CN100376320C - Polyurea coating dicyclopentadiene microcapsule and method for preparing same - Google Patents
Polyurea coating dicyclopentadiene microcapsule and method for preparing same Download PDFInfo
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- CN100376320C CN100376320C CNB2005100431978A CN200510043197A CN100376320C CN 100376320 C CN100376320 C CN 100376320C CN B2005100431978 A CNB2005100431978 A CN B2005100431978A CN 200510043197 A CN200510043197 A CN 200510043197A CN 100376320 C CN100376320 C CN 100376320C
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- dicyclopentadiene
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Abstract
The invention relates to a polyurea packed dicyclopentadiene microcapsule and relative preparation. Wherein, the invention is characterized in that: it comprises isocyanate, amine, dicyclopentadiene, inhibitor, water, acetone, surface activator and defoaming agent. And the preparation comprises: adding water solution of surface activator into the flask of mixer, adding dicyclopentadiene with inhibitor, defoaming agent; mixing at normal temperature and adding isocyanate solution diluted by acetone; adding amine water solution; mixing and increasing temperature slowly; then keeping the temperaur and ending reaction; washing the product by water for several times; filtering and drying to obtain micro capsule. Since the polyurea is heat convertible resin crossed by amine polymers, it has better water resistance, mechanical strength and thermal stability; and the invention has simple process, while the yield is 80-90%.
Description
Technical field:
The present invention relates to a kind of polyurea coating dicyclopentadiene microcapsule and preparation method thereof.
Background technology:
In recent years, because the application of microcapsules in the composite selfreparing makes the composite self-repair technology that qualitative leap arranged.But the kind of microcapsules that can be used for the composite selfreparing at present is few, therefore syntheticly can be used for realizing that with research the microcapsules of composite selfreparing have obtained paying close attention to widely.The synthetic selection that can be used in the microcapsule wall material of composite selfreparing has strict condition, require microcapsule wall material to have better heat-resisting and mechanical property on the one hand, excellent to guarantee microcapsules embedding in the machine-shaping process of composite; On the other hand, the mechanical property of microcapsule wall material can not be too high, and to guarantee cracking under the situation of damage at composite of microcapsules, microcapsules break under the effect of crack stress and discharge the capsule-core material to crack surface.At present, adopting situ aggregation method, is that the technology of the synthetic microcapsules of wall material raw material is comparatively ripe with urea, formaldehyde, in fields such as agricultural chemicals, medicine, commodity, materials application is all arranged for the synthetic microcapsules of wall material with the uramit.Wherein, be the wall material with the ureaformaldehyde, be that the synthetic microcapsules of capsule-core have obtained using in polymer matrix composites and better to the repairing effect of material with the dicyclopentadiene.But, adopt the process time of the microcapsules that can be used for polymer matrix composites with the uramit for the wall material is synthetic longer, comparatively strict for the pH value control of solution in the building-up process, these give the synthetic certain difficulty of having brought of microcapsules.Simultaneously, the wall material owing to the microcapsules that are used for the composite selfreparing is single at present, makes the scope that is used for composite selfreparing field reduce.Therefore select other wall material, and the development of the synthetic microcapsules of technology simple to operate is to press for.
Summary of the invention:
The technical problem that solves:
For fear of the deficiencies in the prior art part, the present invention proposes a kind of polyurea coating dicyclopentadiene microcapsule and preparation method thereof.Can provide a kind of novel wall material to synthesize and have suitable hear resistance and the sealing microcapsules that can be used for the polymer matrix composites selfreparing good, that include renovation agent.
Technical scheme:
Technical characterictic of the present invention is: component is: isocyanates: 5～15b, amine substance: 5～20b, dicyclopentadiene (DCPD): 5～50b, polymerization inhibitor: 0.1～5b, water: 20～800b, acetone: 0～200b, surfactant: 0～40b, defoamer: 0～20b, wherein b is a unit of weight.
Preparation process is:
A, in disposing the four-hole boiling flask of agitator, add the aqueous solution contain surfactant;
B, slow adding under agitation contain the dicyclopentadiene of polymerization inhibitor, add defoamer again, and normal temperature stirs 20～30min down;
C, the adding isocyanate solution of acetone diluted, the slow amine substance aqueous solution that adds dilute with water controls certain rotating speed behind the 5min, slowly is warming up to 40～80 ℃, insulation 1～4h, end is reacted;
D, with the washed several times with water of synthetic product with 60 ℃, obtain microcapsule product through suction filtration, drying.
Described isocyanates is following any: Toluene-2,4-diisocyanate, 4-vulcabond, hexamethylene diisocyanate, polymethylene polyphenyl group diisocyanate, XDI.
Described amine substance is following any: 1, and 6-hexamethylene diamine, ethylenediamine, propane diamine, m-phenylene diamine (MPD), methylene diamine, piperazine, diethyl triamine, triethyl group tetramine, 1,3,5-benzene triamine, 2,4,6-three amido toluene, tetraethylenepentamine, five ethyl hexamines, polymine, 1,3,6-three amido naphthalenes, 3,4,5-three amidos-1,2,4-triazole three cyanamides, 1,4,5, the 8-tetra-amino anthraquinone.
Described polymerization inhibitor is following any: resorcinol, hydroquinones, tert-butyl catechol, contraposition benzoquinones.
Described surfactant is following any: lauryl sodium sulfate (K
12), neopelex (DBS), styrene-maleic anhydride copolymer (SMA), ethene-copolymer-maleic anhydride, gum arabic, polyoxyethylene sorbitan fatty acid ester, gelatin, polyvinyl alcohol (PVA), polyethylene glycol.
Described defoamer is following any: lower alcohols, polar organic compounds system, mineral oil, silicone resin.
Described lower alcohol defoamer is following any: methyl alcohol, ethanol, isopropyl alcohol, n-butanol, sec-butyl alcohol; Polar organic compounds has amylalcohol, diisobutyl carbinol (DIBC), octanol, phosphate, dehydration sorbic alcohol trioleate, polypropylene glycol.
Beneficial effect: because polyureas is that condensation polymer by isocyanates and amine is through the crosslinked thermosetting resin that forms, have resistance to water, mechanical strength and heat endurance preferably, therefore can give good hear resistance of microcapsules and mechanical property as the wall material with polyureas.In addition, be raw material with isocyanates and amine, utilizing the interface polymerization reaction technology, synthetic with the polyureas to be that the microcapsules of wall material have a technological operation simple, the advantage that the reaction time is short, and also polyureas has better heat-resisting performance and mechanical property.Therefore, employing is the wall material with the polyureas, with dicyclopentadiene (DCPD) is that the synthetic microcapsules of capsule-core not only can shorten the process time, has advantage simple to operate, simultaneously can also give microcapsules and have higher mechanical property and hear resistance, increase the kind that can be used for the composite self-repairing microcapsule, expansion composite selfreparing theory.
Adopt the synthetic micro capsule technology of polyurea coating dicyclopentadiene simple to operate, synthetic microcapsules have better heat-resisting, sealing property and mechanical property, and synthetic yield is 80～90%, utilize the microcapsules performance of foregoing invention preparation as follows:
The performance of table 1 microcapsules
| Performance | Feature |
| Outward appearance | The rotatable spheric granules of white |
| Particle diameter | 10～1000μm |
| Wall thickness | 1～60μm |
| The following storage life of room temperature | 〉=6 months |
| The stored frozen phase | 〉=12 months |
| Hear resistance | ～220℃ |
| Rupture strength | 0.2～1.5μN |
The specific embodiment:
Now the present invention is further described:
In the present invention, the synthetic of polyurea coating dicyclopentadiene microcapsule is raw material with isocyanates, amine substance, dicyclopentadiene mainly.For the reaction rate of controlling, use behind the adding acetone solvent in the isocyanates, amine substance is diluted with water to the aqueous solution and uses.In order to guarantee the chemical stability of dicyclopentadiene, add polymerization inhibitor.
Embodiment 1: add in disposing the 250ml four-hole boiling flask of agitator and contain 1% DBS deionized water solution 50ml, the rotating speed of setting agitator is 350rpm, add then and contain 0.2g resorcinol and 20gDCPD, add n-octyl alcohol 0.1g again, add the 10g toluene 2 that contains useful 20ml acetone diluted behind 20～30min, 4-vulcabond solution, add with the water-reducible 10gl of 20ml deionization with buret behind the 5min, 6-hexamethylene diamine solution, adding amine aqueous solution speed is controlled at 1～2h and finishes, temperature with reaction system slowly rises to 60 ℃ at last, and insulation 2～3h finishes reaction.Synthetic product is washed 5～6 times with 60 ℃ deionization, obtained microcapsule product through suction filtration, drying.
Embodiment 2: add in disposing the 1000ml four-hole boiling flask of agitator and contain 1% DBS deionized water solution 200ml, the rotating speed of setting agitator is 500rpm, add then and contain 0.4g resorcinol and 80gDCPD, add the 0.4g n-octyl alcohol again, add the 60g hexamethylene diisocyanate solution that contains useful 80ml acetone diluted behind 20～30min, add with the water-reducible 60gl of 80ml deionization with buret behind the 10min, 6-hexamethylene diamine solution, adding amine aqueous solution is controlled at 1～2h and finishes, temperature with reaction system slowly rises to 65 ℃ at last, insulation 2～3h, finish reaction synthetic product is washed 5～6 times with 60 ℃ deionization, through suction filtration, drying obtains microcapsule product.
Claims (7)
1. polyurea coating dicyclopentadiene microcapsule, it is characterized in that: component is: isocyanates: 5～15b, amine substance: 5～20b, dicyclopentadiene DCPD:5～50b, polymerization inhibitor: 0.1～5b, water: 20～800b, acetone: 0～200b, surfactant: 0～40b, defoamer: 0～20b, wherein b is a unit of weight; Preparation process is:
A, in disposing the four-hole boiling flask of agitator, add the aqueous solution contain surfactant;
B, slow adding under agitation contain the dicyclopentadiene of polymerization inhibitor, add defoamer again, and normal temperature stirs 20～30min down;
C, the adding isocyanate solution of acetone diluted, the slow amine substance aqueous solution that adds dilute with water controls certain rotating speed behind the 5min, slowly is warming up to 40～80 ℃, insulation 1～4h, end is reacted;
D, with the washed several times with water of synthetic product with 60 ℃, obtain microcapsule product through suction filtration, drying.
2. polyurea coating dicyclopentadiene microcapsule according to claim 1, it is characterized in that: described isocyanates is following any: Toluene-2,4-diisocyanate, 4-vulcabond, hexamethylene diisocyanate, polymethylene polyphenyl group diisocyanate, XDI.
3. polyurea coating dicyclopentadiene microcapsule according to claim 1, it is characterized in that: described amine substance is following any: 1,6-hexamethylene diamine, ethylenediamine, propane diamine, m-phenylene diamine (MPD), methylene diamine, piperazine, diethyl triamine, triethyl group tetramine, 1,3,5-benzene triamine, 2,4,6-three amido toluene, tetraethylenepentamine, five ethyl hexamines, polymine, 1,3,6-three amido naphthalenes, 3,4,5-three amidos-1,2,4-triazole three cyanamides, 1,4,5, the 8-tetra-amino anthraquinone.
4. polyurea coating dicyclopentadiene microcapsule according to claim 1 is characterized in that: described polymerization inhibitor is following any: resorcinol, hydroquinones, tert-butyl catechol, contraposition benzoquinones.
5. polyurea coating dicyclopentadiene microcapsule according to claim 1 is characterized in that: described surfactant is following any: lauryl sodium sulfate K
12, neopelex DBS, styrene-maleic anhydride copolymer SMA, ethene-copolymer-maleic anhydride, gum arabic, polyoxyethylene sorbitan fatty acid ester, gelatin, polyvinyl alcohol (PVA), polyethylene glycol.
6. polyurea coating dicyclopentadiene microcapsule according to claim 1 is characterized in that: described defoamer is following any: lower alcohols, polar organic compounds system, mineral oil, silicone resin.
7. polyurea coating dicyclopentadiene microcapsule according to claim 6 is characterized in that: described lower alcohol defoamer is following any: methyl alcohol, ethanol, isopropyl alcohol, n-butanol, sec-butyl alcohol; Polar organic compounds has amylalcohol, diisobutyl carbinol (DIBC), octanol, phosphate, dehydration sorbic alcohol trioleate, polypropylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100431978A CN100376320C (en) | 2005-09-06 | 2005-09-06 | Polyurea coating dicyclopentadiene microcapsule and method for preparing same |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100431978A CN100376320C (en) | 2005-09-06 | 2005-09-06 | Polyurea coating dicyclopentadiene microcapsule and method for preparing same |
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| CN1927445A CN1927445A (en) | 2007-03-14 |
| CN100376320C true CN100376320C (en) | 2008-03-26 |
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| CNB2005100431978A Expired - Fee Related CN100376320C (en) | 2005-09-06 | 2005-09-06 | Polyurea coating dicyclopentadiene microcapsule and method for preparing same |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301789B (en) * | 2013-06-07 | 2016-05-25 | 深圳大学 | A kind of taking phenolic resins as wall material is for the preparation method of the microcapsules of self-repair material |
| CN105080441B (en) * | 2015-07-28 | 2017-10-13 | 西北工业大学 | A kind of preparation method for coating liquid olefinic microcapsules |
| CN105669932B (en) * | 2016-01-13 | 2018-05-11 | 中山大学 | A kind of smooth self-repairing cross-linked polymer and its preparation method and application |
| CN110527063A (en) * | 2019-07-09 | 2019-12-03 | 华伦纳路新材料有限公司 | Polyurethane-modified aqueous alkide resin of dicyclopentadiene and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789494A (en) * | 1995-02-17 | 1998-08-04 | Medlogic Global Corporation | Encapsulated materials |
| CN1252012A (en) * | 1997-04-07 | 2000-05-03 | 美国3M公司 | Encapsulation process and encapsulated products |
| CN1348832A (en) * | 2000-10-16 | 2002-05-15 | 拜尔公司 | Micro capsule having carbamide resin wall |
| CN1509298A (en) * | 2001-02-13 | 2004-06-30 | ����ŵ˹��ѧ���»� | Multifunctional autonomically healing composite material |
-
2005
- 2005-09-06 CN CNB2005100431978A patent/CN100376320C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789494A (en) * | 1995-02-17 | 1998-08-04 | Medlogic Global Corporation | Encapsulated materials |
| CN1252012A (en) * | 1997-04-07 | 2000-05-03 | 美国3M公司 | Encapsulation process and encapsulated products |
| CN1348832A (en) * | 2000-10-16 | 2002-05-15 | 拜尔公司 | Micro capsule having carbamide resin wall |
| CN1509298A (en) * | 2001-02-13 | 2004-06-30 | ����ŵ˹��ѧ���»� | Multifunctional autonomically healing composite material |
Non-Patent Citations (1)
| Title |
|---|
| 具有自修复能力的聚合物材料. 陈大柱等.化学通报. 2004 * |
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