CN114515017B - Water explosion bead with high water retention performance and preparation method and application thereof - Google Patents
Water explosion bead with high water retention performance and preparation method and application thereof Download PDFInfo
- Publication number
- CN114515017B CN114515017B CN202210092773.1A CN202210092773A CN114515017B CN 114515017 B CN114515017 B CN 114515017B CN 202210092773 A CN202210092773 A CN 202210092773A CN 114515017 B CN114515017 B CN 114515017B
- Authority
- CN
- China
- Prior art keywords
- water
- beads
- explosion
- needle head
- external phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011324 bead Substances 0.000 title claims abstract description 122
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000004880 explosion Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000011162 core material Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 41
- 206010016807 Fluid retention Diseases 0.000 claims description 29
- 238000001723 curing Methods 0.000 claims description 28
- 239000002360 explosive Substances 0.000 claims description 13
- 238000000016 photochemical curing Methods 0.000 claims description 9
- 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 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 229940005550 sodium alginate Drugs 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
- 229920002545 silicone oil Polymers 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 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
- 230000000391 smoking effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 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
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000013355 food flavoring agent Nutrition 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 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
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims 1
- 239000005454 flavour additive Substances 0.000 claims 1
- 235000019504 cigarettes Nutrition 0.000 abstract description 9
- 230000009172 bursting Effects 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 47
- 239000010410 layer Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 15
- 239000002775 capsule Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005615 natural polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 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
- 239000000839 emulsion Substances 0.000 description 4
- 239000003960 organic solvent 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 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
- 238000005086 pumping Methods 0.000 description 3
- 239000002994 raw material Substances 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
- -1 cyanoacrylate compound Chemical class 0.000 description 2
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000003205 fragrance Substances 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008385 outer phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 244000061176 Nicotiana tabacum 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019634 flavors Nutrition 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
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 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
- 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
- 230000001681 protective effect Effects 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
- 238000011895 specific detection Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
- A24D3/04—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
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a water explosion bead with high water retention performance, which comprises a wall material and a water-based core material, wherein the wall material is formed by curing a photo-curable mixture, and the viscosity of the mixture is 1000 mPas-15000 mPas; the particle size of the water explosion beads is 2.0mm-4.5mm; the crushing strength is 1N-25N; concentricity is more than 87%, sphericity is more than 94%; the water content of the water burst bead core body can reach 100wt%; the water retention rate can reach 95wt% after 7 days. The water-explosion beads can be prepared by a one-step method by utilizing the formula of the invention, and the prepared water-explosion beads have high water content and good water retention performance. The mechanical strength of the bursting beads is moderate, the bursting beads are easy to pinch while the mechanical performance of the bursting beads is provided, and when the bursting beads are applied to cigarettes, good application experience can be provided.
Description
Technical Field
The invention belongs to the technical field of cigarettes, and particularly relates to a water explosion bead with high water retention performance, a preparation method and application thereof.
Background
The cigarette bursting beads take natural polymer materials or synthetic polymer materials as wall materials, various tobacco essences are wrapped in a tiny airtight spherical capsule in the form of solid, liquid or gas, one or more easily-pinched fragrant capsules are implanted in the production process of the filter tip, the characteristic fragrance release which is manually controllable 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 caused are reduced, and the effects of increasing the humidity of smoke and improving the fragrance interception effect of the filter stick are achieved. Meanwhile, the aroma components in the capsules volatilize, so that the functions of enhancing the aroma and enriching the taste level of the cigarettes can be realized.
Since oily core material beads have been produced in early stages, and the use of an organic solvent for the oily core material has required the use of an organic solvent, the safety of the beads has been poor, and water beads using water or a water-soluble substance as a core material have recently become a research focus. The water is used as the bead-explosion 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 often use water-soluble natural polymers such as gelatin, acacia, alginate and the like, and have the problems of low water retention rate, poor mechanical stability and the like when being used as the wall material of the water explosion beads due to certain water solubility. The water explosion beads prepared from water-soluble wall materials such as alginate and gelatin can completely lose water within one day, and cannot be put into practical use.
In order to solve the leakage problem of the water explosion bead wall material, the prior art adopts a multi-step method to carry out multi-layer coating on the explosion beads so as to improve the water retention property of the explosion beads. For example, CN110250549a discloses a water-carrying capsule with high leakage resistance, wherein the capsule comprises at least three layers, including a core layer, a wall layer and a first water-resistant layer, and it discloses that the water-resistant layer formed by cyanoacrylate compound is formed on the outer surface of the wall layer of natural polymer to improve the water-retaining property of the explosion bead formed by preparing natural polymer. However, this mode of operation requires at least two or more preparation steps, and the wall thickness is difficult to control, resulting in uneven bead size and difficulty in addition to the filter; the prior art CN111758999a discloses that the anti-leakage performance of the explosion bead is improved by further performing electroless plating on the surface of the natural polymer wall material to increase the compactness of the natural polymer structure. 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 disclosed technology discloses a one-step molding process, which adopts a high polymer material with low water permeability to solve the problem of low water retention rate. Application numbers CN201910090596.1 and CN201811372831.6 respectively adopt hydrophobic wall materials such as polylactic acid or polyethylene to prepare water explosion beads by a coagulation bath method, but the water explosion beads need to use organic solvents such as dichloromethane or acetone, cannot be applied to the field of foods, and are not environment-friendly. The application number CN202010841260.7 adopts light-cured resin as a wall material to prepare water explosion beads in a self-assembly mode, but the resin needs to be dissolved by using an organic solvent, and a photoinitiator is added into a water core, so that the water explosion beads have higher biotoxicity and cannot be applied to the field of foods. The application number CN201820575981.6 is characterized in that a channel and a photo-curing device are generated by three-dimensional copolymerization Jiao Ruhua of liquid drops, photo-curing resin is used as a wall material to prepare water explosion beads, and because the device is in a horizontal flowing mode, the emulsified liquid drops adhere to the wall of the tube due to unbalance of gravity and buoyancy, and ultraviolet radiation is used for curing when the water explosion beads are collected, and the water explosion beads are easy to adhere to each other before curing. The application number CN201910618056.6 prepares water burst beads by adopting light-cured resin and paraffin as wall materials in a coaxial drop forming mode, but when the liquid drops drop to the liquid level of the protective liquid, the liquid drops are impacted by the liquid level to deform, so that the sphericity of the burst beads is difficult to control, the dropping speed of the liquid drops is not controllable, the light-curing time is difficult to be ensured, and the problem of incomplete curing is easily caused.
Microfluidic is an emerging technology developed in recent years that can accurately manipulate microscale fluids. Millifluidic is a technology developed on the basis of microfluidics, and can be used for controlling various mutually-insoluble fluids to generate millimeter-scale composite emulsion drops. At present, three millifluidic devices for preparing composite emulsion particles are mainly used: double tee, flow focusing, and coaxial flow. Wherein, the shearing force applied by the continuous phase in the coaxial millifluidic device is more uniform, and the monodispersity of the prepared composite emulsion particles is better. The water-explosion beads with good monodispersity can be obtained by using the coaxial millifluidic device, adopting water as an internal phase, light-cured resin as an intermediate phase, and liquid which is not mutually soluble with the resin as an external phase to prepare composite emulsion drops, and using ultraviolet radiation to cure the intermediate phase.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a photo-curable water explosion bead with high water retention performance, and a preparation method and application thereof. The water explosion beads can be molded in one step by the coaxial millifluidic device and the photo-curing method which are vertically arranged. The water explosion beads prepared by the method have 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 explosion bead with high water retention property, which comprises a wall material and an aqueous core material, wherein the wall material is formed by curing a photo-curable mixture. In the invention, if the viscosity of the mixture is less than 1000 mPa.s, the concentricity of the product explosion beads is low and the breakage rate is high; if the viscosity of the mixture is more than 15000 mPa-s, the mixture is difficult to extrude from the needle. It is therefore reasonable that the viscosity of the mixture is from 1000 mPas to 15000 mPas. In a proper photo-curing mixture viscosity range, the higher viscosity is more favorable for obtaining the explosion beads with low shell thickness and high water carrying rate by adjusting the process, and the lower viscosity is more favorable for the extrusion speed of the mixture, so that the production efficiency is improved. Therefore, the further preferable viscosity of the mixture is 8000 mPas to 10000 mPas. The water explosion beads can be prepared by setting the viscosity of the photo-curing mixture in a proper viscosity range in a millifluidic mode, namely, the reaction wall material can be extruded from a millifluidic needle head, and the formed water explosion beads have high water content and moderate crushing strength.
Further, the photocurable mixture includes 60wt% to 99wt% of a prepolymer, 0wt% to 30wt% of a diluent, and 1wt% to 10wt% of a 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-trimethyl benzoyl) phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxy cyclohexyl phenyl ketone, diphenyl- (4-phenylthio) 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 90-100 wt%, or 95-100 wt%, or 99-100 wt%.
The aqueous core material may further comprise one or more of water-soluble flavoring agent additive, plant extract, and surface tension regulator.
The surface tension regulator can be any one selected from Tween 80, APG 0810, poloxamer 407 and the like; the content of the surface tension regulator in the water-based core material is 0wt% to 5wt%.
The invention also provides a method for preparing the water-explosion beads with high water retention, which adopts millifluidic method to prepare the water-explosion beads, 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 a liquid pump;
(2) The liquid pump with core material, wall material and outer phase liquid is connected to the inner phase needle, middle phase needle and outer phase needle to form coaxial needle.
(3) The coaxial needle is connected with a curing tube filled with external phase liquid, the coaxial needle is immersed below the liquid level of the external phase liquid in 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 through the coaxial needle at the same time, the 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 a viscosity of 10 mPas-500 mPas (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 capable of transmitting ultraviolet light, such as a quartz tube.
The flow rate of the internal phase pump is 0.05mL/min-1.00mL/min, the flow rate of the intermediate phase pump is 0.01mL/min-0.20mL/min, and the flow rate of the external phase pump is 5mL/min-30mL/min.
The millifluidic preparation method can be used for obtaining the water explosion beads by a one-step method, and the obtained water explosion beads have high water content, good water retention performance and moderate crushing strength.
The formed water explosion beads are spherical, the sphericity is more than 94%, further can be more than 96%, or more than 97%.
The average particle size of the water burst beads is 2.0mm-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, etc.
The burst strength of the water burst beads is about 1N-25N, preferably 7N-16N, or 9N-15N. In the crushing strength range, the water explosion bead product has good mechanical strength, is suitable for transportation and storage, is convenient to crush during use, and has good application experience.
The water content of the water explosion beads can reach 100wt%, and the initial water carrying rate can reach 70wt% or more than 80 wt%; the 7 day water retention exceeds 70wt%, or exceeds 95%.
The invention also provides application of the water-explosion beads with high water retention property, and the water-explosion beads are applied to cigarettes. The water explosion beads have good water retention performance, so that the storage performance and the quality stability of the water explosion beads can be improved.
The water explosion bead product is prepared by millifluidic method, the water explosion bead can be prepared by one-step method, the sphericity of the water explosion bead is high, and the water content of the formed water explosion bead is high, the water retention property is good, and the crushing strength is moderate by selecting the photo-curable raw material with proper viscosity through selecting the wall material. Compared with the water explosion beads in the prior art, the water explosion beads have better water retention performance and higher water content, and can be molded in one step. The water explosion beads prepared by the raw materials have moderate particle size and crushing strength, are convenient to be added into cigarettes, and are easy to pinch and explode while keeping the mechanical properties of the water explosion beads.
Drawings
Fig. 1: the invention provides a schematic diagram of a device for preparing photo-curable and high-moisture-retention water explosion beads by millifluidic method
The list of structures in the figure is 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. solidifying the tube; 15. a valve; 16. and an exhaust device.
Fig. 2: schematic structure of coaxial needle 7
The list of structures in the figure is as follows: 7. a coaxial needle; 4. an outlet of the inner layer of the coaxial needle; 5. an outlet of the middle layer of the coaxial needle head; 6. an outer outlet of the coaxial needle.
Fig. 3: schematic structural view of curing tube 11
The list of structures in the figure is as follows: 11. solidifying the tube; 12. a curing tube inlet; 13. a curing tube outlet; 14. solidifying pipe branch pipe orifice.
Detailed Description
Example 1
The millifluidic method is adopted to prepare the water explosion beads. The millifluidic device is shown in figure 2. Pumping by an internal phase pump 1 with a flow rate set to 0.20mL/min and extruding from an internal layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07 mm) of a three-layer coaxial needle 7 by taking 1wt% of Tween 80 as an internal phase; 97% polyurethane acrylate prepolymer (viscosity 8000 mPa.s, 25 ℃) and 3% diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide are taken as intermediate phases, pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and extruded from a three-layer coaxial needle intermediate outlet 5 (inner diameter 1.6mm and outer diameter 2.1 mm); a3 wt% polyvinyl alcohol solution (viscosity: 100 mPa.s) was used as an external phase, and the solution was pumped by an external phase pump 3 at a flow rate of 8mL/min, sucked from a collecting device 8, and extruded from a three-layer coaxial needle outer layer outlet 6 (inner diameter: 3mm, outer diameter: 3.5 mm). The three-phase liquid is extruded through the needle head to form emulsified liquid drops, and after the liquid drops flow to the area of the photo-curing device 9, the intermediate phase is cured under the irradiation of ultraviolet radiation to generate water-soluble core material explosion beads, and the water-soluble core material explosion beads are taken out from the collecting device 8, washed and dried.
Example 2
The millifluidic method is adopted to prepare the water explosion beads. The millifluidic device is shown in figure 2. Pumping by an internal phase pump 1 with a flow rate set to 0.20mL/min and extruding from an internal layer outlet 4 (inner diameter 0.67mm, outer diameter 1.07 mm) of a three-layer coaxial needle 7 by taking 1wt% of Tween 80 as an internal phase; 97% polyurethane acrylate prepolymer (viscosity 8000 mPa.s, 25 ℃) and 3% diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide are taken as intermediate phases, pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and extruded from a three-layer coaxial needle intermediate outlet 5 (inner diameter 1.6mm and outer diameter 2.1 mm); the silicone oil having a viscosity of 100 mPas was used as an external phase and pumped by an external phase pump 3 at a flow rate of 8mL/min, sucked from a collecting device 8, and extruded from a three-layer coaxial needle external layer outlet 6 (inner diameter 3mm, outer diameter 3.5 mm). The three-phase liquid is extruded through the needle head at the same time to generate emulsified liquid drops, and after the liquid drops flow to the area of the photo-curing device 9, the intermediate phase is cured under the irradiation of ultraviolet radiation to generate water-soluble core material explosion beads, and the water-soluble core material explosion beads are taken out from the collecting device 8, washed and dried.
Example 3
The millifluidic method is adopted to prepare the water explosion beads. The millifluidic device is shown in figure 2. Pumping through an internal phase pump 1 with water as an internal phase, wherein the flow rate is set to be 0.20mL/min, and extruding from an inner layer outlet 4 (with the inner diameter of 0.67mm and the outer diameter of 1.07 mm) of a three-layer coaxial needle 7; 97% polyurethane acrylate prepolymer (viscosity 14000 mPa.s, 25 ℃) and 3% diphenyl- (2, 4, 6-trimethylbenzoyl) phosphorus oxide are taken as intermediate phases, pumped by an intermediate phase pump 2, the flow rate is set to be 0.04mL/min, and extruded from an intermediate layer outlet 5 (inner diameter 1.6mm and outer diameter 2.1 mm) of a three-layer coaxial needle 7; the silicone oil having a viscosity of 100 mPas was used as an external phase and pumped by the external phase pump 3 at a flow rate of 8mL/min, sucked from the collecting device 8, and extruded from the external layer outlet 6 (inner diameter 3mm, outer diameter 3.5 mm) of the three-layer coaxial needle 7. The three-phase liquid is extruded through the needle head at the same time to generate emulsified liquid drops, and after the liquid drops flow to the area of the photo-curing device 9, the intermediate phase is cured under the irradiation of ultraviolet radiation to generate water-soluble core material explosion beads, and the water-soluble core material explosion beads are taken out from the collecting device 8, washed and dried.
Example 4
The same as in example 1, except that 95% of the epoxy acrylate prepolymer, 5% of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate were used as the intermediate phase (intermediate phase viscosity 10000 mPa.s, 25 ℃ C.).
Example 5
The same as in example 1, except that 82% of urethane acrylate prepolymer, 15% of hydroxyethyl methacrylate, 3% of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus were used as the intermediate phase (intermediate phase viscosity 1000 mPa.s, 25 ℃ C.).
Comparative example 1
The calcium alginate water explosion beads are prepared by a conventional dripping method. 2.01g of Sodium Alginate (SA) solid powder is weighed, added into 400mL of deionized water, swelled for 4 hours at room temperature, transferred into a water bath kettle at 55 ℃, mechanically stirred for 6 hours, and kept stand for defoaming for 24 hours, thus obtaining 0.5wt% of pale yellow transparent SA solution. 6.091g of carboxymethyl cellulose (CMC) solid powder is weighed, added into 400mL of deionized water, swelled for 4 hours at room temperature, transferred into a water bath kettle at 90 ℃, mechanically stirred for 6 hours, and kept stand for defoaming for 24 hours, thus obtaining 1.5wt% of clear transparent CMC solution. Weigh 4.04g CaCl 2 The solids were added to 1.5w of defoamedIn the solution of the CMC with the concentration of t percent, stirring until the solid is completely dissolved, standing and defoaming for 24 hours to obtain clear and transparent CMC with the concentration of 1.5 percent by weight and CaCl with the concentration of 1.0 percent by weight 2 Is a mixed solution of (a) and (b).
1.5wt% CMC/1.0wt% CaCl using a single channel injection push pump at a push rate of 0.5mL/min and a drop height of 10cm 2 The solution was vertically dropped into the continuously stirred SA solution through a needle having an inner and outer diameter of 0.41/0.71mm, the dropping was stopped after 15min, stirring was continued for 15min, the screen was filtered, the capsule was washed three times with deionized water to remove residual uncrosslinked SA solution on the surface thereof, and finally the capsule was transferred to 100mL of 2.0wt% CaCl 2 Solidifying 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 urethane acrylate prepolymer, 20% of hydroxyethyl methacrylate, 3% of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus were used as the intermediate phase (viscosity of the intermediate phase: 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 ℃).
Specific test method
Quality of
50 explosion beads are randomly taken, and the average value of the single mass is calculated after the explosion bead mass is weighed by using an electronic balance.
Particle size
Taking 10 explosive beads randomly, photographing by using a microscope, marking 12 point coordinates of the outer contour of the explosive bead shell by using Image-Pro Plus software, fitting a circle by using a least square method, and taking the diameter of the fitted circle as the particle size of the explosive beads.
Shell thickness
10 explosive beads were randomly taken, photographed by a microscope, and the shell thicknesses of 12 parts were measured using Image-Pro Plus software, and the average value thereof was used as the shell thickness of the explosive beads.
Roundness of
10 explosive beads are randomly taken, photographed by a microscope, and 12 points of the outer outline of the shell of the explosive beads are marked by using Image-Pro Plus softwareFitting the coordinates to a circle by using a least square method to obtain a radius R of the circle 1 And the coordinates O of the circle center. Calculating the distance from the coordinates of 12 points of the outer contour of the explosion shell to the coordinates O of the circle center, which is the maximum, of the explosion shell by using Image-Pro Plus software, wherein the distance is d max Minimum is d min The roundness s of the explosion bead can be calculated by the following formula (1):
concentricity of
Randomly taking 10 explosion beads, photographing by using a microscope, marking 12 point coordinates of the outer contour of the explosion bead shell layer and 12 point coordinates of the inner contour of the explosion bead shell layer by using Image-Pro Plus software, fitting an inner circle and an outer circle by using a least square method, and obtaining the radius R of the outer circle 1 Radius R of inner circle 2 Distance d between two circle centers o Concentricity c of the explosive bead can be calculated by the following formula (2):
crushing strength
Randomly taking 20 burst beads, and testing the crushing strength of the burst beads by using a burst bead comprehensive tester.
Water carrying rate
The total mass of the explosion beads is m, and the mass of water is m Water and its preparation method The water carrying rate formula of the explosion beads can be calculated by the following formula (3):
water content
The mass of the core liquid of the explosion beads is m Core(s) The mass of water is m Water and its preparation method The water content formula of the explosion beads can be calculated by the following formula (4):
water retention rate of 7 days
50 explosive beads were randomly placed in a petri dish and placed in a constant temperature and humidity box at 25℃and 35% RH for 7 days. The mass of the explosive beads at the starting moment is recorded as m 0 The mass of the explosion beads after 7 days is m 7 Weighing the weight of the shell layer of the completely dried explosion beads to be m Shell and shell The 7-day water retention formula of the burst beads can be calculated by the following formula (5):
the products obtained in examples and comparative examples were measured for weight and particle size, and the detection results are shown in Table 1 below.
TABLE 1
From the specific detection data of the examples and the comparative examples, the water explosion beads with high water content, good water retention and moderate crushing strength can be prepared by the conception of the invention. Compared with the traditional alginate water explosion beads, the water explosion beads obtained by the method have higher water content, the water explosion beads are prepared by adopting a one-step milliflow control method, the wall material can be extruded from the milliflow control needle head through the selection of the wall material polymerization raw material, and the water explosion beads with high water content and moderate crushing strength are formed. The prepolymer in comparative example 3 had a viscosity that was too high to be extruded from the needle and not effectively formed a water burst product; the prepolymer in comparative example 2 has too low viscosity, so that the concentricity of the formed water explosion beads is lower, the water retention performance is reduced, the breakage rate is high, the 7-day water retention rate is low, and the water explosion beads with high-efficiency water carrying cannot be formed.
Claims (7)
1. The utility model provides a water burst pearl of high water retention which characterized in that: the wall material is formed by curing a photo-curable mixture, and the viscosity of the mixture is 1000 mPas-15000 mPas; the particle size of the water explosion beads is 2.0mm-4.0mm; the crushing strength is 1N-25N, the water carrying rate of the water burst beads is more than 60wt percent, and the 7-day water retention rate is more than 70wt percent;
the water explosion beads with high water retention property are prepared by adopting a millifluidic method;
the millifluidic method comprises the following steps: (1) Respectively filling the water-based core material, the wall material and the external phase liquid into a liquid pump; (2) The liquid pump filled with the water-based core material, the wall material and the external phase liquid is respectively connected with the internal phase needle head, the intermediate phase needle head and the external phase needle head, and the internal phase needle head, the intermediate phase needle head and the external phase needle head form a coaxial needle head together; (3) Connecting the coaxial needle with a curing tube filled with external phase liquid, arranging ultraviolet lamp beads at two sides of the curing tube, extruding the core material, the wall material and the silicone oil through the coaxial needle at the same time, allowing the extrudate to pass through the curing tube and be cured in the curing tube, and collecting the 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 mPas-500 mPas;
the mixture capable of photo-curing reaction comprises 60-99 wt% of prepolymer, 0-30 wt% of diluent and 1-10 wt% of photoinitiator;
the prepolymer is one or more of polyurethane acrylate prepolymer, epoxy acrylate prepolymer and epoxy modified polyurethane prepolymer; the diluent is one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate and butyl acrylate; the photoinitiator is one or more of diphenyl- (2, 4, 6-trimethyl benzoyl) phosphorus oxide, 2-hydroxy-2-methyl-1-phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, diphenyl ethanone and diphenyl- (4-phenylthio) phenyl sulfonium hexafluoroantimonate;
the external phase solution is sodium alginate solution, carboxymethyl cellulose solution, chitosan solution, polyvinyl alcohol solution, silicone oil, vegetable oil or mineral oil.
2. A high water retention water burst according to claim 1, wherein: the main substance of the water-based core material is water, and the water content of the core material is 90-100 wt%.
3. A high water retention water burst according to claim 1, wherein: the core material also comprises one or more of water-soluble flavoring additive, plant extractant or surface tension regulator.
4. A method for preparing the water-exploded beads with high water retention according to any one of claims 1 to 3, characterized in that: the preparation method is carried out by millifluidic method.
5. A method of preparing the water-explosive beads with high water retention according to claim 4, 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) The liquid pump filled with the water-based core material, the wall material and the external phase liquid is respectively connected with the internal phase needle head, the intermediate phase needle head and the external phase needle head, and the internal phase needle head, the intermediate phase needle head and the external phase needle head form a coaxial needle head together; (3) Connecting the coaxial needle with a curing tube filled with external phase liquid, arranging ultraviolet lamp beads at two sides of the curing tube, extruding the core material, the wall material and the silicone oil through the coaxial needle at the same time, allowing the extrudate to pass through the curing tube and be cured in the curing tube, and collecting the water explosion beads at an outlet of the curing tube; the external phase liquid is incompatible with the wall material and has a viscosity of 10 mPas to 500 mPas.
6. A method for preparing the water-explosive beads with high water retention according to claim 5, which is characterized in that: the curing tube is made of ultraviolet light-transmitting materials.
7. Use of a water-explosive bead according to any one of claims 1 to 3 or prepared by a method according to any one of claims 4 to 6 in a smoking article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210092773.1A CN114515017B (en) | 2022-01-26 | 2022-01-26 | Water explosion bead with high water retention performance and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210092773.1A CN114515017B (en) | 2022-01-26 | 2022-01-26 | Water explosion bead with high water retention performance and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114515017A CN114515017A (en) | 2022-05-20 |
| CN114515017B true CN114515017B (en) | 2024-03-26 |
Family
ID=81596671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210092773.1A Active CN114515017B (en) | 2022-01-26 | 2022-01-26 | Water explosion bead with high water retention performance and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114515017B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108378417A (en) * | 2018-04-20 | 2018-08-10 | 广西中烟工业有限责任公司 | A kind of preparation method of the quick-fried pearl of water-soluble core material based on milli fluidics |
| WO2018202868A1 (en) * | 2017-05-05 | 2018-11-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Barrier encapsulation of water-based systems on the basis of uv-curable shell systems |
| CN109222223A (en) * | 2018-08-28 | 2019-01-18 | 中国烟草总公司郑州烟草研究院 | A kind of wax water-in type cigarette is with quick-fried pearl and preparation method thereof |
| CN110419774A (en) * | 2019-07-10 | 2019-11-08 | 云南巴菰生物科技有限公司 | A kind of quick-fried pearl of water and preparation method thereof with double rubber layers |
| CN111602847A (en) * | 2020-05-12 | 2020-09-01 | 武汉市昱宸峰科技有限公司 | Water-based blasting bead for cigarettes and preparation method thereof |
| CN113662245A (en) * | 2021-08-23 | 2021-11-19 | 上海烟草集团有限责任公司 | Explosion bead capable of wrapping water-soluble core material, preparation method, equipment and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6780507B2 (en) * | 2000-02-09 | 2004-08-24 | Analytical Research Systems, Inc. | Hydrocapsules and method of preparation thereof |
-
2022
- 2022-01-26 CN CN202210092773.1A patent/CN114515017B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018202868A1 (en) * | 2017-05-05 | 2018-11-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Barrier encapsulation of water-based systems on the basis of uv-curable shell systems |
| CN108378417A (en) * | 2018-04-20 | 2018-08-10 | 广西中烟工业有限责任公司 | A kind of preparation method of the quick-fried pearl of water-soluble core material based on milli fluidics |
| CN109222223A (en) * | 2018-08-28 | 2019-01-18 | 中国烟草总公司郑州烟草研究院 | A kind of wax water-in type cigarette is with quick-fried pearl and preparation method thereof |
| CN110419774A (en) * | 2019-07-10 | 2019-11-08 | 云南巴菰生物科技有限公司 | A kind of quick-fried pearl of water and preparation method thereof with double rubber layers |
| CN111602847A (en) * | 2020-05-12 | 2020-09-01 | 武汉市昱宸峰科技有限公司 | Water-based blasting bead for cigarettes and preparation method thereof |
| CN113662245A (en) * | 2021-08-23 | 2021-11-19 | 上海烟草集团有限责任公司 | Explosion bead capable of wrapping water-soluble core material, preparation method, equipment and application |
Non-Patent Citations (2)
| Title |
|---|
| 国内爆珠专利技术分析;陈婉等;《中国烟草学报》;20201231;第26卷(第1期);118-128 * |
| 浅析香精爆珠制造工艺参数的设计与应用;江文斌;《中国新技术新产品》;20211231(第3期);63-65 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114515017A (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101627086B (en) | Granulated water absorbent containing water-absorbing resin as the main component | |
| CN102675794B (en) | Particle-shaped water absorbing agent and method for producing the same | |
| CN109012521B (en) | Water-encapsulated microcapsule taking water-insoluble polymer as capsule wall material and preparation method thereof | |
| CN110302727B (en) | Millimeter-sized microcapsule and preparation method thereof | |
| CN102690645A (en) | Sustained-release gel-breaking type fracturing propping agent and preparation method thereof | |
| CN109482111B (en) | Bullet-shaped non-spherical microparticles and microcapsules and preparation method thereof | |
| CN107922636A (en) | The method for preparing super absorbent polymer | |
| CN107854449A (en) | A kind of composite nano-microsphere with medicine controlled releasing performance and its preparation method and application | |
| JPS58164622A (en) | Manufacture of porous body with adjustable total pore volume, adjustable pore diameter and adjustable pore wall | |
| CN113198041B (en) | Visible monodisperse embolism microsphere with internal radiation therapeutic performance and preparation method thereof | |
| CN102114006B (en) | Preparation method of chitosan hollow and core-shell microcapsule with pH-sensitive burst release property | |
| CN108479652B (en) | Shape-controllable shell-core vitamin E microcapsule and preparation method thereof | |
| CN102120854B (en) | Temperature-responsive three-dimensional ordered macroporous controlled-release material | |
| CN114515017B (en) | Water explosion bead with high water retention performance and preparation method and application thereof | |
| JPH1147581A (en) | Slow release capsule and its preparation | |
| CN101522719A (en) | Method for the production of water absorbent polymer particles by polymerizing drops of a monomer solution | |
| WO2021023041A1 (en) | Preparation method for non-spherical hydrogel microparticle embolic agent | |
| WO2018124404A1 (en) | Super absorbent polymer and manufacturing method therefor | |
| CN101670255A (en) | Method for preparing functional magnetic high molecular microsphere by super-thick emulsion method | |
| CN109480331B (en) | Preparation method and device of water blasting bead | |
| CN102936390B (en) | Collagen-g-polymer/Ag multi-hole nano antibacterial film material and preparation method thereof | |
| CN114534648B (en) | Device for preparing photo-curing water-carrying capsule and preparation method of photo-curing water-carrying capsule | |
| CN107596445A (en) | Poly- citrate performed polymer/chitin nano whisker slurry and preparation method thereof | |
| CN109265711B (en) | Preparation method of polymer particles | |
| CN114380956B (en) | Preparation method of asymmetric water-absorbent resin and drop former used for preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |