CN108057402A - A kind of method for preparing the microcapsules containing pure polyamine and its microlayer model makeup are put - Google Patents
A kind of method for preparing the microcapsules containing pure polyamine and its microlayer model makeup are put Download PDFInfo
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- CN108057402A CN108057402A CN201810106854.6A CN201810106854A CN108057402A CN 108057402 A CN108057402 A CN 108057402A CN 201810106854 A CN201810106854 A CN 201810106854A CN 108057402 A CN108057402 A CN 108057402A
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- polyamine
- microcapsules
- preparing
- microlayer model
- containing pure
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- 229920000768 polyamine Polymers 0.000 title claims abstract description 99
- 239000003094 microcapsule Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000012459 cleaning agent Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000004809 Teflon Substances 0.000 claims description 33
- 229920006362 Teflon® Polymers 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 238000005086 pumping Methods 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 5
- 235000005513 chalcones Nutrition 0.000 claims description 5
- 229960002725 isoflurane Drugs 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 claims description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004914 cyclooctane Substances 0.000 claims description 3
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 229920000333 poly(propyleneimine) Polymers 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 9
- 239000002775 capsule Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- -1 polypropylene cyanogen Polymers 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 206010011732 Cyst Diseases 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 208000031513 cyst Diseases 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
Classifications
-
- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- 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
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
- B01J13/043—Drying and spraying
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a kind of methods for preparing the microcapsules containing pure polyamine and its microlayer model makeup to put, a kind of method for preparing the microcapsules containing pure polyamine, including following preparation process：(1) configure reaction solution and stir；(2) microlayer model processing is carried out to polyamine, and added in reaction solution；(3) just microcapsules processed are made；(4) just microcapsules processed are cleaned with cleaning agent, and obtains finished microcapsule after the drying.The invention also discloses the microlayer model makeups for preparing the microcapsules containing pure polyamine to put.The present invention provides a kind of method for preparing the microcapsules containing pure polyamine and its microlayer model makeup is put, it can complete the preparation to pure polyamine microcapsules, a kind of brand-new method is provided for the preparation of pure polyamine, and provide corresponding microlayer model makeup and put, it can be good at completing the microlayer model to pure polyamine.
Description
Technical field
The invention belongs to microencapsulation field, in particular to a kind of methods for preparing the microcapsules containing pure polyamine and its micro-
Droplet treatment device.
Background technology
Microencapsulation technology is a kind of micro- glue for manufacturing shell material containing protective and wrapped various difference in functionality cores
The technology of capsule.No matter these cores are any forms before being wrapped, and solid-state, therefore microcapsules have been reformed into after being wrapped
After change to these substances use and dispose all can be more convenient.After substance is wrapped, completely cut off with external environment, this
Sample can reduce its volatilization, cover its smell, enhance its stability, protect its active ingredient and control its release.Microencapsulation
Technology by academia with regard to having been carried out extensively and in depth having studied since it is by invention, while it is also extensive in industrial quarters
Ground application.According to the difference of cyst wall permeability, microcapsules can play different functions.When effect microcapsule wall leakproofness is relatively good
When, microcapsules can be used for storing the substance of various difference in functionality, such as repair liquid (US6518330 B2), phase-change accumulation energy material
Material, fire retardant etc.；And when effect microcapsule wall has the permeability that can regulate and control, it may be used as sustained release or controlled release
Carrier, release drug, anti-fouling agent, corrosion inhibiter etc..
In order to meet prepare containing difference in functionality microcapsules the needs of, had been developed in the past few decades it is various not
Same microencapsulation technology.According to the difference and generation shell material mode for generating the droplet/little particle mode for being used for package not
Together, traditional Microencapsulation Method can be roughly divided into three classes, i.e. physical method, physical chemistry composite algorithm and chemical method.Its
Middle in-situ polymerization and interfacial polymerization are to be made two methods with the most use in chemical method, in both approaches, either water
Bag oil or Water-In-Oil, after stable lotion is formed, the drop in lotion can be aggregated heavy by shape shell monomer in system
Product is wrapped in oil/water interface.
However, though microencapsulation technique for packing greatly, still do not do by some substances so far
Method is wrapped up with existing method, such as polyamine.It is organic as a kind of compound containing two or more amino
Polyamine is widely used as curing agent or the chain extender of epoxy resin, polyureas, nylon etc..But due to its molecule knot
Existing hydrophobic part also has hydrophilic segment in structure, and organic multicomponent amine can almost be dissolved in most polarity or weak polar solvent
In, such as water, benzene, toluene etc..Therefore have no idea to emulsify pure organic multicomponent amine in certain solvent, be formed steady
Fixed lotion.Further, since organic multicomponent amine can react with many shape shell monomers used today or can influence its reaction, this
Kind high activity is also the very challenging reason of its microencapsulation.
Because polyamine all has very high activity to epoxy group and isocyanate group, by polyamine wrap up into
And it prepares self-repair material and has been attempted a very long time.In selfreparing field, the epoxy-amine based on microencapsulation is certainly
Reparation system and the quick self-healing system of isocyanates-amine based on microencapsulation have attracted more and more concerns.For
Manufacture above-mentioned self-repair material, academia have carried out substantial amounts of effort for the microencapsulation of polyamine.It is hollow except utilizing
Pipeline loads polyamine and prepares outside self-repair material, and researcher also prepares other various carriers to load polynary amine curing agent,
Such as hollow polyureas urea formaldehyde (PUF) microcapsules, hollow glass micropearl (US9522843 B2) and hollow polypropylene cyanogen nanometer
Fiber.After these microcarriers are prepared, polynary amine curing agent is then loaded in these carriers again.In the process of loading
In, it can be selected to accelerate loading process using vacuum according to actual conditions.Although it can be used for selfreparing purpose above-mentioned
Method load polyamine, but these methods are comparatively all more complicated.Lee (Li) et al. claims that they utilize solvent
Volatility process has successfully wrapped up polyether polyamine, i.e. Jeffamine D230.Pair based on the microcapsules and epoxy microcapsule simultaneously
Component epoxy-amine self-healing system shows good repairing effect in selfreparing epoxy resin.But according to their report
It leads, the content of amine is very low in the microcapsules finally obtained.After package condition is optimized, highest content is also only general
20wt%.Scientific research personnel also uses pik woods (Pickering) emulsion method to wrap up pure polyamine.Contain although having prepared
The microballoon of polyamine, but they obtain be solid microsphere rather than with nucleocapsid structure microcapsules.They do not have yet simultaneously
Have and further prepare based on the self-repair material of this microcapsules to verify the prepared application containing pure polyamine microcapsules.
It is successfully wrapped using allocation rule of the polyamine in water and low polarity carbohydrate solvent, Lee (Li) et al. and easy (Yi) et al.
The aqueous solution of polyamine rather than pure polyamine are wrapped up in.Due to profit, prepared effect microcapsule wall is very fragile in this way, this
A little researchers remove before further this microcapsules are used even without by the water in microcapsules.Old (Chen) et al. profit
The secondary double emulsion generated with a kind of extremely complex and accurate microfluidic device, successfully wrapped up diethylenetriamine (DETA) and
The aqueous solution of triethylene tetramine (TETA).By the precise controlling to microencapsulation processes, this method can prepare scale
Homogeneous, the uniform microcapsules of wall thickness.Since the thermostabilization of used polyacrylic acid cyst wall is relatively good, vacuum can be used
Water in capsule is removed completely.Nevertheless, due to the cyst wall of this capsule is thicker and raw capsules in contain larger proportion
Moisture, the polynary amine content in final microcapsules is also comparatively than relatively low.In addition, because cured using DETA or TETA
Epoxy cross-linking density it is higher, using this microcapsules prepare selfreparing epoxy resin the reparation of fracture toughness is less managed
Think.
As seen from the above, a kind of method currently not yet, can prepare with nucleocapsid structure, core content is higher and
The controllable microcapsules containing pure polyamine of core composition.In addition, for this microcapsules containing polyamine, also there is one kind two
Difficulty border, i.e., in the selfreparing application of this microcapsules, it is intended that the amine activity wrapped up is the higher the better, but utilizes and pass
The method of system during this microcapsules are prepared, the higher amine of activity its be more difficult to be wrapped.In this case, if we want to
Wrap up pure polyamine, it would be desirable to explore and develop a kind of new method to realize its package.In this invention, we describe
A kind of complex method that T junction microfluidic device and interfacial polymerization are used in combination realizes the microencapsulation of pure polyamine.
The content of the invention
It is an object of the invention to overcome the above problem, provide a kind of method for preparing the microcapsules containing pure polyamine and its
Microlayer model makeup puts, the preparation to pure polyamine microcapsules can be completed, for pure polyamine preparation provide it is a kind of completely newly
Method, and provide corresponding microlayer model makeup and put, it can be good at completing the microlayer model to pure polyamine.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method for preparing the microcapsules containing pure polyamine, including following preparation process：
(1) reaction solution is configured, and reaction solution is carried out to continue stirring；
(2) microlayer model processing is carried out to polyamine, and the polyamine microlayer model after microlayer model is added in into reaction solution
In；
(3) reaction solution for adding polyamine drop is heated to 40-60 DEG C, and adjusts mixing speed to keep to anti-
Answer the lasting stirring of solution, and stir 2-6 it is small when after obtain just microcapsules processed；
(4) just microcapsules processed are cleaned with cleaning agent, and obtains finished microcapsule after the drying.
Reaction solution described in step (1) by diisocyanate monomer/performed polymer, surfactant, catalyst and
Cannot dissolve or can only the nonpolar or weak polar solvent of oligodynamical polyamine mix, wherein, two is different in every part of solute
The weight ratio of cyanate ester monomer/performed polymer, surfactant and catalyst is 4-8：0.05-1：0-1, and every part of solute then with
50ml cannot dissolve or can only the nonpolar or weak polar solvent of oligodynamical polyamine be engaged, the reaction solution that will have been configured
It is placed in the environment of room temperature and is stirred with the speed of 80-180r/min.
It is different that the diisocyanate monomer/performed polymer includes hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydrides two
In cyanate, isoflurane chalcone diisocyanate and toluene di-isocyanate(TDI) any one or any one more than composition,
Either by hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, isoflurane chalcone diisocyanate, two
What any one in methylenebis phenyl isocyanate or toluene di-isocyanate(TDI) generated dissolves in the performed polymer of reaction liquor；
The surfactant then selects to promote to form the surfactant of reversed-phase emulsion；
The catalyst includes that the triethylene diamine of polyamine and isocyanate-monomer/prepolymer reaction, 2,4 can be promoted,
Any one in (dimethylamino methyl) phenol of 6- tri- or dibutyl tin laurate；
Cannot dissolve or can only nonpolar or low pole the solvent of oligodynamical polyamine include containing 6-18 carbon atom
Liquid fat hydrocarbon, in cycloalkane such as hexamethylene, cycloheptane, cyclooctane, cyclodecane, decahydronaphthalenes any one or it is any one
Kind or more mixture.
Microlayer modelization processing in step (2) is then that microlayer model makeup is selected to put completion；The polyamine includes second two
In amine condensation polymer, polyetheramine, fatty amine, polypropylene amine and aromatic amine any one or any one more than mixture.
Mode of heating in step (3) is：
(31) reaction solution for adding polyamine drop is heated to 40 DEG C, is stirred with the mixing speed of 200-250r/min
Mix 1 it is small when；
(32) temperature is promoted to 50 DEG C, when small with the mixing speed stirring 2 of 200-250r/min；
(33) temperature is promoted to 60 DEG C, with the mixing speed of 200-250r/min stirring 2 it is small when after obtain the just micro- glue of system
Capsule.
Cleaning process in step (4) is：
First, cleaning agent is added in first microcapsules processed, and is stood after being stirred for uniformly, until being removed after solid precipitation
Supernatant lays equal stress on to be added with and it is cleaned 3-6 times into cleaning agent, until supernatant is clarified；Then, clear supernatant is removed
Liquid, and the microcapsules after cleaning are placed in air, until having obtained pure microcapsules after cleaning agent volatilization completely；
The cleaning agent is nonpolar solvent, and optimal cleaning agent is then pure hexamethylene.
A kind of microlayer model makeup for preparing the microcapsules containing pure polyamine is put, and including thick teflon pipe, is inserted into thick Teflon
Pipe the thin teflon pipe of any position and is individually connected to thick teflon pipe and thin teflon pipe in addition to head and the tail both ends
On pump out device；Wherein, what is be connected with thick teflon pipe pumps out device for pumping out common stream phase, is connected with thin teflon pipe
What is connect pumps out device with pumping out polyamine.
Preferably, the quantity of the thin teflon pipe is one or more, it is independent on each thin teflon pipe
There are one connections pumps out device, and this pumps out device as syringe pump or constant displacement pump；The common stream be mutually by surfactant and
Cannot dissolve or can only oligodynamical polyamine nonpolar or low pole solvent with 0.05-1g：The w/v of 50ml
The solution mixed.
A kind of microlayer model makeup for preparing the microcapsules containing pure polyamine is put, and including pumping out device, is connected with pumping out device
The flat mouth metal needle for connecing and being vertically arranged, the metallic conductor being arranged on immediately below flat mouth metal needle and anode flat mouth gold
Category syringe needle is connected, the high voltage power supply that cathode is connected with metallic conductor；Between the flat mouth metal needle and metallic conductor
Spacing is 10-50cm, and the voltage of high voltage power supply is 5-15KV.
A kind of microlayer model makeup for preparing the microcapsules containing pure polyamine is put, and the pressure of two conduits is inserted with including top
Tank, wherein a conduit stretches into the bottom of pressurized tank, another conduit is arranged on the top of pressurized tank, with stretching into pressure pot bottom
The atomizer that is connected of conduit and the top with being arranged on pressurized tank the gas tank that is connected of conduit；Wherein in gas tank
Compressed gas be any one non-acid gases.
Compared with prior art, the present invention haing the following advantages and advantageous effect：
(1) The inventive process provides a kind of brand-new thinking, the making bottleneck of existing polyamine microcapsules is breached,
It can be good at completing the making of pure polyamine microcapsules, promote the development of enterprise and industry well.
(2) microlayer model of the invention makeup is put there are three types of different composition structures, and different setting sides is provided for enterprise
Formula, so be easy to use when made choice according to actual demand, greatly improve the flexibility that product uses.
Description of the drawings
Fig. 1 is the structure diagram that the first microlayer model makeup of the present invention is put.
Fig. 2 is the structure diagram that second of microlayer model makeup of the present invention is put.
Fig. 3 is the structure diagram that the third microlayer model makeup of the present invention is put.
Reference sign：1st, device is pumped out；2nd, thick teflon pipe；3rd, thin teflon pipe；4th, flat mouth metal needle；5th, it is high
Voltage source；6th, metallic conductor；7th, gas tank；8th, pressurized tank；9th, atomizer.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
Present embodiment discloses a kind of method for preparing the microcapsules containing pure polyamine, including following preparation process：
(1) reaction solution is configured, and reaction solution is carried out to continue stirring；
The reaction solution by diisocyanate monomer/performed polymer, surfactant, catalyst and cannot dissolve or
Can only the nonpolar or weak polar solvent of oligodynamical polyamine mix, wherein, diisocyanate monomer in every part of solute/
The weight ratio of performed polymer, surfactant and catalyst is 6：0.05：0, and every part of solute cannot then dissolve with 50ml or can only
The nonpolar or weak polar solvent of oligodynamical polyamine is engaged, and the reaction solution configured is placed in the environment of room temperature
And it is stirred with the speed of 80-180r/min.
Wherein, catalyst can be without using when that is, the weight ratio of catalyst wherein be 0.The use of catalyst be in order to
The further polyamine microlayer model that improves can preferably ensure micro- glue in the formation speed into reaction solution rear casing
Capsule quickly forms.
It is different that the diisocyanate monomer/performed polymer includes hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydrides two
In cyanate, isoflurane chalcone diisocyanate and toluene di-isocyanate(TDI) any one or any one more than composition,
Either by hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, isoflurane chalcone diisocyanate, two
What any one in methylenebis phenyl isocyanate or toluene di-isocyanate(TDI) generated dissolves in the performed polymer of reaction liquor；
The surfactant then selects to promote to form the surfactant of reversed-phase emulsion, which is poly-
The poly- hydroxy stearic acid ester of ethylene oxide or sorbitan fatty ester, wherein optimal for span 80.
The catalyst includes that the triethylene diamine of polyamine and isocyanate-monomer/prepolymer reaction, 2,4 can be promoted,
Any one in (dimethylamino methyl) phenol of 6- tri- or dibutyl tin laurate；
Cannot dissolve or can only nonpolar or low pole the solvent of oligodynamical polyamine include containing 6-18 carbon atom
Liquid fat hydrocarbon, in cycloalkane such as hexamethylene, cycloheptane, cyclooctane, cyclodecane, decahydronaphthalenes any one or it is any one
Kind or more mixture.
(2) microlayer model processing is carried out to polyamine, and the polyamine microlayer model after microlayer model is added in into reaction solution
In；
Microlayer modelization processing is then that microlayer model makeup is selected to put completion；The polyamine includes ethylenediamine condensation polymer, gathers
In ether amines, fatty amine, polypropylene amine and aromatic amine any one or any one more than mixture.
Polyamine after microlayer model is melted by microlayer model into after reaction solution, will rapidly with diisocyanate monomer/
Performed polymer is reacted, and polyamine and the diisocyanate monomer/prepolymer reaction on microlayer model surface form housing with to inside
Pure polyamine wrapped up, avoid internal polyamine continue with diisocyanate monomer/prepolymer reaction, and then form
Required polyamine microcapsules.
(3) reaction solution for adding polyamine drop is heated to 40-60 DEG C, and adjusts mixing speed to keep to anti-
Answer the lasting stirring of solution, and stir 2-6 it is small when after obtain just microcapsules processed；
Mode of heating is：
(31) reaction solution for adding polyamine drop is heated to 40 DEG C, 1 is stirred with the mixing speed of 200r/min
Hour；
(32) temperature is promoted to 50 DEG C, when small with the mixing speed stirring 2 of 200r/min；
(33) temperature is promoted to 60 DEG C, with the mixing speed of 200r/min stirring 2 it is small when after obtain just microcapsules processed.
(4) just microcapsules processed are cleaned with cleaning agent, and obtains finished microcapsule after the drying.
Cleaning process is：
First, cleaning agent is added in first microcapsules processed, and is stood after being stirred for uniformly, until being removed after solid precipitation
Supernatant lays equal stress on to be added with and it is cleaned 3-6 times into cleaning agent, until supernatant is clarified；Then, clear supernatant is removed
Liquid, and the microcapsules after cleaning are placed in air, until having obtained pure microcapsules after cleaning agent volatilization completely；
The cleaning agent is nonpolar solvent, and optimal cleaning agent is then pure hexamethylene.
The content of amine is about 80wt%, and the thermal stability of the housing of microcapsules in the microcapsules made by this method
Relatively good, heat decomposition temperature is at 200 degrees Celsius or more.
Embodiment 2
The present embodiment only difference is that with embodiment 1：
The weight ratio of diisocyanate monomer/performed polymer, surfactant and catalyst is 8 in every part of solute：1：1.
Mixing speed when adding the reaction solution of polyamine drop is 250r/min.
Embodiment 3
The present embodiment only difference is that with embodiment 1：
The weight ratio of diisocyanate monomer/performed polymer, surfactant and catalyst is 6 in every part of solute：0.6：
0.5。
Mixing speed when adding the reaction solution of polyamine drop is 225r/min.
Embodiment 4
It to be put as shown in Figure 1, present embodiment discloses a kind of microlayer model makeups for preparing the microcapsules containing pure polyamine, including
Thick teflon pipe 2 is inserted into thick teflon pipe 2 and the thin teflon pipe 3 of any position and individually connects in addition to head and the tail both ends
It is connected on thick teflon pipe 2 and thin teflon pipe 3 and pumps out device 1；Wherein, device 1 is pumped out with what thick teflon pipe 2 was connected
For pumping out common stream phase, what is be connected with thin teflon pipe 3 pumps out device 1 with pumping out polyamine.
The quantity of the thin teflon pipe 3 is one or more, and independent connection has one on each thin teflon pipe 3
It is a to pump out device 1, and this pumps out device 1 as syringe pump or constant displacement pump；The common stream is mutually by surfactant and cannot be molten
Solution or can only oligodynamical polyamine nonpolar or low pole solvent with 0.05-1g：50ml w/v mixing and
Into solution.
Flow rate of liquid in thick teflon pipe and thin teflon pipe controlled by pumping out device, and is being pumped out
In the process, the flow rate of liquid in thick teflon pipe is more than the flow rate of liquid in thin teflon pipe, to ensure that polyamine can flow
Become microlayer model in dynamic process.
Embodiment 5
As shown in Fig. 2, a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine is put, including pumping out device 1, with pump
Go out the flat mouth metal needle 4 that device 1 is connected and is vertically arranged, the metallic conductor 6 being arranged on immediately below flat mouth metal needle 4,
And the high voltage power supply 5 that anode flat mouth metal needle 4 is connected, cathode is connected with metallic conductor 6；The flat mouth metal needle
Spacing between 4 and metallic conductor 6 is 10-50cm, and the voltage of high voltage power supply 5 is 5-15KV.
Polyamine will be charged when by flat mouth metal needle, and close to metallic conductor under electric field action, and then
It is dropped in the bogey for being arranged on and being set above metallic conductor, forms microcapsules.To adjust the drippage scope of microlayer model
The upper area of plane of metallic conductor can then be changed, it then can be by adjusting pumping rate or height to the size for adjusting microlayer model
The voltage value of voltage source is completed.
Embodiment 6
As shown in figure 3, a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine is put, being inserted with two including top leads
The pressurized tank 8 of pipe, wherein a conduit stretches into the bottom of pressurized tank 8, another conduit is arranged on the top of pressurized tank 8, with stretching
Enter what the conduit at atomizer 9 that the conduit of 8 bottom of pressurized tank is connected and the top with being arranged on pressurized tank 8 was connected
Gas tank 7；Compressed gas wherein in gas tank 7 is any one non-acid gases.
Compressed gas in gas tank can be very good to ensure that the gas will not carry out instead with polyamine using non-acid gases
Should, and then ensure the pure property of polyamine.Polyamine enters atomizer under the pressure of air pressure by conduit, and is sprayed by atomization
Head carries out microlayer model ejection.It can change the big of microlayer model by adjusting atomizer model and gas tank pressure size
It is small.
As described above, the present invention can be realized well.
Claims (10)
1. a kind of method for preparing the microcapsules containing pure polyamine, including following preparation process：
(1) reaction solution is configured, and reaction solution is carried out to continue stirring；
(2) microlayer model processing is carried out to polyamine, and the polyamine microlayer model after microlayer model is added in reaction solution；
(3) reaction solution for adding polyamine drop is heated to 40-60 DEG C, and adjusts mixing speed to keep to reacting molten
The lasting stirring of liquid, and stir 2-6 it is small when after obtain just microcapsules processed；
(4) just microcapsules processed are cleaned with cleaning agent, and obtains finished microcapsule after the drying.
2. a kind of method for preparing the microcapsules containing pure polyamine according to claim 1, it is characterised in that：Step (1)
Described in reaction solution by diisocyanate monomer/performed polymer, surfactant, catalyst and cannot dissolve or can only be micro-
The nonpolar or weak polar solvent of amount dissolving polyamine mixes, wherein, diisocyanate monomer/pre-polymerization in every part of solute
The weight ratio of body, surfactant and catalyst is 4-8：0.05-1：0-1, and every part of solute cannot then be dissolved with 50ml or only
The nonpolar or weak polar solvent of energy oligodynamical polyamine is engaged, and the reaction solution configured is placed on to the environment of room temperature
In and be stirred with the speed of 80-180r/min.
3. a kind of method for preparing the microcapsules containing pure polyamine according to claim 2, it is characterised in that：Described two is different
Cyanate ester monomer/performed polymer includes hexamethylene diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, isophorone
In diisocyanate and toluene di-isocyanate(TDI) any one or any one more than composition or by hexa-methylene
Diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanates, isoflurane chalcone diisocyanate, diphenylmethane diisocyanate
What any one in ester or toluene di-isocyanate(TDI) generated dissolves in the performed polymer of reaction liquor；
The surfactant then selects to promote to form the surfactant of reversed-phase emulsion；
The catalyst includes that the triethylene diamine of polyamine and isocyanate-monomer/prepolymer reaction, 2,4,6- tri- can be promoted
Any one in (dimethylamino methyl) phenol or dibutyl tin laurate；
Cannot dissolve or can only oligodynamical polyamine nonpolar or weak polar solvent include the liquid containing 6-18 carbon atom
In aliphatic hydrocarbon, cycloalkane such as hexamethylene, cycloheptane, cyclooctane, cyclodecane, decahydronaphthalenes any one or any one more than
Mixture.
4. a kind of method for preparing the microcapsules containing pure polyamine according to claim 3, it is characterised in that：Step (2)
In microlayer modelization processing then be select microlayer model makeup put completion；The polyamine include ethylenediamine condensation polymer, polyetheramine,
In fatty amine, polypropylene amine and aromatic amine any one or any one more than mixture.
5. a kind of method for preparing the microcapsules containing pure polyamine according to claim 4, it is characterised in that：Step (3)
In mode of heating be：
(31) reaction solution for adding polyamine drop is heated to 40 DEG C, 1 is stirred with the mixing speed of 200-250r/min
Hour；
(32) temperature is promoted to 50 DEG C, when small with the mixing speed stirring 2 of 200-250r/min；
(33) temperature is promoted to 60 DEG C, with the mixing speed of 200-250r/min stirring 2 it is small when after obtain just microcapsules processed.
6. a kind of method for preparing the microcapsules containing pure polyamine according to claim 5, it is characterised in that：Step (4)
In cleaning process be：
First, cleaning agent is added in first microcapsules processed, and is stood after being stirred for uniformly, until removing supernatant after solid precipitation
Liquid lays equal stress on to be added with and it is cleaned 3-6 times into cleaning agent, until supernatant is clarified；Then, clear supernatant is removed, and
Microcapsules after cleaning are placed in air, until having obtained pure microcapsules after cleaning agent volatilization completely；
The cleaning agent is nonpolar solvent, and optimal cleaning agent is then pure hexamethylene.
7. a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine described in claim 1-6 any one is put, special
Sign is：Including thick teflon pipe (2), the thin teflon pipe of thick teflon pipe (2) any position in addition to head and the tail both ends is inserted into
(3) and individually it is connected on thick teflon pipe (2) and thin teflon pipe (3) and pumps out device (1)；Wherein, with thick spy
What teflon tube (2) was connected pumps out device (1) for pumping out common stream phase, and what is be connected with thin teflon pipe (3) pumps out device (1)
With with pumping out polyamine.
8. a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine according to claim 7 is put, it is characterised in that：
The quantity of the thin teflon pipe (3) is one or more, and there are one pumps for independent connection on each thin teflon pipe (3)
Go out device (1), and this pumps out device (1) as syringe pump or constant displacement pump；The common stream is mutually by surfactant and cannot be molten
Solution or can only oligodynamical polyamine nonpolar or low pole solvent with 0.05-1g：50ml w/v mixing and
Into solution.
9. a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine described in claim 1-6 any one is put, special
Sign is：Including pumping out device (1), the flat mouth metal needle (4) that is connected and is vertically arranged with pumping out device (1) is arranged on
Metallic conductor (6) and anode flat mouth metal needle (4) immediately below flat mouth metal needle (4) are connected, cathode and metal are led
The high voltage power supply (5) that body (6) is connected；Spacing between the flat mouth metal needle (4) and metallic conductor (6) is 10-50cm,
The voltage of high voltage power supply (5) is 5-15KV.
10. a kind of microlayer model makeup for preparing the microcapsules containing pure polyamine described in claim 1-6 any one is put, special
Sign is：The pressurized tank (8) of two conduits is inserted with including top, wherein a conduit stretches into the bottom of pressurized tank (8), Ling Yigen
Conduit is arranged on the top of pressurized tank (8), the atomizer (9) being connected with the conduit for stretching into pressurized tank (8) bottom, Yi Jiyu
It is arranged on the gas tank (7) that the conduit at the top of pressurized tank (8) is connected；Compressed gas wherein in gas tank (7) is any one
Non-acid gases.
Priority Applications (3)
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| CN201810106854.6A CN108057402A (en) | 2018-02-02 | 2018-02-02 | A kind of method for preparing the microcapsules containing pure polyamine and its microlayer model makeup are put |
| PCT/CN2018/078099 WO2019148577A1 (en) | 2018-02-02 | 2018-03-06 | Method for preparing microcapsule containing pure polyamine and microdroplet forming device thereof |
| PCT/CN2019/072936 WO2019149129A1 (en) | 2018-02-02 | 2019-01-24 | Method for preparing microcapsules containing pure polyamine and microdroplet generator therefor |
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