CN1248928A - Encapsulation - Google Patents
Encapsulation Download PDFInfo
- Publication number
- CN1248928A CN1248928A CN 97181767 CN97181767A CN1248928A CN 1248928 A CN1248928 A CN 1248928A CN 97181767 CN97181767 CN 97181767 CN 97181767 A CN97181767 A CN 97181767A CN 1248928 A CN1248928 A CN 1248928A
- Authority
- CN
- China
- Prior art keywords
- mixture
- colloidal state
- cover material
- acid
- state aggregation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J13/025—Applications of microcapsules not provided for in other subclasses
Abstract
A colloidal aggregate suitable for use in the curing of resins comprises a continuous phase of a water based encapsulent material and a dispersed phase comprising one or more strong acids. The continuous phase advantageously comprises a mixture of gelatin and xanthan gum. The aggregate is sonicated to encapsulate the acid in the encapsulent material. The encapsulated acid is mixed with a curable resin. The acid capsules may be ruptured by any suitable means, but particularly ultrasound, to release the acid to initiate curing of the resin.
Description
The present invention relates to microcapsules and the equipment of use and their production method of acid.The present invention especially but not only relates to the catalyst that is used for curable synthetic resin and/or the microcapsules of initator.
In great majority were used, the processing of resin and curing were to carry out under the condition of control.But following situation takes place, promptly when for reaching the optimum utilization of resin, in due course between before must control/prevent resin solidification.
Use heat to come cured resin in the application of most of thermosetting resins, the interlinkage that the application of heat causes catalyst in the resin and/or promoter to quicken molecular resin.But even do not use heat, resin also can solidify after several days, thereby had limited the time that uncured resin can be stored.So as seen by above-mentioned, one when resin mixes mutually with catalyst and is used to specific application, race against time makes the arrival of resin/catalyst system that the position should be arranged.
Industrial recognized this problem and by the exploitation waited some effort to solve this problem with the light radiation-hardenable is resin dedicated.
Diameter is made into less than the ultrafine microencapsulated of 100 μ, and when these microcapsules were scattered in the whole resin, when they were the use of thermosetting resin field, its size was suitable.When microcapsules are like this hour, their can be disperseed and can't be deposited in resin equably.
A kind of resin of special classification is a phenolic resins, and it is the product between phenols (being generally phenol) and the aldehydes (being generally formaldehyde).Using a major advantage of phenolic resin system in the thermosetting resin industry is that resin contains the meltable solid resin of low-molecular-weight at first, and this resin can easily be handled, and resin-shaped becomes HMW, firm heat proof material when solidified thereafter.
Phenolic resins is usually through adding strong acid initiation/catalysis, these strong acid such as sulfuric acid, hydrochloric acid, phosphoric acid, toluenesulfonic acid or the like, they all have very strong corrosivity and are difficult to handles, the corrosivity of acid is to be difficult to one of principal element with sour encapsulate unusually, do not have certain type encapsulate or control to discharge, it is impossible that acid control is released in the resin.Another kind of resin is that the urine formaldehyde resin also is to make the people interested.
An object of the present invention is to provide a kind of can easily be scattered in the resin material and do not have the strong acid capsule of the leakage of acid.
And the present invention also attempts to be provided for the curable resin system that hard product is produced, and wherein this resin can be solidified easily and apace, but remain with the long shelf life it is specially adapted in the thermosetting resin industry.
According to one aspect of the present invention, provide a kind of colloidal state aggregation that is applicable to resin solidification, comprise the continuous phase and the decentralized photo that comprises one or more strong acid of water base cover material, wherein continuous phase can be destroyed to discharge acid by the energy of outside.
Preferred cover material comprises acidproof water base gelatin.
Strong acid can comprise sulfuric acid, hydrochloric acid, phosphoric acid and toluenesulfonic acid or their mixture.
According to another aspect of the present invention, provide a kind of resin system that hard product is produced that is used for, wherein said resin system comprises resin and dispersed catalyst/initator, described catalyst is the colloidal state aggregation that comprises the continuous phase of water base cover material and comprise the decentralized photo of one or more strong acid, wherein continuous phase can enter resin to discharge acid by the energy of outside is destroyed, thereby initiation/catalytic resin is cured.
Such encapsulate than an advantage of prior art is, the reactant of encapsulate was produced to do capsule form in the past, when it and mixed with resin, often disperse bad, and colloidal state aggregation of the present invention is easy to be disperseed to guarantee fully to be scattered in the resin, and reduces the possibility that the big cohesion agglomerate of capsule exists significantly.
The present invention has general application aspect following: be dispersed with therein colloidal state capsule dipping the resin of absorber material can be shaped to final shape, destroy the capsule of colloidal state by for example heating or electromagnetic energy, to discharge catalyst or promoter, cause resin and absorber material in described net shape to solidify.
In another embodiment of the invention, the catalyst of encapsulate mixes with curable resinousness material, then by resinousness material soaking fiber carrier layer.
Fibrage can not be formed as any desired shape when resin is cured, as the molded parts of little ship shape or vehicle, then, by heating or electromagnetic energy cured resin to destroy the capsule of colloidal state.
The capsule carrier material of resin/colloidal state preferably has a kind of fibrous pieces structure, comprises the fiber of pad, coiled material or disordered orientation, and these fibers can be the fibers in glass fibre and/or natural and synthetic source.
According to another aspect of the present invention, a kind of method of little glue encapsulate that the resin solidification reaction is used as one or more strong acid of catalyst, promoter or initator that is used for being adapted at also is provided, and it comprises the steps: mixed acid, water base cover material and water; The formed mixture of sonicated so that in cover material encapsulate go into acid and from mixture, remove remaining water basically so that in cover material, form the colloidal state aggregation of acid.
As a specific example, when acidproof gelatin was used, the application of gelatin caused the free yl induction of protein molecule crosslinked in ultrasonic energy or the sonicated step.High activity base, particularly H and OH are generated by water through ultrasonic, and with solution/air in the molecular oxygen reaction that exists form peroxide HO
2Peroxide and protein molecule reaction between cysteine residues, formation usually cystine linkage.Ultrasonic can produce high concentration, usually at the narrow size distribution protein shape colloidal state capsule of 1-20 μ scope.
The typical ultrasonic response equipment that is used for the present invention's preparation comprises from the 20Khz ray of the next collimation of the zirconates titanate converter of lead.Reaction can preferably be carried out under ar gas environment at the indifferent gas environment in the sonicated groove of glass.Preferably can be fixed on the proximity transducer place and be used for amplifying its signal by the amplification angle (horn) of titanium system.Because temperature is owing to reaction is carried out raising, so the sonicated groove preferably is placed in the water-bath.Can also can be used by audible sound.
Be preferably in and remove in the step of anhydrating, the capsule aqueous mixture that will in the sonicated step, form, heating is about 24 hours under certain temperature below about 80 ℃ fail temperature, preferably heating between 60 ℃ and 70 ℃.
Will be clearer by following example to the present invention, these examples have been narrated as encapsulate polymerisation catalysts/initator, the strong acid in water base cover material.
Example 1
The curing of phenolic resins causes and catalysis by adding strong acid usually.Reaction is carried out at normal temperatures.
Be the appropriate mixture of phosphoric acid and toluenesulfonic acid by the curing agent of encapsulate in this example.
The acid blend of 1 weight portion is mixed with 3 weight portion food-grade gelatins (200Bloom) in being dispersed in 3 parts of water.
Use the 20Khz probe with said mixture sonicated 3 minutes (100W power).This high strength supersonic is producing intermediate protein shape capsule in the water-bearing media basically, and the favourable size less than 100 μ is arranged, and wherein capsule 2 is dispersed in the water, and comprises the gelatin skin 4 to the strong acid heart 6 encapsulates.
But find that because acid blend contains strong acid, gel/water termination causes acid to be spread by shell around the acid catalyst expansion.It seems that this is owing to being present in the water of each capsule neutralization around each capsule shells acid to be played carrier function.
Find, produce improved encapsulate product by the water in the elimination aqueous mixture and cross cyst wall to prevent acid thereafter.Therefore, the mixture of sonicated is heated in 70 ℃ of baking ovens, be removed, form end product colloidal state aggregation until 3 parts of water.
Example 2
In another test, with 10% heavy acid blend and 10% acidproof gelatin (Gelatex, Chem.Colloids Ltd) and 10% water mixes and used 20KHz probe (70W) sonicated mixture 3 minutes, generation has less than 100 μ particle sizes, advantageously the protein shape colloidal state capsule between 1 and 20 μ.
The colloid of gelatin/water/acid was heated 24 hours in 60 ℃ of baking ovens, anhydrate so that remove, and to stay gelatine capsule from gelatin/water termination.
Found the storage period that acid blend gelatine capsule of the present invention has at least 3 months,, heated its sample to 90 ℃, can reach curing in 5 minutes when in the presence of phenolic resins.
Cover material can be got many multi-form.
For example comprise that the material that gelatin and xanthans mix has been found the encapsulate that has useful especially long-term acid corrosion-resistant and be easy to acid, and the combination property that encapsulate destroys easily when using as ultrasonic extra power.
Said components preferably be formulated as following ranges:
Xanthans 0.1-50.1
Gelatin 99.9-49.9
Be coated with bonding, the agglomeration of gelatin and xanthans and bag and produce this material.Remove above-mentioned component mixture, following component also can be used in following component mixture:
(a) gelatin 99.9-49.9
Glue gel (Cellan Gum) 0.1-50.1
(b) Arabic gum 99.9-49.9
Xanthans 0.1-50.1
(c) Arabic gum 99.9-49.9
Glue gel 0.1-50.1
(d) gelatin 99.9-49.9
Bassora gum 0.1-50.1
(e) Arabic gum 99.9-49.9
Bassora gum 0.1-50.1
(f) gelatin 99.9-49.9
Arabic gum 0.1-50.1
(g) gelatin 99.9-49.9
Polyethylene glycol alginates 0.1-50.1
The admixture of all said mixtures also can be used.
In any mixture that comprises gelatin, following any substitute that can be used as is used.
---the gelatin after the hydrolysis
---alginates
---deer horn glue (Kappa, lota and Lambda)
---locust bean gum
---Arabic gum
---HM
---glue gel
---methylcellulose and methyl carboxy-propyl cellulose or their any mixture/modifier
---agar
In any mixture that comprises xanthans, following any substitute that can be used as is used:
---carboxyethyl cellulose
---carboxymethyl cellulose
---Arabic gum
---bassora gum
---glue gel
---the sulfuric acid monoester of bassora gum
---the polyethylene glycol alginates
---LM
In above-mentioned, following term has following connotation:
(a) gelatin after gelatin and the hydrolysis
From animal collagen (the comprising fish) protein that hydrolysis obtains or form amino acid whose
What short chain mixture.
(b) deer horn glue and agar
From the Bostrychia montagnei of the galactolipin skeleton that fuses by the glycosidic inkage that replaces, extract
Product.
(c) guar gum, locust bean gum, Caesalpinia spinosaKuntze glue, senna glue, mesquite gum and Hu Lu
Crust glue
The D-mannose residue that galactomannans-a series of connects based on β (1-4)
The linear polysaccharide enzyme.
(d) Arabic gum, bassora gum and karaya
Exudate glue-obtain from a kind of tree and shrubs, it is in a liquid state earlier and at sunlight
With form transparent lump behind the air drying.
(e) xanthans and glue gel
The special bacteria through fermentation of biosynthetic polysaccharase glue-use generates.
(f) alginates and alginate esters
The degree of polymerization of the salt of alginic acid-have usually 100-3000 is equivalent to about 20,000
-600,000 molecular weight.
Propanediol alginate (PGA) is a kind of ester of alginic acid and propane diols.
(g) methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose and carboxymethyl fibre
Dimension is plain
Cellulose ethers-generate " alkali cellulose " by cellulose and alkali reaction, and
The back at (or under diluent free) in the presence of the inert diluent by alkylation or alkoxyl
Change or make by the Williamson esterification.
(h) LM and HM
Pectin is composite construction part cleavage product in the plant cell wall (being generally fruit).
They generate high methoxyl and LM through the de-esterification modification.
The capsule of acid can be with any suitable method and the mixed with resin that will solidify.Resin can be phenolic aldehyde or pollopas, and very little capsule size helps disperseing in resin.Mixed process is low energy consumption, low-shearing force, to avoid the too early destruction of capsule.Suitable mixer pattern can be a paddle mixer.Comprise that the product shelf life of wanting cured resin and encapsulate acid can satisfy the requirement of consumer wants.Can reach at least three months and the storage life of possibility more than 1 year.
The capsule that is scattered in the resin can make its destruction with any suitable method, causes curing to discharge acid.Suitable method comprises heating, sound, ultrasonic, radio wave, microwave or pressure.At the product that comprises that originally working pressure is produced, for example in the laminate product with pressure method perhaps advantageous particularly.
Should know only purpose for example of the foregoing description of having been narrated, be possible without prejudice to the various changes of scope of the present invention.
Claims (25)
1. colloidal state aggregation that is suitable for using in resin solidification comprises the continuous phase of water base cover material and comprises the decentralized photo of one or more strong acid that wherein continuous phase can be destroyed to discharge acid by extra power.
2. colloidal state aggregation as claimed in claim 1, wherein cover material comprises water base acidproof gelatin.
3. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of gelatin and xanthans.
4. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of gelatin and glue gel.
5. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of Arabic gum and xanthans.
6. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of gelatin and bassora gum.
7. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of Arabic gum and bassora gum.
8. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of gelatin and Arabic gum.
9. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of gelatin and polyethylene glycol alginates.
10. as the colloidal state aggregation of claim 1 or 2, wherein cover material comprises the mixture of Arabic gum and glue gel.
11. as arbitrary colloidal state aggregation of claim 3 to 10, wherein the mutual ratio of two components is 99.9-49.9 and 0.1-50.1 scope.
12. colloidal state aggregation as claimed in claim 1, wherein cover material comprises gelatin, alginates, deer horn glue (Kappa, lota and Lambda), locust bean gum, Arabic gum, HM, glue gel, methylcellulose and methylhydroxypropylcellulose or their any mixture or the agar after the hydrolysis.
13. colloidal state aggregation as claimed in claim 1, wherein cover material comprises the xanthans that mixes with one of the sulfuric acid monoester of following hydroxyethylcellulose, carboxymethyl cellulose, Arabic gum, bassora gum, glue gel, bassora gum, polyethylene glycol alginates, LM etc.
14. as the colloidal state aggregation of claim 1 or 2, wherein strong acid comprises sulfuric acid, hydrochloric acid, phosphoric acid, toluenesulfonic acid or their mixture.
15. press the colloidal state aggregation of example 1 or example 2.
16. one kind is used for the resin system that hard product is produced, wherein said resin system comprises resin and dispersed catalyst/initator, described catalyst is the colloidal state aggregation, include the continuous phase and the decentralized photo that comprises one or more strong acid of water base cover material, wherein continuous phase can be destroyed to discharge acid by extra power and enter in the resin, thereby initiation/catalytic resin solidifies.
17. with the impregnated fiber carrier layer of the resin system of claim 16.
18. as the fiber carrier layer of claim 17, it when uncured by moulding.
19. as the fiber carrier layer of claim 17 or 18, it has fibrous chip architecture, comprises the fiber of pad, coiled material or disordered orientation.
20. as the fibrous carrier layer of claim 19, wherein fiber is a glass fibre.
21. one kind is used for producing the method that resin solidification reacts the micro-capsule encapsulate of one or more strong acid that are used as catalyst, promoter or initator that is adapted at, it comprises the steps: to make acid, water base cover material and water to mix; Formed mixture is carried out sonicated so that encapsulate acid in cover material, and from mixture, remove remaining water basically, so that in cover material, form this sour colloidal state aggregation.
22. as the method for claim 21, wherein mixture is handled with ultrasonic wave.
23. as the method for claim 22, wherein mixture is with hearing that sound wave handles.
24. as claim 21,22 or 23 method, wherein the capsule that will form in the sonicated step had been lower than under 80 ℃ of temperature heating about 24 hours.
25. as the method for claim 24, wherein with the temperature heating of capsule between 60 ℃ and 70 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9626152.4A GB9626152D0 (en) | 1996-12-17 | 1996-12-17 | Encapsulation |
| GB9626152.4 | 1996-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1248928A true CN1248928A (en) | 2000-03-29 |
Family
ID=10804552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97181767 Pending CN1248928A (en) | 1996-12-17 | 1997-12-16 | Encapsulation |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0948397A1 (en) |
| JP (1) | JP2001507051A (en) |
| CN (1) | CN1248928A (en) |
| AU (1) | AU727915B2 (en) |
| CA (1) | CA2275377A1 (en) |
| GB (1) | GB9626152D0 (en) |
| NO (1) | NO992932L (en) |
| WO (1) | WO1998026865A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9909763D0 (en) * | 1998-09-12 | 1999-06-23 | Cehmcolloids Ltd | Cluring of resins |
| JP2005146064A (en) * | 2003-11-13 | 2005-06-09 | Konica Minolta Medical & Graphic Inc | Dispersion of microcapsuled dye dispersion, its manufacturing process, and photosensitive material for thermal development photography |
| FI20085831L (en) * | 2008-09-05 | 2010-03-06 | Graveolens Oy A | Subject composition and use thereof |
| DE102009046244A1 (en) | 2009-10-30 | 2011-05-19 | Evonik Röhm Gmbh | Encapsulation of reactive components for 1-component systems using coaxial nozzles |
| DE102009046251A1 (en) | 2009-10-30 | 2011-05-19 | Evonik Röhm Gmbh | Reactive 1-component road markings |
| CN112079993A (en) * | 2020-09-22 | 2020-12-15 | 肇庆市海特复合材料技术研究院 | Preparation method of epoxy resin latent curing agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1388786A (en) * | 1972-04-03 | 1975-03-26 | Scherer Corp R P | Integral solid gel-lattice dosage form of high-moisture content |
| DE3447833A1 (en) * | 1984-12-29 | 1986-07-10 | Allan Gerhard 8047 Karlsfeld Frühauf | Cloth or the like with microcapsules containing an active ingredient |
-
1996
- 1996-12-17 GB GBGB9626152.4A patent/GB9626152D0/en active Pending
-
1997
- 1997-12-16 JP JP52742798A patent/JP2001507051A/en active Pending
- 1997-12-16 EP EP97949004A patent/EP0948397A1/en not_active Withdrawn
- 1997-12-16 AU AU77366/98A patent/AU727915B2/en not_active Ceased
- 1997-12-16 CN CN 97181767 patent/CN1248928A/en active Pending
- 1997-12-16 WO PCT/GB1997/003346 patent/WO1998026865A1/en not_active Application Discontinuation
- 1997-12-16 CA CA002275377A patent/CA2275377A1/en not_active Abandoned
-
1999
- 1999-06-16 NO NO992932A patent/NO992932L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998026865A1 (en) | 1998-06-25 |
| EP0948397A1 (en) | 1999-10-13 |
| GB9626152D0 (en) | 1997-02-05 |
| CA2275377A1 (en) | 1998-06-25 |
| JP2001507051A (en) | 2001-05-29 |
| AU727915B2 (en) | 2001-01-04 |
| NO992932L (en) | 1999-08-04 |
| AU7736698A (en) | 1998-07-15 |
| NO992932D0 (en) | 1999-06-16 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |