CN114468353A - Thermosensitive response essence slow-release microcapsule and preparation method and application thereof - Google Patents
Thermosensitive response essence slow-release microcapsule and preparation method and application thereof Download PDFInfo
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- CN114468353A CN114468353A CN202210191438.7A CN202210191438A CN114468353A CN 114468353 A CN114468353 A CN 114468353A CN 202210191438 A CN202210191438 A CN 202210191438A CN 114468353 A CN114468353 A CN 114468353A
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- essence
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- release microcapsule
- thermosensitive
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 54
- 230000004044 response Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 105
- 239000000377 silicon dioxide Substances 0.000 claims description 50
- 239000002775 capsule Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000011162 core material Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- BESKSSIEODQWBP-UHFFFAOYSA-N 3-tris(trimethylsilyloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C BESKSSIEODQWBP-UHFFFAOYSA-N 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229960002089 ferrous chloride Drugs 0.000 claims description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 9
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 241000402754 Erythranthe moschata Species 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000796 flavoring agent Substances 0.000 claims description 5
- 235000019634 flavors Nutrition 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- NBOCBWJUDBATAS-UHFFFAOYSA-N [2-hydroxy-3-[3-[methyl-bis(trimethylsilyloxy)silyl]propoxy]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COCCC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C NBOCBWJUDBATAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 3
- 235000005976 Citrus sinensis Nutrition 0.000 claims description 3
- 240000002319 Citrus sinensis Species 0.000 claims description 3
- 244000061176 Nicotiana tabacum Species 0.000 claims description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 3
- 229940043350 citral Drugs 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 3
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 claims description 3
- 239000010502 orange oil Substances 0.000 claims description 3
- 239000010671 sandalwood oil Substances 0.000 claims description 3
- ZHLSOSXEBSWGDW-UHFFFAOYSA-N 3-aminopropyl triethyl silicate Chemical compound CCO[Si](OCC)(OCC)OCCCN ZHLSOSXEBSWGDW-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000010648 geranium oil Substances 0.000 claims description 2
- 235000019717 geranium oil Nutrition 0.000 claims description 2
- POVQBCXZUZAICL-UHFFFAOYSA-N methoxy trimethyl silicate Chemical compound [Si](OC)(OC)(OC)OOC POVQBCXZUZAICL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010666 rose oil Substances 0.000 claims description 2
- 235000019719 rose oil Nutrition 0.000 claims description 2
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 claims description 2
- VGOXVARSERTCRY-UHFFFAOYSA-N trimethylsilylmethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC[Si](C)(C)C VGOXVARSERTCRY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007967 peppermint flavor Substances 0.000 claims 2
- 235000006679 Mentha X verticillata Nutrition 0.000 description 13
- 235000002899 Mentha suaveolens Nutrition 0.000 description 13
- 235000001636 Mentha x rotundifolia Nutrition 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000003205 fragrance Substances 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 241000628997 Flos Species 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000391 smoking effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/02—Manufacture of tobacco smoke filters
- A24D3/0204—Preliminary operations before the filter rod forming process, e.g. crimping, blooming
- A24D3/0212—Applying additives to filter materials
- A24D3/0216—Applying additives to filter materials the additive being in the form of capsules, beads or the like
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D1/00—Cigars; Cigarettes
- A24D1/002—Cigars; Cigarettes with additives, e.g. for flavouring
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
Abstract
The invention discloses a thermosensitive response essence slow-release microcapsule and a preparation method and application thereof.
Description
Technical Field
The invention relates to the field of tobacco essence, in particular to a thermosensitive response essence slow-release microcapsule and a preparation method and application thereof.
Background
With the development of the cigarette industry, the carrier technology stably and controllably adds flavor to cigarettes through the compatibility of essence, and is receiving more and more attention. Therefore, carriers such as microcapsules, liposomes, gels and the like are continuously developed to meet the application requirements of essence slow release. These carrier technologies encapsulate solids or liquids into small particles by film-forming materials, which release the encapsulated components under controlled conditions. This technique can prevent the volatilization of low boiling point components, and can prevent the occurrence of side reactions such as oxidation, etc. when the raw materials are exposed to air for a long period of time. Therefore, the carrier technology is widely applied to the fields of medicine, cosmetics, agriculture and the like.
The existing carrier technology mainly depends on a cross-linking agent, an organic monomer and an organic solvent, and forms a capsule wall on the surface of essence particles through chemical reaction under the stability of a surfactant. However, there are still some limitations in these methods.
For example, chinese patent publication No. CN106281676A discloses a microcapsule slow-release essence, which comprises a nano core material, an essence and a coating material; the essence is filled in the porous structure of the nano core material, and the coating material wraps the nano core material filled with the essence to form the microcapsule slow-release essence; the microcapsule slow-release essence comprises the following components in parts by weight: 5-15 parts of a nano core material, 5-15 parts of essence and 70-90 parts of a coating material; the essence is one or more of flos Osmanthi Fragrantis essence, flos Jasmini sambac essence, and flos Rosae Rugosae essence; the nano core material is porous resin or nano silicon dioxide; the coating material is PEG or monoglyceride with pharmaceutical grade, although the microcapsule has long fragrance retention time, the microcapsule has insufficient encapsulation efficiency and uneven capsule wall, and the encapsulated raw material is easy to rupture and release in advance, so that the problem of low fragrance concentration in use is caused.
Disclosure of Invention
In order to solve the problems, the invention provides the thermosensitive response essence slow-release microcapsule, and the preparation method and the application thereof, wherein the microcapsule has good encapsulation effect and high aroma concentration during aroma release.
The inventor finds that poly (N-isopropylacrylamide) -polyacrylamide serving as a capsule shell has good toughness and cohesiveness, the capsule shell is not easy to break and is in a hydrophilic conformation at room temperature, when the temperature is higher than 32 ℃, the polymer can form a hydrophobic state and agglomerate and coagulate, and the capsule shell can be opened to form an open pore structure so as to release essence, so that at the temperature lower than 32 ℃, under the condition that the capsule shell has good toughness and cohesiveness, the essence raw material coated by the poly (N-isopropylacrylamide) -polyacrylamide cannot be released in advance, the encapsulation effect is good, the essence is not easy to lose, and after the use condition is reached, the essence release concentration is high, and the fragrance release effect is good.
According to a first aspect of the invention, a thermosensitive response essence slow-release microcapsule is provided, which comprises a capsule shell and a core material coated in the capsule shell, wherein the core material is essence-loaded mesoporous silica, and the capsule shell is poly (N-isopropylacrylamide) -polyacrylamide.
Preferably, the essence is a solid essence or a liquid essence, specifically, the essence comprises one or a combination of at least two of mint essence, sweet orange oil, citral, rose oil, geranium oil, lavender oil, sandalwood oil and a musk ethanol mint essence solution, and preferably mint essence or musk ethanol mint essence.
According to a second aspect of the invention, a preparation method of a thermosensitive response essence slow-release microcapsule is provided, which comprises the following steps:
s1, obtaining mesoporous silicon dioxide;
s2, adding the essence solution into the mesoporous silica under a vacuum condition to obtain essence-loaded mesoporous silica;
s3, mixing and dispersing the essence-loaded mesoporous silica, the comonomer, the temperature-sensitive monomer and the silane coupling agent in water, sequentially adding hydrogen peroxide and ferrous chloride, and stirring to react to obtain the heat-sensitive response essence slow-release microcapsule, wherein the weight ratio of the comonomer, the temperature-sensitive monomer and the silane coupling agent is 6:3:1-4:6:1, such as 6:3:1, 5:3:1, 7:4:1, 6:4:1, 5:4:1, 7:5:1, 6:5:1 and 5:5: 1.
The mechanism of the reaction is that the comonomer can provide toughness and cohesiveness of the coating, the temperature-sensitive monomer can provide a corresponding dynamic structure for stimulation, the silane coupling agent can form covalent connection between the poly (N-isopropylacrylamide) -polyacrylamide coating and silicon dioxide, the comonomer and the temperature-sensitive monomer carry out copolymerization reaction under the action of hydrogen peroxide and ferrous chloride to form poly (N-isopropylacrylamide) -polyacrylamide, and the mesoporous silicon dioxide loaded with essence is covalently connected and coated, so that the heat-sensitive response essence slow-release microcapsule is obtained, and the essence coated inside the heat-sensitive response essence slow-release microcapsule is slowly released based on the heat-sensitive response essence slow-release microcapsule, so that high-concentration fragrance can be persistently released.
Preferably, the comonomer comprises at least one of acrylamide and acrylic acid.
Preferably, the temperature-sensitive monomer comprises at least one of N, N-dimethylacrylamide, N-diethylacrylamide and N-isopropylacrylamide, and is preferably N-isopropylacrylamide.
Preferably, the silane coupling agent comprises at least one of 3- (methacryloxy) propyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethylsilane, methacryloxypropyltris (trimethylsiloxy) silane, γ -aminopropyltriethoxysilane, (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane, preferably methacryloxypropyltris (trimethylsiloxy) silane.
Preferably, the weight ratio of the comonomer to the temperature-sensitive monomer is (2-1): 1.
Preferably, the mesoporous silica is obtained by the following method:
K1. sequentially adding a surfactant and terphenyl into a mixed solution of water, isopropanol and ammonia water, and then dropwise adding a silicon source to perform solution-gel reaction to obtain a solution-gel reaction product, wherein the volume ratio of the water, the isopropanol and the ammonia water is (3-7) to (8-12) to (0.5-1.5), and preferably 5:10: 1;
K2. calcining the solution gel reaction product at the temperature of 300-600 ℃, and then cooling and grinding to obtain the mesoporous silicon dioxide;
wherein the temperature of the solution-gel reaction is 40-80 ℃; the solution-gel reaction time is 20-30 h; the calcination temperature is 350-550 ℃; the calcination time is 3-5 h;
it is worth noting that in the present invention, the porosity of the mesoporous silica can be controlled by adjusting the addition amount of the surfactant to change the loading rate of the essence, wherein the surfactant is one or a combination of at least two of sodium dodecyl sulfate, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate, preferably cetyl trimethyl ammonium bromide.
Preferably, the silicon source comprises at least one of tetraethoxysiloxane, tetramethoxysiloxane, 3-aminopropyl triethoxy siloxane or 3-mercapto triethoxy siloxane, preferably tetraethoxysiloxane.
According to a third aspect of the invention, there is provided a use of a thermo-responsive flavour sustained release microcapsule as an additive in tobacco.
The invention has the beneficial effects that: the thermosensitive response essence slow-release microcapsule has the advantages of high encapsulation efficiency, uniform capsule wall, lasting essence storage, high fragrance concentration of fragrance release, strong lasting power, good smoking feeling, no residual organic solvent and high safety.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available by purchase.
Example 1
A thermosensitive response essence slow-release microcapsule comprises a capsule shell and a core material coated in the capsule shell, wherein the core material is mesoporous silicon dioxide loaded with mint essence, the capsule shell is poly (N-isopropylacrylamide) -polyacrylamide, and the essence is sandalwood oil.
Example 2
A thermosensitive response essence slow-release microcapsule comprises a capsule shell and a core material coated in the capsule shell, wherein the core material is mesoporous silicon dioxide loaded with musk ethanol mint essence, the capsule shell is poly (N-isopropyl acrylamide) -polyacrylamide, and the essence is the musk ethanol mint essence.
Example 3
A thermosensitive response essence slow-release microcapsule comprises a capsule shell and a core material coated in the capsule shell, wherein the core material is mesoporous silicon dioxide loaded with musk ethanol mint essence, the capsule shell is poly (N-isopropylacrylamide) -polyacrylamide, and the essence is an equal-ratio molar mixture of citral and the musk ethanol mint essence.
Example 4
A preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, purchasing mesoporous silicon dioxide on the market, wherein the CAS number is 7631-86-9;
s2, adding 10g of mesoporous silica into a three-necked bottle, vacuumizing, and adding 100 mu L of mint essence solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylamide, N-isopropylacrylamide and methacryloxypropyltris (trimethylsiloxy) silane into water, fully stirring and dissolving, wherein the weight ratio of the acrylamide to the N-isopropylacrylamide to the methacryloxypropyltris (trimethylsiloxy) silane is 6:3:1, sequentially adding 5 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 2 hours, and purifying and drying to obtain the heat-sensitive response essence slow-release microcapsule.
Example 5
A preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, purchasing mesoporous silicon dioxide on the market, wherein the CAS number is 7631-86-9;
s2, adding 10g of mesoporous silica into a three-necked bottle, vacuumizing, and adding 150 mu L of sweet orange oil solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylamide, N-diethylacrylamide and (3-methacryloxy-2-hydroxypropoxy) propyl bis (trimethylsiloxy) methylsilane into the three-necked bottle, fully stirring and dissolving the mixture in water, wherein the weight ratio of the acrylamide to the N, N-diethylacrylamide to the (3-methacryloxy-2-hydroxypropoxy) propyl bis (trimethylsiloxy) methylsilane is 6:5:1, sequentially adding 5 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 2 hours, and purifying and drying to obtain the thermosensitive response essence microcapsule slow release.
Example 6
A preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, purchasing mesoporous silicon dioxide on the market, wherein the CAS number is 7631-86-9;
s2, adding 10g of mesoporous silica into a three-mouth bottle, vacuumizing, and adding 200 mu L of lavender oil solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylic acid, N-isopropyl acrylamide and methacryloxypropyl tris (trimethylsiloxy) silane into water, fully stirring and dissolving, wherein the weight ratio of the acrylic acid to the N-isopropyl acrylamide to the methacryloxypropyl tris (trimethylsiloxy) silane is 7:4:1, then sequentially adding 3 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 3 hours, purifying and drying to obtain the thermosensitive response essence slow-release microcapsule.
Example 7
Firstly, preparing mesoporous silicon dioxide: adding 500 mL of water, isopropanol and ammonia water solution into a three-neck flask, uniformly stirring, wherein the volume ratio of the water to the isopropanol to the ammonia water is 5:10:1, sequentially adding 32 mL of hexadecyl trimethyl ammonium bromide and 3g of terphenyl under the continuous stirring state, slowly adding 10g of tetraethoxy siloxane into the system, uniformly dissolving, reacting at 60 ℃ for 24 hours, calcining the product in a muffle furnace at 500 ℃ for 4 hours, cooling to room temperature, and grinding the product to obtain mesoporous silica;
a preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, weighing 10g of the mesoporous silica;
s2, adding 10g of mesoporous silica into a three-necked bottle, vacuumizing, and adding 100 mu L of liquid mint essence solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylamide, N-diethylacrylamide and methacryloxypropyltris (trimethylsiloxy) silane into water, fully stirring and dissolving, wherein the weight ratio of the acrylamide to the N, N-diethylacrylamide to the methacryloxypropyltris (trimethylsiloxy) silane is 6:3:1, then sequentially adding 5 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 2h, purifying and drying to obtain the thermosensitive response essence slow-release microcapsule.
Example 8
Firstly, preparing mesoporous silicon dioxide: adding 500 mL of water, isopropanol and ammonia water solution into a three-neck flask and uniformly stirring, wherein the volume ratio of the water, the isopropanol and the ammonia water is 4:8:1, sequentially adding 60mL of sodium dodecyl sulfate and 3g of terphenyl under the continuous stirring state, slowly adding 10g of 3-aminopropyltriethoxysilane into the system, uniformly dissolving, reacting for 20h at 40 ℃, calcining the product for 4h in a muffle furnace at 550 ℃, cooling to room temperature, and grinding the product to obtain mesoporous silica;
a preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, weighing 10g of the mesoporous silica;
s2, adding 10g of mesoporous silica into a three-necked bottle, vacuumizing, and adding 100 mu L of liquid mint essence solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylic acid, N-isopropylacrylamide and gamma-aminopropyltriethoxysilane into the three-necked bottle, fully stirring and dissolving the mixture in water, wherein the weight ratio of the acrylic acid to the N-isopropylacrylamide to the gamma-aminopropyltriethoxysilane is 7:5:1, sequentially adding 5 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 2 hours, purifying and drying to obtain the thermosensitive response essence slow-release microcapsule.
Example 9
Firstly, preparing mesoporous silicon dioxide: adding 500 mL of water, isopropanol and ammonia water solution into a three-neck flask and uniformly stirring, wherein the volume ratio of the water, the isopropanol and the ammonia water is 4:8:1, sequentially adding 60mL of sodium dodecyl sulfate and 3g of terphenyl under the continuous stirring state, slowly adding 10g of 3-aminopropyltriethoxysilane into the system, uniformly dissolving, reacting for 20h at 40 ℃, calcining the product for 4h in a muffle furnace at 550 ℃, cooling to room temperature, and grinding the product to obtain mesoporous silica;
a preparation method of a thermosensitive response essence slow-release microcapsule comprises the following steps:
s1, weighing 10g of the mesoporous silica;
s2, adding 10g of mesoporous silica into a three-necked bottle, vacuumizing, and adding 100 mu L of liquid mint essence solution to obtain essence-loaded mesoporous silica;
s3, adding 10g of essence-loaded mesoporous silica into a three-necked bottle, adding 15g of acrylamide, N-isopropylacrylamide and gamma-aminopropyltriethoxysilane into water, fully stirring and dissolving, wherein the weight ratio of the acrylamide to the N-isopropylacrylamide to the gamma-aminopropyltriethoxysilane is 7:5:1, sequentially adding 5 mL of hydrogen peroxide and 1g of ferrous chloride, reacting for 3 hours, purifying and drying to obtain the heat-sensitive response essence slow-release microcapsule.
Test example 1
The content determination of the essence of the thermosensitive response essence slow-release microcapsule in the examples 4 to 9 was carried out: weighing 3g of thermosensitive response essence slow-release microcapsules, adding the microcapsules into a closed container, standing for 24h, measuring the release amount of essence by using a gas chromatograph, further measuring the thermosensitive release characteristic, heating the closed container to 40 ℃, measuring the release concentration of the essence by using the gas chromatograph under the same condition, and measuring the test results as shown in table 1:
TABLE 1 Release concentration of essence at different temperatures
Test example 2
The finished product sustained-release microcapsules prepared in the examples 4 to 9 are mixed with acetate fibers to prepare cigarette holders, the cigarette holders are divided into 8 equal parts, and the storage stability and the temperature-sensitive release of the products are tested. Directly adding essence without carrier as control group.
The method comprises the following specific steps: weighing the finished product of the slow-release essence, adding the slow-release essence into a closed container, standing for 24 hours, measuring the release amount of the essence by using a gas chromatograph, further measuring the temperature-sensitive release of the essence, heating the closed container to 40 ℃, and similarly measuring the release concentration of the essence by using a gas chromatograph, wherein the results are shown in table 2:
table 2 microcapsule stability testing
As can be seen from the above, the directly perfumed sample released fragrance quickly in the early stage, and hardly released fragrance after 20 days. The finished essence slow-release microcapsule prepared by the preparation method of the invention has no obvious release during storage, and shows obvious release after heating. Therefore, the thermosensitive response essence slow-release microcapsule prepared by the invention has better effects of storing and releasing essence.
Test example 3
When the thermosensitive response essence slow-release microcapsule prepared in the embodiments 4-9 of the invention is added into cigarettes, 10 professionals are selected to evaluate smoking, the evaluation standard is shown in table 3, and the evaluation result is shown in table 4, compared with the cigarettes added with common essence.
TABLE 4 Scoring criteria for assessment
TABLE 5 assessment scoring results
Those of ordinary skill in the art will understand that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same, although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it is possible to modify the solutions described in the previous embodiments or to substitute some or all of the technical features thereof without departing from the scope of the claims.
Claims (10)
1. The thermosensitive response essence slow-release microcapsule is characterized by comprising a capsule shell and a core material coated in the capsule shell, wherein the core material is mesoporous silicon dioxide loaded with essence, and the capsule shell is poly (N-isopropylacrylamide) -polyacrylamide.
2. The thermally responsive flavor slow-release microcapsule according to claim 1, wherein the flavor comprises one or more of peppermint flavor, sweet orange oil, citral, rose oil, geranium oil, lavender oil, sandalwood oil, and musk ethanol peppermint flavor.
3. A method for preparing a thermo-responsive essence slow-release microcapsule according to any one of claims 1-2, comprising the steps of:
s1, obtaining mesoporous silicon dioxide;
s2, adding the essence solution into the mesoporous silica under a vacuum condition to obtain essence-loaded mesoporous silica;
and S3, mixing and dispersing the essence-loaded mesoporous silica, the comonomer, the temperature-sensitive monomer and the silane coupling agent in water, sequentially adding hydrogen peroxide and ferrous chloride, and stirring for reaction to obtain the heat-sensitive response essence slow-release microcapsule.
4. The method for preparing the thermosensitive response essence slow-release microcapsule according to claim 3, wherein the comonomer comprises at least one of acrylamide and acrylic acid.
5. The method for preparing the thermosensitive response essence slow-release microcapsule according to claim 3, wherein the thermosensitive monomer comprises at least one of N, N-dimethylacrylamide, N-diethylacrylamide and N-isopropylacrylamide.
6. The method for preparing the slow-release microcapsule of the heat-sensitive response essence as claimed in claim 3, wherein the silane coupling agent comprises at least one of 3- (methacryloxy) propyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethylsilane, methacryloxypropyltris (trimethylsiloxy) silane, γ -aminopropyltriethoxysilane, (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane.
7. The preparation method of the thermosensitive response essence slow-release microcapsule according to claim 3, wherein the weight ratio of the comonomer to the thermosensitive monomer is (2-1): 1.
8. The preparation method of the thermosensitive response essence slow-release microcapsule according to claim 3, wherein the mesoporous silica is obtained by the following method:
K1. sequentially adding a surfactant and terphenyl into a mixed solution of water, isopropanol and ammonia water, and then dropwise adding a silicon source to perform solution-gel reaction to obtain a solution-gel reaction product;
K2. calcining the solution gel reaction product at the temperature of 300-600 ℃, and then cooling and grinding to obtain the mesoporous silicon dioxide.
9. The method for preparing a slow-release microcapsule of a thermosensitive response essence according to claim 8, wherein the silicon source comprises at least one of tetraethoxysiloxane, tetramethoxysiloxane, 3-aminopropyl triethoxy siloxane or 3-mercapto triethoxy siloxane.
10. Use of a thermo-responsive flavour release microcapsule according to any of claims 1-2 as an additive in tobacco.
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