resins that the wall material of described microcapsules is crosslinking curing, core is bicyclopentadiene. The present invention also provides taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material, and it comprises the steps: to produce first rank thermosetting resin, obtains reactant liquor; Produce core emulsion; At 60～65 DEG C, described core emulsion is mixed with described reactant liquor, obtain mixed liquor, regulate described pH of mixed value to 2.5～1, be warming up to 70～80 DEG C, react 1.5～2 hours, be warming up to again 85～90 DEG C, react 1.5～2 hours, obtain microcapsules precipitation, suction filtration, 40～60 DEG C dry, obtains described taking phenolic resins as wall material is for the microcapsules of self-repair material.
Description
Technical field
The invention belongs to self-repair material technical field, be specifically related to a kind of taking phenolic resins as wall material for fromMicrocapsules of repair materials and preparation method thereof.
Background technology
Phenolic resins is industrial widely used a kind of polymer, and it has remarkable adhesiveness, goodAnti-ablation ability and the good anti-flammability of heat resistance, uniqueness, and synthesis technique is simple, cheap. PhenolUrea formaldehyde is the large class synthetic resin forming by phenol and aldehyde polycondensation, and conventional phenol has: phenol, cresols,Mixture cresol, nonyl phenol, octyl phenol, xylenol, anacardol, aralkyl phenol, bisphenol-A etc., conventional aldehydeHave: formaldehyde, paraformaldehyde, furfural, acetaldehyde etc., wherein with phenol (Phenol) and formaldehyde (Formaldehyde)Synthetic phenolic resins (PF) is the most frequently used.
The synthetic reaction of phenolic resins is in two steps: the first step is addition reaction, is that formaldehyde and phenol effect generateOne methylol and hydroxymethyl-phenol; Second step is condensation and polycondensation reaction, is hydroxymethylphenol and phenol,Or progressively chain propagation reaction between hydroxymethylphenol. Structure and the character of the PF polymer finally obtainingDepend mainly on the Acidity of Aikalinity of chemical constitution, phenol/aldehyde mol ratio (P/F) and the reaction medium of raw material. It is logicalOften be divided into two kinds of thermoplastic resin (Novolak) and thermosetting resins (Resole). Novolak forms barPart is generally: pH<3, P/F>1, reaction temperature>60 DEG C; And the formation condition of Resole is: pH>7,P/F<1, reaction temperature>60 DEG C. Novolak and Resole are solvable fusible, just have after only having crosslinking curingGood mechanical property, electrical insulation capability, chemical stability and heat endurance, but Novolak can not consolidate voluntarilyChange, need to add catalyst and formaldehyde, Resole can heat or directly solidify in acid medium. According to solidThe difference of change degree, is divided into Resole first rank, second rank and the third rank conventionally. First rank Resole dissolves in alkaline waterSolution, ethanol, acetone etc.; Second rank Resole can only be dissolved in or even be partially soluble in ethanol or acetone, noBe dissolved in alkaline aqueous solution; The third rank are crosslinking curing completely, is not dissolved in any solvent, does not also melt. ConventionallyTo 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,Be widely used pollopas, melamine resin and polyureas than at present as the wall material of microcapsules and should have more advantage. ?Some report demonstrations, phenolic resins is good microcapsule wall material, the microcapsule preparation process taking it as wall materialAlso also uncomplicated, as document one [plastics industry, 39 (2011) 89-92] has been prepared by situ aggregation method(average grain diameter only has 7.5 μ m) to the tiny microcapsules of phenolic aldehyde encapsulated red phosphorus. Document two [Chinese invention patent,Publication number CN101249409B, 2008] prepare the ultra-fine of the coated amine hardener of phenolic aldehyde by situ aggregation methodMicrocapsules (particle diameter hundreds of nanometer is to several microns) can make amine ooze out, cured epoxy at 120 DEG C. DocumentThree [Chinese invention patent, publication number CN100496698C, 2006] are with thermosetting phenolic resin (first rankResole) be raw material, first make the microcapsules of the coated alkane of Resole phenolic aldehyde by the coacervation that is separated, then addHeat is solidified phenolic aldehyde wall material. Document four [Chinese invention patent, publication number CN102618223A, 2012]Also taking thermosetting phenolic resin as raw material, but adopt situ aggregation method to prepare the microcapsules of the coated alkane of phenolic aldehyde.
Do not see up to now about taking phenolic resins as wall material is for the report of the microcapsules of self-repair material.A possible reason is that the conventional epoxy resin of self-repair material does renovation agent, and phenolic resins and epoxy are each otherCuring agent, perhaps this makes the microcapsules of the coated epoxy of novolak resin become difficulty.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect of prior art, provides a kind of and sets with phenolic aldehydeFat is wall material for microcapsules of self-repair material and preparation method thereof.
The present invention be achieved in that provide a kind of taking phenolic resins as wall material the micro-glue for self-repair materialCapsule, the phenolic resins that its wall material is crosslinking curing, core is bicyclopentadiene.
It is a kind of taking phenolic resins as wall material is for the system of the microcapsules of self-repair material that the embodiment of the present invention also providesPreparation Method, it comprises the steps:
Produce first rank thermosetting resin: regulate pH value to 8～10 of phenol and aldehyde mixed aqueous solution, be warming up to60～65 DEG C, stir, then be warming up to 70～90 DEG C of reactions, obtain reactant liquor, wherein, described phenol and aldehyde mixThe mol ratio of phenol in aqueous solution and aldehyde is 1:1～3;
Produce core emulsion: get 40～120% of phenol and aldehyde quality summation in described phenol and aldehyde mixed aqueous solutionBicyclopentadiene, polyacrylic acid and water mix, be warming up to 50～80 DEG C, stir, obtain core emulsion, itsIn, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:0.5～2:3～14;
At 60～65 DEG C, described core emulsion is mixed with described reactant liquor, obtain mixed liquor, regulate described mixedClose liquid pH value to 2.5～1, be warming up to 70～80 DEG C, react 1.5～2 hours, then be warming up to 85～90 DEG C,React 1.5～2 hours, obtain microcapsules precipitation, suction filtration, 40～60 DEG C are dry, obtain described with phenolic resinsFor wall material is for the microcapsules of self-repair material.
Provided by the invention taking phenolic resins as wall material is for the microcapsules of self-repair material, size is large, formRegular, wall thickness is even, sticky glutinous, easily disperse, cyst wall densification, hard and crisp, easily triggered and break by stressBroken, be particularly suitable for self-repair material and use. Further, because the phenolic resins after curing cross-linked is hard and crisp,Be especially suitable for use as the wall material of the self-repairing microcapsule of mechanics triggering.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare taking phenolic resins as wall material is for the microcapsules of self-repair materialOptical microscope photograph;
Fig. 2 be the embodiment of the present invention 1 prepare taking phenolic resins as wall material is for the microcapsules of self-repair materialStereoscan photograph;
Fig. 3 be the embodiment of the present invention 2 prepare taking phenolic resins as wall material is for the microcapsules of self-repair materialOptical microscope photograph;
Fig. 4 be the embodiment of the present invention 2 prepare taking phenolic resins as wall material is for the microcapsules of self-repair materialStereoscan photograph.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and realityExecute example, the present invention is further elaborated. Only should be appreciated that specific embodiment described hereinOnly, in order to explain the present invention, be not intended to limit the present invention.
It is a kind of taking phenolic resins as wall material is for the microcapsules of self-repair material that the embodiment of the present invention provides, its wallMaterial is the phenolic resins of crosslinking curing, and core is bicyclopentadiene (DCPD).
Wherein, described microcapsules are of a size of 30～1000 μ m.
It is a kind of taking phenolic resins as wall material is for the system of the microcapsules of self-repair material that the embodiment of the present invention also providesPreparation Method, comprises the steps:
S01: produce first rank thermosetting resin: regulate pH value to 8～10 of phenol and aldehyde mixed aqueous solution, riseTemperature, to 60～65 DEG C, stirs, then is warming up to 70～90 DEG C of reactions, obtains reactant liquor, wherein, and described phenol and aldehydeIn mixed aqueous solution, the mol ratio of phenol and aldehyde is 1:1～3;
S02: produce core emulsion: get 40 of phenol and aldehyde quality summation in described phenol and aldehyde mixed aqueous solution～120% bicyclopentadiene, polyacrylic acid and water mix, and are warming up to 50～80 DEG C, stir, and obtain core breastLiquid, wherein, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:(0.5～2): (3～14);
S03: at 60～65 DEG C, described core emulsion is mixed with described reactant liquor, obtain mixed liquor, regulateDescribed pH of mixed value to 2.5～1, is warming up to 70～80 DEG C, reacts 1.5～2 hours, then is warming up to85～90 DEG C, react 1.5～2 hours, obtain microcapsules precipitations, suction filtration, 40～60 DEG C are dry, described in acquisitionTaking phenolic resins as wall material is for the microcapsules of self-repair material.
Particularly, in step S01, described phenol is at least one in phenol, cresols, mixture cresol, preferablyFor phenol; Described aldehyde is at least one in formaldehyde, paraformaldehyde, furfural, acetaldehyde, is preferably formaldehyde;Described phenol/aldehyde mol ratio is 1:(1.2～2.0), preferably 1:1.5; Described adjusting phenol and aldehyde pH value of water solutionSelect the 5wt%NaOH aqueous solution.
In 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 temperature to 60～65 DEG C of described core emulsion, and regulate stir speed (S.S.) extremely280～550 rpms, by described reactant liquor, Resole solution is all added in described core emulsion;
S032: acid adjustment second processed rank Resole cyst wall: add pH value in the reactant liquor of S031 and core emulsionConditioning agent, regulates pH value to 2.5～1, keeps temperature and stir speed (S.S.) in S031 step constant;
S033: heat up and solidify system the third rank Resole cyst wall: maintain in S032 step stir speed (S.S.) constant, firstTemperature is adjusted to 70～80 DEG C, and insulation reaction 1.5～2 hours, then temperature is risen to 85～90 DEG C, protectTemperature reaction 1.5～2 hours, obtains the spherical microcapsules precipitation of rufous, and gained sediment vacuum filters, 40～60 DEG CDry, obtain target product. Wherein, described pH value regulates the aqueous hydrochloric acid solution of selecting 2wt%.
Provided by the invention taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material, energyEnough avoid the Microcapsules Size of background technology Literature one and two preparation too small, and be not suitable for self-repair material and makeWith defect, (30～1000 μ phenolic aldehyde m) is coated DCPD microcapsules can to have prepared large particle diameter.
Below by specific embodiment illustrate above-mentioned taking phenolic resins as wall material for self-repair materialThe preparation of microcapsules.
Embodiment mono-:
Weigh respectively 5g phenol (P) and 6.5g formaldehyde (F), be placed in 500mL condenser pipe backflow dress is housedIn the there-necked flask of putting, add the 5wt%NaOH aqueous solution to regulate pH value to 9, first at 65 DEG C, stir10 minutes, be then warming up to 70 DEG C and insulation reaction 2 hours, obtain 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 the conduct of 50g distilled waterContinuous phase, is heated to 70 DEG C, stirs 20 minutes with the rates of rotation of 1000 rpms, obtains DCPD white breastLiquid. Regulate DCPD emulsion temperature to 65 DEG C, reducing stir speed (S.S.) is 500 rpms, by first rank ResoleSolution is all added drop-wise in DCPD emulsion with the every 4 seconds speed of one, after mixing, slowly drips 2%Hydrochloric acid solution, regulate pH value to 1, be then warming up to 70 DEG C, insulation reaction 2 hours, then rise to 90 DEG C,Insulation reaction 2 hours, stops stirring, cooling, obtains the spherical microcapsules of rufous in reactant liquor bottom.
By product vacuum filter, clear water washing, 40～60 DEG C are dry after 4 hours, by setting with phenolic aldehyde of obtainingFat is that wall material carries out optics for the microcapsules of self-repair material and scanning electron microscopy is observed, and Fig. 1 is opticsDisplaing micro picture, Fig. 2 is ESEM picture. As shown in the figure, capsule grain diameter is 60～300 μ m, and wall thickness approximatelyBe 3 μ m.
Embodiment bis-:
Weigh respectively 5g phenol (P) and 7.5g formaldehyde (F), be placed in 500mL condenser pipe backflow dress is housedIn the there-necked flask of putting, add the 5wt%NaOH aqueous solution to regulate pH value to 10, first at 65 DEG C, stir10 minutes, be then warming up to 80 DEG C and insulation reaction 1.5 hours, obtain rufous first rank Resole solution.
Be equipped with in the 500mL there-necked flask of agitator, thermometer at another, add 14g dicyclopentadiene(DCPD) do as emulsifying agent and 100g distilled water as core, 20g polyacrylic acid (pH=6～7)For continuous phase, be heated to 70 DEG C, stir 20 minutes with the rates of rotation of 1000 rpms, obtain DCPD whiteEmulsion. Regulate DCPD emulsion temperature to 65 DEG C, reducing stir speed (S.S.) is 300 rpms, by first rankResole solution directly all joins in DCPD emulsion, after mixing, slowly drips 2% hydrochloric acidSolution, regulates pH value to 2, is then warming up to 75 DEG C, insulation reaction 2 hours, then rise to 90 DEG C, protectTemperature reaction 2 hours, stops stirring, cooling, obtains the spherical microcapsules of rufous in reactant liquor bottom.
By product vacuum filter, clear water washing, 40～60 DEG C are dry after 4 hours, by setting with phenolic aldehyde of obtainingFat is that wall material carries out optics for the microcapsules of self-repair material and scanning electron microscopy is observed, and Fig. 3 is opticsDisplaing micro picture, Fig. 4 is ESEM picture. As can be seen from the figure, Microcapsules Size is 400～1000 μ m,Wall thickness is about 3 μ m.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, not all at thisAny amendment of doing within bright spirit and principle, be equal to and replace and improvement etc., all should be included in the present inventionProtection domain within.
Claims (8)
1. taking phenolic resins as wall material is for microcapsules for self-repair material, it is characterized in that, described micro-The phenolic resins that the wall material of capsule is crosslinking curing, core is bicyclopentadiene, described microcapsules are of a size of30～1000μm。
2. taking phenolic resins as wall material is for a preparation method for the microcapsules of self-repair material, it comprise asLower step:
Produce first rank thermosetting resin: regulate pH value to 8～10 of phenol and aldehyde mixed aqueous solution, be warming up to60～65 DEG C, stir, then be warming up to 70～90 DEG C of reactions, obtain reactant liquor, wherein, described phenol and aldehyde mixThe mol ratio of phenol in aqueous solution and aldehyde is 1:1～3;
Produce core emulsion: get 40～120% of phenol and aldehyde quality summation in described phenol and aldehyde mixed aqueous solutionBicyclopentadiene, polyacrylic acid and water mix, be warming up to 50～80 DEG C, stir, obtain core emulsion, itsIn, the mass ratio of bicyclopentadiene, polyacrylic acid and water is 1:0.5～2:3～14;
At 60～65 DEG C, described core emulsion is mixed with described reactant liquor, obtain mixed liquor, regulate described mixedClose liquid pH value to 2.5～1, be warming up to 70～80 DEG C, react 1.5～2 hours, then be warming up to 85～90 DEG C,React 1.5～2 hours, obtain microcapsules precipitation, suction filtration, 40～60 DEG C are dry, obtain described with phenolic resinsFor wall material is for the microcapsules of self-repair material.
3. as claimed in claim 2 taking phenolic resins as wall material is for the preparation of the microcapsules of self-repair materialMethod, is characterized in that, described phenol is at least one in phenol, cresols, mixture cresol, and described aldehyde is firstAt least one in aldehyde, paraformaldehyde, furfural, acetaldehyde.
As claimed in claim 2 or claim 3 taking phenolic resins as wall material for the microcapsules of self-repair materialPreparation method, is characterized in that, described phenol is phenol, and described aldehyde is formaldehyde.
5. as claimed in claim 2 taking phenolic resins as wall material is for the preparation of the microcapsules of self-repair materialMethod, is characterized in that, the mol ratio of described phenol and aldehyde phenol in aqueous solution and aldehyde is 1:1.2～2.0.
As described in claim 2 or 5 taking phenolic resins as wall material for the microcapsules of self-repair materialPreparation method, is characterized in that, the mol ratio of described phenol and aldehyde phenol in aqueous solution and aldehyde is 1:1.5.
7. as claimed in claim 2 taking phenolic resins as wall material is for the preparation of the microcapsules of self-repair materialMethod, is characterized in that, pH value to 8～10 of described adjusting phenol and the aldehyde aqueous solution, select 5wt%NaOHThe aqueous solution regulates.
8. as claimed in claim 2 taking phenolic resins as wall material is for the preparation of the microcapsules of self-repair materialMethod, is characterized in that, described described reactant liquor is all added in described core emulsion, regulates pH valueTo 2.5～1, select the aqueous hydrochloric acid solution of 2wt% to regulate.
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| Application Number | Priority Date | Filing Date | Title |
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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 |
| 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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| CN103301789B true CN103301789B (en) | 2016-05-25 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105032313B (en) * | 2015-07-23 | 2017-04-26 | 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 |
| CN105080441B (en) * | 2015-07-28 | 2017-10-13 | 西北工业大学 | A kind of preparation method for coating liquid olefinic microcapsules |
| CN107224945B (en) * | 2017-06-26 | 2020-04-03 | 西北工业大学 | Dicyclopentadiene microcapsule taking phenolic resin as wall material solid particles as emulsifier and preparation method thereof |
| 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 |
| 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 |
| CN117645430A (en) * | 2023-11-30 | 2024-03-05 | 吉林省水利科学研究院(吉林省水利科技推广总站、吉林省水利水电工程质量检测中心、吉林省灌溉试验中心站) | Double microcapsule preparation method for self-repairing concrete freeze-thawing damage |
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| US20050241934A1 (en) * | 2004-04-28 | 2005-11-03 | Valerie Sauvant-Moynot | Self-repairing structure and coating for corrosive medium |
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| CN100376320C (en) * | 2005-09-06 | 2008-03-26 | 西北工业大学 | Polyurea coating dicyclopentadiene microcapsule and method for preparing same |
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| US20050241934A1 (en) * | 2004-04-28 | 2005-11-03 | Valerie Sauvant-Moynot | Self-repairing structure and coating for corrosive medium |
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