CN112337446A - Small ball capable of quickly removing preservative as well as preparation method and application thereof - Google Patents
Small ball capable of quickly removing preservative as well as preparation method and application thereof Download PDFInfo
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- CN112337446A CN112337446A CN202011116744.1A CN202011116744A CN112337446A CN 112337446 A CN112337446 A CN 112337446A CN 202011116744 A CN202011116744 A CN 202011116744A CN 112337446 A CN112337446 A CN 112337446A
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- Prior art keywords
- preservative
- preparation
- pellets
- solution
- mixed solution
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 38
- 230000002335 preservative effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002537 cosmetic Substances 0.000 claims abstract description 39
- 239000008188 pellet Substances 0.000 claims abstract description 39
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 8
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical group COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 8
- -1 1-p-hydroxycyclohexyl phenyl Chemical group 0.000 claims description 7
- 238000012719 thermal polymerization Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 5
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 4
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 4
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 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 3
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- 229960002216 methylparaben Drugs 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- YHHSONZFOIEMCP-UHFFFAOYSA-O phosphocholine Chemical compound C[N+](C)(C)CCOP(O)(O)=O YHHSONZFOIEMCP-UHFFFAOYSA-O 0.000 claims description 3
- 229950004354 phosphorylcholine Drugs 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 claims description 2
- 229940008099 dimethicone Drugs 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 7
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 7
- 238000011109 contamination Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 206010067484 Adverse reaction Diseases 0.000 description 4
- 230000006838 adverse reaction Effects 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229940083037 simethicone Drugs 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](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]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920002674 hyaluronan Polymers 0.000 description 2
- 229960003160 hyaluronic acid Drugs 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 206010012442 Dermatitis contact Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CMHSKZTVGYZYAK-UHFFFAOYSA-N OC1CCC(CC1)C1(CC=CC=C1)C(=O)C1(CC=CC=C1)C1CCC(CC1)O Chemical compound OC1CCC(CC1)C1(CC=CC=C1)C(=O)C1(CC=CC=C1)C1CCC(CC1)O CMHSKZTVGYZYAK-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 206010046742 Urticaria contact Diseases 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000032823 cell division Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940011871 estrogen Drugs 0.000 description 1
- 239000000262 estrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 230000001706 oxygenating effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention belongs to the technical field of materials, and discloses a small ball capable of quickly removing a preservative, and a preparation method and application thereof. The invention adopts a monomer polymerization method to synthesize preservative removing pellets, which comprises the following steps: 1) adding a monomer solution into a reactor, and adding a cross-linking agent while stirring to obtain a mixed solution; 2) introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, adding an initiator, dropwise adding the solution into a poor solvent under the condition of isolating oxygen, and carrying out polymerization reaction to obtain a solidified small ball; 3) and collecting the solidified pellets, cleaning the solidified pellets with distilled water and ethanol, and drying to obtain the preservative-removed pellets. The preservative removal pellet prepared by the preparation method can quickly adsorb the paraben preservative in the cosmetics to reduce the content of the paraben preservative by more than 90 percent, and has small adsorption on active ingredients in the cosmetics.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a small ball capable of quickly removing a preservative, and a preparation method and application thereof.
Background
The cosmetics are chemical industrial products which are spread on the surface of a human body by smearing, spraying or other similar methods so as to achieve the purposes of cleaning, eliminating bad air temperature, protecting skin, beautifying and modifying. Cosmetics, especially cosmetics with high water content, may be polluted by microbes to deteriorate during production, storage and use, and may damage human body to lose use value. At present, methods for avoiding microbial contamination in cosmetics are:
1) adding a preservative. The antiseptic acts on cell membrane, cell wall or organelle of microorganism to destroy cell proliferation and division, and inhibit growth and reproduction of microorganism to prevent microbial contamination of cosmetics. The technology has the advantages of low cost and good bacteriostatic effect. The disadvantages are: preservatives can cause a series of adverse reactions to the skin and the whole body, especially to sensitive people.
2) And (4) packaging technology. Mainly including sterile single dose packaging techniques for single use and special outlet design techniques for multiple uses. The technology firstly inactivates microorganisms in the cosmetics through a sterilization technology, and then prevents the cosmetics from contacting bacteria in the using process through a packaging technology, so that the contamination of bacteria in the using process is avoided. The advantages of this technique are: the effect of isolating bacterial contamination is good, and meanwhile, the potential risk brought by using the preservative is avoided. The disadvantage is high cost.
The addition of the preservative is the most widely used cosmetic preservation strategy at present, and more than 95% of cosmetics in the market are preserved by adding the preservative. Among them, parabens (parabens) are the most widely used preservatives in cosmetics, because they have a broad antibacterial action against molds, yeasts and bacteria, especially against the former two, and belong to broad-spectrum antibacterial agents; meanwhile, the cosmetic is low in price, colorless and tasteless, and does not influence the use of the cosmetic. However, the safety of the skin care product is controversial, and researches show that the methylparaben is likely to react with UVB ultraviolet rays on the skin, so that the risk of skin aging is increased; meanwhile, part of people are sensitive to the parabens, contact dermatitis can be caused by long-term use of cosmetics containing the parabens, and few patients can generate contact urticaria and stimulation reaction; in addition, research has shown that the paraben components may cause abnormal estrogen secretion in women, thereby causing breast cancer.
Aiming at the series of adverse reactions of the nipagin ester preservative, the current strategy mainly comprises the following steps:
1) harmless preservative is used. Researches show that some natural plant essential oils and polysaccharides have certain bacteriostatic action. However, these substances only have effects on specific flora, and in order to achieve broad-spectrum antibacterial effect, a large amount of various essential oils or polysaccharides need to be added, so that the functions of the components of the cosmetic are complicated, and meanwhile, the problem of solubility of the essential oils is not suitable for the water-based cosmetic, and the water-based cosmetic has high risk of bacterial contamination.
2) Controlling the use amount of the parabens. The maximum allowable addition amount of the nipagin ester preservative in the cosmetics is regulated in all countries, but the adverse reaction of the nipagin ester preservative to users cannot be fundamentally solved by controlling the addition amount.
Disclosure of Invention
In view of the above, the present invention provides a pellet capable of rapidly removing a preservative, which can entrap the preservative by specific adsorption, and a method for preparing the same and an application thereof.
The invention provides a preparation method of a small ball capable of quickly removing preservatives, which comprises the following steps:
1) adding a monomer solution into a reactor, and adding a cross-linking agent while stirring to obtain a mixed solution, wherein the monomer solution is one or more of hydroxyethyl methacrylate, N-vinyl pyrrolidone, cyclohexyl methacrylate, N-dimethylacrylamide and siloxane monomer, cyclohexyl methacrylate, phosphorylcholine and siloxane monomer, hydroxyethyl methacrylate, methacrylic acid, 4-vinylpyridine and acrylic acid;
2) introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, and then adding an initiator;
3) dropwise adding the solution obtained by the treatment in the step 2) into a poor solvent under the condition of isolating oxygen, and carrying out polymerization reaction to obtain a solidified small ball;
4) and collecting the solidified pellets, cleaning the solidified pellets with distilled water and ethanol, and drying the solidified pellets.
Further, the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and N, N' -methylene bisacrylamide.
Further, the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenyl-1-propanone, 1-p-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-p-hydroxy-2-methyl-1- [4- (2-p-hydroxyethoxy) phenyl ] -1-propanone and methyl benzoylformate Or several of them.
Further, the poor solvent in the step 3) is one or more of liquid paraffin, dimethyl silicone oil, soybean oil, peanut oil, linseed oil, castor oil and rapeseed oil.
Further, the polymerization reaction in the step 3) is specifically: and carrying out thermal polymerization reaction by heating, wherein the time of the thermal polymerization reaction is 10-30 h.
Further, the polymerization reaction in the step 3) is specifically: carrying out photopolymerization reaction by ultraviolet irradiation for 10-60 min,
the invention also provides the small ball which is prepared by the preparation method and can quickly remove the preservative.
Furthermore, the diameter of the small ball is 1-10 mm.
The invention also provides application of the small ball in removing the paraben preservative in the solution type or gel type cosmetics.
Further, the nipagin ester preservative is methyl p-hydroxybenzoate or ethyl p-hydroxybenzoate.
Compared with the prior art, the preservative removing microspheres provided by the invention have specificity and rapid adsorption on the paraben preservative in the cosmetics, and less adsorption on other active substances in the cosmetics. On the basis of not losing the efficacy of the cosmetics, the risk of adverse reactions of the cosmetics is reduced, and the cosmetic is particularly suitable for people with preservative sensitivity.
Drawings
FIG. 1 Effect of HEMA/VP beads on the content of ingredients in a home-made cosmetic at different pour-over times.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The invention provides a preparation method of a small ball capable of quickly removing preservatives, which comprises the following steps:
1) adding a monomer solution into a reactor, and adding a cross-linking agent while stirring to obtain a mixed solution;
2) introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, and then adding an initiator;
3) dropwise adding the solution obtained by the treatment in the step 2) into a poor solvent under the condition of isolating oxygen, and carrying out polymerization reaction to obtain a solidified small ball;
4) and collecting the solidified pellets, cleaning the solidified pellets with distilled water and ethanol, and drying the solidified pellets.
Specifically, the monomer solution is added into a reactor, and then the cross-linking agent is added while stirring to obtain a mixed solution. In the invention, the monomer solution is selected from one or more of hydroxyethyl methacrylate, N-vinyl pyrrolidone, cyclohexyl methacrylate, N-dimethylacrylamide and siloxane monomer, cyclohexyl methacrylate, phosphorylcholine and siloxane monomer, hydroxyethyl methacrylate, methacrylic acid, 4-vinylpyridine and acrylic acid, and more preferably is hydroxyethyl methacrylate/4-vinylpyridine; the adopted cross-linking agent is preferably one or more selected from polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and N, N' -methylene bisacrylamide, and more preferably polyethylene glycol dimethacrylate.
And after a mixed solution is obtained, introducing nitrogen into the mixed solution to remove dissolved oxygen, adding an initiator, collecting the solidified pellets, cleaning the solidified pellets with distilled water and ethanol, and drying to obtain the preservative-removed pellets. In this process, the initiator used in the present invention is preferably one member selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenylpropanone, 1-p-hydroxycyclohexylphenylketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-p-hydroxy-2-methyl-1- [4- (2-p-hydroxyethoxy) phenyl ] -1-propanone and methyl benzoylformate One or more, more preferably azobisisobutyronitrile or 2-p-hydroxy-2-methyl-1-phenyl-1-propanone; in the polymerization reaction, preferably, the thermal polymerization reaction is performed by heating or the photopolymerization reaction is performed by ultraviolet irradiation, the time of the thermal polymerization reaction is preferably 10 to 30 hours, more preferably 12 to 24 hours, the time of the photopolymerization reaction is 10 to 60min, and more preferably 15 to 30 min; the poor solvent is one or more of liquid paraffin, dimethyl silicone oil, soybean oil, peanut oil, linseed oil, castor oil and rapeseed oil, and the dimethyl silicone oil is preferred.
And after the polymerization reaction is finished, collecting the pellets, cleaning the pellets by using distilled water and ethanol, and drying the pellets in a drying box to obtain the preservative-removed pellets. Wherein the diameter of the small ball is 1-10 mm, preferably 1.5-5 mm.
The invention also provides the preservative removal pellet prepared by the preparation method.
The invention also provides application of the preservative removing pellet prepared by the preparation method in removing the paraben preservative in solution type or gel type cosmetics.
To further illustrate the present invention, the following examples are given to describe in detail the preparation of the preservative removing pellets provided by the present invention.
Example 1
Preparation of thermally polymerized hydroxyethyl methacrylate/4-vinylpyridine (HEMA/VP) pellets:
(1) after 4g of hydroxyethyl methacrylate and 2g of 4-vinylpyridine were mixed, 0.1g of a crosslinking agent polyethylene glycol dimethacrylate was added with stirring to obtain a mixed solution.
(2) And introducing nitrogen into the mixed solution to remove dissolved oxygen, adding 0.1g of initiator azobisisobutyronitrile, dropwise adding the solution into 65 ℃ simethicone under the condition of isolating oxygen, and carrying out thermal polymerization for 24 hours to obtain the cured pellets.
(3) Collecting the pellets, alternately cleaning the pellets with distilled water and ethanol, and drying to obtain the HEMA/VP pellets.
Example 2
Preparation of photopolymerizable hydroxyethyl methacrylate/4-vinylpyridine (HEMA/VP) beads:
(1) after 4g of hydroxyethyl methacrylate and 2g of 4-vinylpyridine were mixed, 0.1g of a crosslinking agent polyethylene glycol dimethacrylate was added with stirring to obtain a mixed solution.
(2) And introducing nitrogen into the mixed solution to remove dissolved oxygen, adding 0.08g of initiator 2-p-hydroxy-2-methyl-1-phenyl-1-acetone, dropwise adding the solution into simethicone under the condition of isolating oxygen, and irradiating the simethicone for 15min by 365nm ultraviolet rays at room temperature to obtain the cured pellets.
(3) Collecting the pellets, alternately cleaning the pellets with distilled water and ethanol, and drying to obtain the HEMA/VP pellets.
Example 3
Testing the content change of each component after the home-made cosmetic solution flows through the HEMA/VP beads:
to illustrate whether the pellets of the present invention, while removing the paraben preservative, would cause adsorption losses for typical small and large molecule actives in cosmetics. The self-made cosmetic solution is taken as an example for illustration, and the self-made cosmetic solution comprises the following components: 1% nicotinamide, 0.2% hyaluronic acid, 0.2% methylparaben, 0.1% ethylparaben.
Filling 50mL of self-made cosmetic solution into a PVC bottle; the HEMA/VP beads provided in example 1 were fixed using a PVC mesh that fits the mouth of a PVC bottle and then sealed in the PVC mouth. And (3) pouring the self-made cosmetic solution by inverting the light-pressure PVC bottle, simulating the using process, repeatedly pouring for 5 times, pouring about 10mL of the self-made cosmetic solution once, and then measuring the content of each component in the self-made cosmetic solution poured each time.
The effect of the small balls on the content of each component in the self-made cosmetic solution under different pouring times is shown in figure 1, which shows that the content of the preservatives methyl p-hydroxybenzoate and ethyl p-hydroxybenzoate in the poured self-made cosmetic solution is obviously reduced, and the loss of the small molecular active ingredient nicotinamide and the large molecular active ingredient hyaluronic acid is less. The effect of removing the nipagin ester preservative by the small ball is verified again, meanwhile, the small molecular active ingredients and the macromolecular active ingredients in the cosmetics cannot be lost, and the result is unchanged after the small ball is used for multiple times through simulation of multiple dumping.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a small ball capable of quickly removing preservatives is characterized by comprising the following steps:
1) adding a cross-linking agent into the monomer solution while stirring to obtain a mixed solution,
the monomer solution is one or more of hydroxyethyl methacrylate, N-vinyl pyrrolidone, cyclohexyl methacrylate, N-dimethylacrylamide and siloxane monomer, cyclohexyl methacrylate, phosphorylcholine and siloxane monomer, hydroxyethyl methacrylate, methacrylic acid, 4-vinylpyridine and acrylic acid;
2) introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, and then adding an initiator;
3) dropwise adding the solution obtained by the treatment in the step 2) into a poor solvent under the condition of isolating oxygen, and carrying out polymerization reaction to obtain a solidified small ball;
4) and collecting the solidified pellets, cleaning the solidified pellets with distilled water and ethanol, and drying the solidified pellets.
2. The preparation method according to claim 1, wherein the crosslinking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and N, N' -methylenebisacrylamide.
3. The process according to claim 1, wherein the initiator is azobisisobutyronitrile, azobisisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenyl-1-propanone, 1-p-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2, 4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-p-hydroxy-2-methyl-1- [4- (2-p-hydroxyethoxy) phenyl ] - One or more of 1-acetone and methyl benzoylformate.
4. The method according to claim 1, wherein the poor solvent in step 3) is one or more of liquid paraffin, dimethicone, soybean oil, peanut oil, linseed oil, castor oil and rapeseed oil.
5. The preparation method according to claim 1, wherein the polymerization reaction in step 3) is specifically: and carrying out thermal polymerization reaction by heating, wherein the time of the thermal polymerization reaction is 10-30 h.
6. The preparation method according to claim 1, wherein the polymerization reaction in step 3) is specifically: and carrying out photopolymerization reaction by ultraviolet irradiation, wherein the time of the photopolymerization reaction is 10-60 min.
7. A rapidly preservative-removable pellet prepared by the preparation method according to any one of claims 1 to 6.
8. The pellet of claim 7, wherein the pellet has a diameter of 1 to 10 mm.
9. Use of the pellet of claim 7 for removing a paraben preservative from a cosmetic solution or gel.
10. The use according to claim 9, wherein the paraben preservative is methylparaben or ethylparaben.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106554446A (en) * | 2016-10-28 | 2017-04-05 | 佛山科学技术学院 | A kind of fast preparation method of multi-functional fluoropolymer microsphere |
| CN107478731A (en) * | 2016-06-07 | 2017-12-15 | 复旦大学 | The pre-treating method of parabens preservative in a kind of detection cosmetics |
| CN111132640A (en) * | 2017-09-25 | 2020-05-08 | 佛罗里达大学研究基金会股份有限公司 | Removal of preservative from eye drops containing hydrophilic drug |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107478731A (en) * | 2016-06-07 | 2017-12-15 | 复旦大学 | The pre-treating method of parabens preservative in a kind of detection cosmetics |
| CN106554446A (en) * | 2016-10-28 | 2017-04-05 | 佛山科学技术学院 | A kind of fast preparation method of multi-functional fluoropolymer microsphere |
| CN111132640A (en) * | 2017-09-25 | 2020-05-08 | 佛罗里达大学研究基金会股份有限公司 | Removal of preservative from eye drops containing hydrophilic drug |
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