CN114515017A - Water blasting bead with high water retention performance and preparation method and application thereof - Google Patents
Water blasting bead with high water retention performance and preparation method and application thereof Download PDFInfo
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- CN114515017A CN114515017A CN202210092773.1A CN202210092773A CN114515017A CN 114515017 A CN114515017 A CN 114515017A CN 202210092773 A CN202210092773 A CN 202210092773A CN 114515017 A CN114515017 A CN 114515017A
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- water
- bead
- needle
- core material
- high water
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- 239000011324 bead Substances 0.000 title claims abstract description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000005422 blasting Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000011162 core material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000004880 explosion Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 206010016807 Fluid retention Diseases 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- 238000001723 curing Methods 0.000 claims description 25
- 238000000016 photochemical curing Methods 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 230000000391 smoking effect Effects 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- -1 phenyl sulfonium hexafluoroantimonate Chemical compound 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- 230000009172 bursting Effects 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 abstract description 9
- 239000012071 phase Substances 0.000 description 48
- 239000010410 layer Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 17
- 239000002775 capsule Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 6
- 229920005615 natural polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000019634 flavors Nutrition 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 3
- 229920000053 polysorbate 80 Polymers 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000008384 inner phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008385 outer phase Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 229940044476 poloxamer 407 Drugs 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Images
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
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
- A24D3/048—Tobacco smoke filters characterised by their shape or structure containing additives
-
- 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
Abstract
The invention relates to a water-explosion bead with high water retention property, which comprises a wall material and a water-based core material, wherein the wall material is formed by a photo-curable mixture through a curing reaction, and the viscosity of the mixture is 1000-15000 mPa s; the particle size of the water blasting bead is 2.0mm-4.5 mm; the crushing strength is 1N-25N; the concentricity is more than 87 percent, and the sphericity is more than 94 percent; the water content of the water blasting bead core body can reach 100 wt%; the water retention rate in 7 days can reach 95 wt%. The water blasting bead can be prepared by a one-step method by utilizing the formula disclosed by the invention, and the water blasting bead prepared by the formula has high water content and good water retention property. The mechanical strength of the bead is moderate, the bead is easy to pinch and break while the mechanical performance of the bead is provided, and good application experience can be provided when the bead is applied to cigarettes.
Description
Technical Field
The invention belongs to the technical field of cigarettes, and particularly relates to a water blasting bead with high water retention performance, and a preparation method and application thereof.
Background
The cigarette blasting bead takes a natural polymer material or a synthetic polymer material as a wall material, various tobacco essences are wrapped in a micro closed spherical capsule in a solid, liquid or gas form, one or more easily-pinched flavor capsules are implanted in the production process of a filter tip, so that artificially controllable characteristic flavor release in the smoking process of the cigarette is realized, the influence of the external environment on the smoking flavor and the loss of the essences are reduced, and the effects of increasing the smoke humidity and improving the fragrance retaining effect of the filter stick are achieved. Meanwhile, the aroma components in the capsule volatilize, and the functions of increasing aroma and enriching taste levels of cigarettes can be realized.
In recent years, water exploded beads using water or a water-soluble substance as a core material have been studied intensively, because the oily core material is required to use an organic solvent, which causes poor safety of the exploded beads. The water is used as the bead blasting core material, so that the water-soluble essence or other water-soluble components can be added, the smoke is wetted, the smoke temperature is reduced, part of harmful substances in the smoke are absorbed, the smoking experience of the cigarette is improved, and the cigarette is safe and environment-friendly. However, the oil explosion beads usually use water-soluble natural polymers, such as gelatin, arabic gum, alginate, etc., as wall materials, and because of certain water solubility, when the oil explosion beads are used as wall materials of water explosion beads, the water retention rate is low, the mechanical stability is poor, and the like. The water-exploded beads prepared by water-soluble wall materials such as alginate, gelatin and the like can be completely dehydrated within one day and cannot be put into practical application.
In order to improve the leakage problem of the water blasting bead wall material, the water retention property of the blasting bead is improved by adopting a multi-step method to carry out multi-layer coating on the blasting bead in the prior art. For example, CN110250549A discloses a high leakage-proof water-carrying capsule, which has at least three layers including a core layer, a capsule wall layer and a first water-resistant layer, and discloses that the water-resistant layer formed by cyanoacrylate compounds is formed on the outer surface of the capsule wall layer of natural polymer to improve the water-retaining property of the bead burst formed by natural polymer. However, the operation mode needs at least two preparation steps, and the thickness of the wall material is difficult to control, so that the particle size of the exploded beads is not uniform and the exploded beads are difficult to add into the filter tip; the prior art CN111758999A discloses that the surface of the natural polymer wall material is further subjected to chemical plating to increase the compactness of the natural polymer structure, thereby improving the anti-leakage performance of the exploded bead. However, the method still cannot be formed in one step, the process is complex, and the safety of the product is poor.
At present, the published technology discloses a one-step forming process, and a high polymer material with low water permeability is adopted to solve the problem of low water retention rate. The application numbers CN201910090596.1 and CN201811372831.6 are respectively prepared by using hydrophobic wall materials such as polylactic acid or polyethylene through a coagulation bath method, but organic solvents such as dichloromethane or acetone are required, so that the method cannot be applied to the field of food and is not environment-friendly. The application number CN202010841260.7 adopts the photo-curing resin as a wall material to prepare the water blasting bead in a self-assembly mode, but the resin needs to be dissolved by using an organic solvent, and the photoinitiator is added into the water core, so that the water blasting bead has higher biotoxicity and cannot be applied to the field of food. Application number CN201820575981.6 produces passageway and photocuring device through three-dimensional confocal emulsification droplet, adopts photocuring resin as wall material preparation water to explode the pearl, because its device is the horizontally flow mode, the emulsification droplet can be because the unbalance of gravity and buoyancy, glues the pipe wall when flowing, and this method just uses ultraviolet radiation solidification when gathering water and explode the pearl, and the water explodes the pearl and glues each other easily before the solidification. Application number CN201910618056.6 adopts photocuring resin and paraffin as wall material preparation water to explode pearl through the fashioned mode of coaxial system of dripping, but when the liquid drop fell to the protection liquid level, can receive the impact of liquid level and take place deformation, leads to exploding the pearl sphericity and be difficult to control, and the speed of liquid drop whereabouts can't be controlled, and photocuring time is difficult to obtain guaranteeing, causes the solidification incomplete problem easily.
Microfluidics, an emerging technology developed in recent years, can precisely manipulate microscale fluids. Millifluidic is a technology developed on the basis of microfluidics, and can be used for controlling various immiscible fluids to generate millimeter-scale composite emulsion droplets. At present, the millifluidic devices for preparing composite emulsion particles mainly comprise three types: double T-shape, flow focusing, and coaxial flow. Wherein, the shearing force applied by the continuous phase in the coaxial milli-fluidic device is more uniform, and the monodispersity of the prepared composite emulsion particles is better. The composite emulsion droplets are prepared by a coaxial millifluidic device by adopting water as an internal phase, photocuring resin as an intermediate phase and liquid immiscible with the resin as an external phase, and the intermediate phase is cured by ultraviolet radiation, so that the water exploded beads with good monodispersity can be obtained.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a light-curable water-exploded bead with high water retention property, a preparation method and application thereof. The water explosion bead can realize one-step molding of the water explosion bead through the vertically arranged coaxial millifluidic device and the photocuring method. The water explosion bead prepared by the method has good water retention performance, high water content, stable size, moderate crushing strength and good application experience.
In order to achieve the above object, the present invention provides a water-exploded bead with high water retention performance, which comprises a wall material and an aqueous core material, wherein the wall material is formed by a photo-curable mixture through a curing reaction. In the invention, if the viscosity of the mixture is less than 1000mPa & s, the concentricity of the product blasting beads is low, and the breakage rate is high; if the viscosity of the mixture is more than 15000 mPas, the mixture is difficult to extrude from a needle. It is therefore reasonable that the viscosity of the mixture is from 1000 mPas to 15000 mPas. Within a proper viscosity range of the light-cured mixture, the higher the viscosity, the more favorable the process is to obtain the explosion beads with low shell thickness and high water carrying rate, and the lower the viscosity, the more favorable the extrusion speed of the mixture is, thereby improving the production efficiency. Therefore, a more preferable mixture viscosity is 8000 mPas to 10000 mPas. The viscosity of the photocuring mixture is set within a proper viscosity range, the water explosion bead can be prepared in a millifluidic mode, namely, the reaction wall material can be extruded and molded from a millifluidic needle, and the water content of the formed water explosion bead is high and the crushing strength is moderate.
Further, the mixture of the photo-curable reaction comprises 60 wt% -99 wt% of prepolymer, 0 wt% -30 wt% of diluent and 1 wt% -10 wt% of photoinitiator.
The prepolymer is one or more of polyurethane acrylate prepolymer, epoxy modified polyurethane prepolymer and the like; the diluent is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate and the like; the photoinitiator is one or more of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, diphenylethanone, diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluoroantimonate and the like.
The main substance of the water-based core material is water, and the water content of the core material is preferably 90 wt% -100 wt%, or 95 wt% -100 wt%, or 99 wt% -100 wt%.
The aqueous core material may further contain one or more of water-soluble flavor substance additives, plant extracts, surface tension regulators and the like.
The surface tension regulator can be selected from any one of Tween 80, APG 0810, poloxamer 407 and the like; the content of the surface tension regulator in the water-based core material is 0 wt% -5 wt%.
The invention also provides a method for preparing the water blasting bead with high water retention, which adopts a milli-fluidic method to prepare the water blasting bead and comprises the following specific steps:
(1) respectively weighing a core material solution and a wall material, and respectively filling the core material, the wall material and the external phase liquid into liquid pumps;
(2) and respectively connecting a liquid pump filled with a core material, a wall material and an external phase liquid with an internal phase needle, an intermediate phase needle and an external phase needle, wherein the internal phase needle, the intermediate phase needle and the external phase needle jointly form a coaxial needle.
(3) The coaxial needle head is connected with a curing tube filled with the external phase liquid, the coaxial needle head is immersed below the liquid level of the external phase liquid of the curing tube, ultraviolet lamp beads are arranged on two sides of the curing tube, the core material, the wall material and the external phase liquid are extruded out through the coaxial needle head simultaneously, an extrudate passes through the curing tube and is cured in the curing tube, and water explosion beads are collected at the bottom of the curing tube.
The external phase liquid is incompatible with the wall material, and has viscosity of 10-500 mPa.s (25 ℃).
Further, the external phase solution is selected from sodium alginate solution, carboxymethyl cellulose solution, chitosan solution, polyvinyl alcohol solution, silicone oil, vegetable oil or mineral oil.
The curing tube is made of any material which can transmit ultraviolet light, such as a quartz tube.
The flow rate of the inner phase pump is 0.05mL/min-1.00mL/min, the flow rate of the middle phase pump is 0.01mL/min-0.20mL/min, and the flow rate of the outer phase pump is 5mL/min-30 mL/min.
The milliflow control preparation method can obtain the water blasting beads by a one-step method, and the obtained water blasting beads have high water content, good water retention performance and moderate crushing strength.
The formed water blasting beads are spherical, and the sphericity is more than 94%, further more than 96%, or more than 97%.
The average particle diameter of the water blasting beads is 2.0mm to 4.0mm, and further may be about 2.6mm, 2.7mm, 2.8mm, 2.9mm, 3.0mm, 3.1mm, 3.2mm, 3.3mm, 3.4mm, or the like.
The crushing strength of the water blasting bead is about 1N-25N, preferably 7N-16N, or 9N-15N. Within the crushing strength range of the invention, the water blasting bead product has better mechanical strength, is suitable for transportation and storage, is convenient to crush when in use, and has good application experience.
The water content of the water blasting bead can reach 100 wt%, and the initial water carrying rate can reach 70 wt%, or more than 80 wt%; the water retention rate of 7 days is more than 70 wt%, or more than 95%.
The invention also provides application of the water-retaining water-swelling bead to cigarettes. The water-exploded bead has good water-retaining property, so that the storage property and the quality stability of the water-exploded bead can be improved.
The invention obtains the water blasting bead product by the milli-fluidic method, the water blasting bead can be prepared by the one-step method, the sphericity of the water blasting bead is high, and the photo-curable raw material with proper viscosity is selected by selecting the raw material of the wall material, so that the formed water blasting bead has high water content, good water retention performance and moderate crushing strength. Compared with the water blasting bead in the prior art, the water blasting bead has better water retention performance and higher water content, and can be formed in one step. The water blasting bead prepared from the raw materials has moderate diameter and crushing strength, is convenient to add into cigarettes, and is easy to knead and blast while maintaining the mechanical property of the water blasting bead.
Drawings
FIG. 1: the outline of the device for preparing light-curable and high moisture-retention water blasting beads by millifluidic method
The structure in the figure is listed as follows: 1. an internal phase pump; 2. a mesophase pump; 3. an external phase pump; 7. a coaxial needle; 8. a collector; 9. a light-curing device; 10. ultraviolet light lamp beads; 11. curing the tube; 15. a valve; 16. and an exhaust device.
FIG. 2: structure schematic diagram of coaxial needle 7
The structure in the figure is listed as follows: 7. a coaxial needle; 4. an inner layer outlet of the coaxial needle; 5. a coaxial needle intermediate layer outlet; 6. and the coaxial needle is provided with an outer layer outlet.
FIG. 3: schematic structural diagram of curing tube 11
The structures in the figure are listed below: 11. curing the tube; 12. a curing tube inlet; 13. an outlet of the curing tube; 14. and (5) curing the branch pipe orifice of the pipe.
Detailed Description
Example 1
The water blasting bead is prepared by adopting a milli-flow control method. The millifluidic device is shown in figure 2. Using 1 wt% Tween 80 water solution as internal phase, pumping by internal phase pump 1, setting flow rate at 0.20mL/min, extruding from inner layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07mm) of three-layer coaxial needle 7; 97% urethane acrylate prepolymer (viscosity 8000mPa & s, 25 ℃), 3% diphenyl- (2,4, 6-trimethyl benzoyl) oxyphosphorus were used as the intermediate phase, pumped by an intermediate phase pump 2 with the flow rate set to 0.04mL/min, and extruded from a three-layer coaxial needle center outlet 5 (inner diameter 1.6mm, outer diameter 2.1 mm); taking a 3 wt% polyvinyl alcohol solution (viscosity 100 mPas) as an external phase, pumping the external phase by an external phase pump 3 at a flow rate of 8mL/min, sucking the external phase from a collecting device 8, and extruding the external phase from an outlet 6 (inner diameter is 3mm, outer diameter is 3.5mm) of the three-layer coaxial needle. And extruding the three-phase liquid out through a needle simultaneously to form emulsified liquid drops, dripping the liquid drops to the area of a photocuring device 9, curing the mesophase under the irradiation of ultraviolet radiation to generate water-soluble core material blasting beads, taking out the water-soluble core material blasting beads from a collecting device 8, cleaning and drying.
Example 2
The water blasting bead is prepared by adopting a milli-fluidic method. The millifluidic device is shown in figure 2. Using 1 wt% Tween 80 water solution as internal phase, pumping by internal phase pump 1, setting flow rate at 0.20mL/min, extruding from inner layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07mm) of three-layer coaxial needle 7; 97% urethane acrylate prepolymer (viscosity 8000mPa & s, 25 ℃), 3% diphenyl- (2,4, 6-trimethyl benzoyl) oxyphosphorus were used as the intermediate phase, pumped by an intermediate phase pump 2 with the flow rate set to 0.04mL/min, and extruded from a three-layer coaxial needle center outlet 5 (inner diameter 1.6mm, outer diameter 2.1 mm); silicon oil with the viscosity of 100 mPas is used as an external phase, is pumped by an external phase pump 3, is sucked from a collecting device 8 at the flow rate of 8mL/min, and is extruded from an outer layer outlet 6 (the inner diameter is 3mm, and the outer diameter is 3.5mm) of a three-layer coaxial needle. The three-phase liquid is extruded out simultaneously through a needle to generate emulsion droplets, the droplets flow to the area of a light curing device 9, then the intermediate phase is cured under the irradiation of ultraviolet radiation to generate water-soluble core material blasting beads, and the water-soluble core material blasting beads are taken out from a collecting device 8, cleaned and dried.
Example 3
The water blasting bead is prepared by adopting a milli-fluidic method. The millifluidic device is shown in figure 2. Water is used as an internal phase, pumped by an internal phase pump 1, the flow rate is set to be 0.20mL/min, and the water is extruded from an internal layer outlet 4 (the inner diameter is 0.67mm, and the outer diameter is 1.07mm) of a three-layer coaxial needle 7; using 97% urethane acrylate prepolymer (viscosity 14000mPa & s, 25 ℃), 3% diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus as an intermediate phase, pumping by an intermediate phase pump 2, setting the flow rate at 0.04mL/min, and extruding from an intermediate layer outlet 5 (inner diameter 1.6mm, outer diameter 2.1mm) of a three-layer coaxial needle 7; silicone oil with the viscosity of 100 mPas is used as an external phase, is pumped by an external phase pump 3, is sucked from a collecting device 8 at the flow rate of 8mL/min, and is extruded from an outer layer outlet 6 (the inner diameter is 3mm, and the outer diameter is 3.5mm) of a three-layer coaxial needle 7. The three-phase liquid is extruded out simultaneously through a needle to generate emulsion droplets, the droplets flow to the area of a light curing device 9, then the intermediate phase is cured under the irradiation of ultraviolet radiation to generate water-soluble core material blasting beads, and the water-soluble core material blasting beads are taken out from a collecting device 8, cleaned and dried.
Example 4
The same as in example 1 except that 95% of an epoxy acrylate prepolymer and 5% of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate were used as a mesophase (mesophase viscosity 10000 mPas, 25 ℃ C.).
Example 5
The same as in example 1 except that 82% of urethane acrylate prepolymer, 15% of hydroxyethyl methacrylate and 3% of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus were used as a mesophase (mesophase viscosity 1000 mPas, 25 ℃ C.).
Comparative example 1
Preparing calcium alginate water blasting beads by a conventional dripping method. Weighing 2.01g Sodium Alginate (SA)Adding the solid powder into 400mL of deionized water, swelling for 4h at room temperature, transferring into a 55 ℃ water bath kettle, mechanically stirring for 6h, standing and defoaming for 24h to obtain a light yellow transparent SA solution with the weight percent of 0.5. 6.091g of carboxymethyl cellulose (CMC) solid powder is weighed and added into 400mL of deionized water, the mixture is swelled at room temperature for 4h, transferred into a 90 ℃ water bath kettle, mechanically stirred for 6h, and kept stand for defoaming for 24h, so that 1.5 wt% of clear and transparent CMC solution is obtained. Weighing 4.04g of CaCl2Adding the solid into defoamed 1.5 wt% CMC solution, stirring until the solid is completely dissolved, standing for defoaming for 24h to obtain clear and transparent 1.5 wt% CMC/1.0 wt% CaCl2The mixed solution of (1).
1.5 wt% CMC/1.0 wt% CaCl with a single-channel injection push pump at a push rate of 0.5mL/min and a drop height of 10cm2The solution is vertically dripped into the SA solution continuously stirred through a needle with the inner and outer diameters of 0.41/0.71mm, the dripping is stopped after 15min, the stirring is continued for 15min, the solution is filtered by a screen, the capsule is washed by deionized water for three times to remove the residual uncrosslinked SA solution on the surface, and finally the capsule is transferred to 100mL of 2.0 wt% CaCl2Solidifying in the solution for 15min, and washing with deionized water for three times to obtain calcium alginate capsule.
Comparative example 2
The same as in example 1 except that 77% of the urethane acrylate prepolymer, 20% of hydroxyethyl methacrylate and 3% of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus were used as the intermediate phase (intermediate viscosity 600 mPas, 25 ℃ C.).
Comparative example 3
The same as in example 1 except that the urethane acrylate had a viscosity of 16000 mPas (25 ℃ C.).
Specific test method
Quality of
And (4) randomly taking 50 exploded beads, weighing the mass of the exploded beads by using an electronic balance, and calculating the average value of the single mass.
Particle size
Randomly taking 10 exploding beads, taking a picture by using a microscope, marking 12 point coordinates of the outer contour of a shell layer of the exploding beads by using Image-Pro Plus software, fitting a circle by using a least square method, and fitting the diameter of the circle to be used as the grain diameter of the exploding beads.
Thickness of shell
10 popping beads were randomly picked, photographed by a microscope, and the shell thicknesses of 12 sites were measured using Image-Pro Plus software, and the average value was taken as the shell thickness of the popping beads.
Roundness degree
Randomly taking 10 exploded beads, taking pictures by using a microscope, marking 12 point coordinates of the outer contour of an explosion bead shell layer by using Image-Pro Plus software, and fitting a circle by using a least square method to obtain the radius R of the circle1And a coordinate O of the center of the circle. Calculating the distance from 12 point coordinates of the outer contour of the shell of the shot marked by Image-Pro Plus software to a coordinate O of the center of a circle, wherein the maximum distance is dmaxMinimum is dminThe roundness s of the popped bead can be calculated by the following formula (1):
concentricity of
Randomly taking 10 exploding beads, taking a picture by using a microscope, marking 12 point coordinates of the outer contour of an exploding bead shell layer and 12 point coordinates of the inner contour of the exploding bead shell layer by using Image-Pro Plus software, fitting an inner circle and an outer circle by using a least square method to obtain the radius R of the outer circle1Radius of the inner circle R2Two circle center distance doThe concentricity c of the exploding beads can be calculated by the following formula (2):
crushing strength
And randomly taking 20 blasting beads, and testing the crushing strength by using a blasting bead comprehensive tester.
Water carrying capacity
The total mass of the blasting beads is m, the mass of the water is mWater (W)Then, the formula of the water carrying rate of the exploding bead can be calculated by the following formula (3):
water content ratio
The mass of the core liquid of the blasting bead is mCoreMass of water mWater (W)Then, the formula of the water content of the explosion beads can be calculated by the following formula (4):
water retention rate of 7 days
50 beads were randomly placed in a petri dish and placed in a constant temperature and humidity chamber at 25 ℃ and 35% RH for 7 days. Remembering the initial moment of bead blasting with mass m0Weighing the mass of the blasting beads after 7 days as m7Weighing the shell layer of the completely dried blasting bead to be mShellThe formula of the 7-day water retention rate of the exploded bead can be calculated by the following formula (5):
the products obtained in the examples and comparative examples were measured for weight and particle size, and the results of the measurements are shown in table 1 below.
TABLE 1
As can be seen from the specific detection data of the examples and the comparative examples, the water blasting beads with high water content, good water retention performance and moderate crushing strength can be prepared by the concept of the invention. Compared with the traditional water-blown bead of alginate brine, the water-blown bead obtained by the method has higher water content, the water-blown bead product is prepared by adopting one-step milliflow control, the wall material can be extruded from the milliflow control needle head by selecting the polymerization raw material of the wall material, and the water-blown bead product with high water content and moderate crushing strength is formed. The viscosity of the prepolymer in comparative example 3 was too high to allow it to be extruded from a needle and effectively form a water-beading product; the prepolymer in comparative example 2 has too low viscosity, resulting in lower concentricity of the formed water blasting bead product, reduced water retention property, high breakage rate, low water retention rate in 7 days, and failure to form water blasting beads with high water carrying efficiency.
Claims (10)
1. The utility model provides a water of high water retentivity explodes pearl which characterized in that: the wall material is formed by a photo-curable mixture through a curing reaction, and the viscosity of the mixture is 1000-15000 mPa.s; the particle size of the water blasting bead is 2.0mm-4.0 mm; the crushing strength is 1N-25N, the water carrying rate of the water-exploded bead is more than 60 wt%, the water retention rate in 7 days is more than 70 wt%, and further the water-exploded bead can reach 95 wt%.
2. The high water retention water-exploded bead of claim 1, wherein: the main substance of the water-based core material is water, the water content of the core material is preferably 90 wt% -100 wt%, and the water content of the core material is more preferably 99 wt% -100 wt%.
3. The high water retention water-exploded bead of claim 1, wherein: the core material also comprises one or more of water-soluble flavoring substance additive, plant extractant or surface tension regulator.
4. The high water retention water-exploded bead of claim 1, wherein: the mixture of the photo-curing reaction comprises 60 wt% -99 wt% of prepolymer, 0 wt% -30 wt% of diluent and 1 wt% -10 wt% of photoinitiator.
5. The high water retention water bursting bead as claimed in claim 1 or claim 4 which comprises: the prepolymer is one or more of polyurethane acrylate prepolymer, epoxy modified polyurethane prepolymer and the like; the diluent is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate and the like; the photoinitiator is one or more of diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus, 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, diphenylethanone, diphenyl- (4-phenyl sulfur) phenyl sulfonium hexafluoroantimonate and the like.
6. A process for preparing the photo-curable and high water retention water-exploded bead as claimed in any one of claims 1 to 5, wherein: is prepared by millifluidic method.
7. The method for preparing the photosetting and high water retention water-exploded bead of claim 6, wherein the millifluidic method comprises the steps of: (1) respectively filling the water-based core material, the wall material and the external phase liquid into a liquid pump; (2) connecting a liquid pump filled with a water-based core material, a wall material and an external phase liquid with an internal phase needle, an intermediate phase needle and an external phase needle respectively, wherein the internal phase needle, the intermediate phase needle and the external phase needle form a coaxial needle together; (3) connecting a coaxial needle head with a curing tube filled with external phase liquid, arranging ultraviolet lamp beads on two sides of the curing tube, extruding a core material, a wall material and silicon oil out through the coaxial needle head, allowing an extrudate to pass through the curing tube and be cured in the curing tube, and collecting water explosion beads at an outlet of the curing tube; the external phase liquid is incompatible with the wall material, and the viscosity is 10 mPa.s-500 mPa.s.
8. The method for preparing the photosolidable and high water retention water-exploded bead of claim 6, wherein the external phase solution is incompatible with the intermediate phase and can be selected from sodium alginate solution, carboxymethyl cellulose solution, chitosan solution, polyvinyl alcohol solution, silicone oil, vegetable oil or mineral oil.
9. A method for preparing the photosolidable and high water content water-exploded bead as claimed in claim 7, characterized in that: the curing tube is made of ultraviolet light transmitting materials.
10. Use of a water blown bead according to any one of claims 1 to 4 or a water blown bead produced by a method according to any one of claims 5 to 8 in a smoking article.
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