CN112316922B - Preservative adsorption microsphere as well as preparation method and application thereof - Google Patents
Preservative adsorption microsphere as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN112316922B CN112316922B CN202011116345.5A CN202011116345A CN112316922B CN 112316922 B CN112316922 B CN 112316922B CN 202011116345 A CN202011116345 A CN 202011116345A CN 112316922 B CN112316922 B CN 112316922B
- Authority
- CN
- China
- Prior art keywords
- preservative
- solution
- reactor
- adsorption
- cosmetics
- 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
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 239000003755 preservative agent Substances 0.000 title claims abstract description 56
- 230000002335 preservative effect Effects 0.000 title claims abstract description 51
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002537 cosmetic Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- -1 nipagin ester Chemical class 0.000 claims abstract description 17
- 239000000725 suspension 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 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 30
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 24
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 claims description 17
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical group COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 claims description 17
- 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 claims description 14
- 229920002674 hyaluronan Polymers 0.000 claims description 14
- 229960003160 hyaluronic acid Drugs 0.000 claims description 14
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 claims description 13
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 claims description 13
- 229960002216 methylparaben Drugs 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 claims description 12
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 claims description 12
- 229960003966 nicotinamide Drugs 0.000 claims description 12
- 235000005152 nicotinamide Nutrition 0.000 claims description 12
- 239000011570 nicotinamide Substances 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000012719 thermal polymerization Methods 0.000 claims description 4
- 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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 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 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
- 229960001617 ethyl hydroxybenzoate Drugs 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229940095102 methyl benzoate 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
- 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 2
- 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 2
- 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 2
- 230000003020 moisturizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002087 whitening effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 20
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- 230000008569 process Effects 0.000 description 8
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 206010067484 Adverse reaction Diseases 0.000 description 4
- 230000006838 adverse reaction Effects 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000012536 packaging technology Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000341 volatile oil Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- YHHSONZFOIEMCP-UHFFFAOYSA-O phosphocholine Chemical compound C[N+](C)(C)CCOP(O)(O)=O YHHSONZFOIEMCP-UHFFFAOYSA-O 0.000 description 2
- 229950004354 phosphorylcholine Drugs 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UXOWGYHJODZGMF-QORCZRPOSA-N Aliskiren Chemical compound COCCCOC1=CC(C[C@@H](C[C@H](N)[C@@H](O)C[C@@H](C(C)C)C(=O)NCC(C)(C)C(N)=O)C(C)C)=CC=C1OC UXOWGYHJODZGMF-QORCZRPOSA-N 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 description 1
- 206010012442 Dermatitis contact Diseases 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
- 238000002835 absorbance Methods 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229960004601 aliskiren Drugs 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000001045 blue dye Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 208000010247 contact dermatitis Diseases 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 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
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- GYCKQBWUSACYIF-UHFFFAOYSA-N o-hydroxybenzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1O GYCKQBWUSACYIF-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/28019—Spherical, ellipsoidal or cylindrical
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The invention belongs to the technical field of materials, and discloses a preservative adsorption microsphere as well as a preparation method and application thereof. The invention synthesizes preservative adsorption microsphere by adopting a monomer polymerization method, which comprises the following steps: 1) Adding a monomer solution into a reactor, and sequentially adding a cross-linking agent and a solvent containing a stabilizer 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, sealing a reactor to isolate oxygen, and performing polymerization reaction under the stirring condition to obtain a suspension; 3) And (3) leading out the suspension from the reactor, centrifuging, cleaning the solid obtained by centrifuging with distilled water, and drying to obtain the preservative removal microsphere. The preservative desorption and removal microsphere prepared by the preparation method can rapidly adsorb the nipagin ester preservative in the cosmetics, so that the content of the nipagin ester preservative is reduced by more than 90%, and the adsorption of active ingredients in the cosmetics is small.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preservative adsorption microsphere and a preparation method and application thereof.
Background
Cosmetics are a type of chemical industry that is spread on the surface of the human body by painting, spraying or other similar methods to achieve the purposes of cleaning, eliminating bad air temperature, skin care, beauty and finishing. Cosmetics, particularly cosmetics with higher water content, can be polluted by microorganisms to deteriorate during production, storage and use, and damage to human bodies to lose use value. At present, the methods for avoiding microbial contamination in cosmetics are as follows:
(1) Adding preservative. The preservative can destroy cell proliferation and division by acting on cell membrane, cell wall or organelle of microorganism, inhibit growth and proliferation of microorganism, and further prevent cosmetic microorganism pollution. The technology has the advantages of low cost and good antibacterial effect. The defects are as follows: preservatives can cause a series of adverse reactions to the skin and the whole body, especially for sensitive people.
(2) Packaging technology. Mainly comprises a sterile single-dose packaging technology for single use and a special outlet design technology for multiple use. The technology firstly makes the microorganism in the cosmetics inactive through a sterilization technology, and then makes the cosmetics avoid contacting bacteria in the use process through a packaging technology, thereby avoiding the contamination of bacteria in the use process. The advantages of this technique are: the effect of isolating bacterial pollution is good, and the potential risk brought by using the preservative does not exist. The disadvantage is the high cost.
The preservative is the most widely used cosmetic preservative strategy at present, and more than 95% of cosmetics in the market are preserved by adopting the preservative. Among them, parabens (paraben) are the most widely used preservatives in cosmetics, because they have a broad antibacterial effect on mold, yeast and bacteria, especially on the former two, and are broad-spectrum antibacterial agents; meanwhile, the price is low, the color and smell are colorless and odorless, and the use of the cosmetics is not affected. However, the safety is continuously controversial, and researches show that the methyl parahydroxybenzoate possibly reacts with UVB ultraviolet rays on the skin, so that the risk of skin aging is increased; meanwhile, part of people can be 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 stimulus response; in addition, studies have shown that the nipagin ester component may cause abnormal estrogen secretion in women, thereby causing breast cancer.
Aiming at the series of adverse reactions of the parabens preservative, the current strategies mainly comprise:
(1) Harmless preservative is used. Research shows that some natural plant essential oils and polysaccharides have certain antibacterial effect. However, these substances only have effects for specific flora, and in order to achieve broad-spectrum antibacterial effect, a large amount of various essential oils or polysaccharides are required to be added, so that the functions of the components of the cosmetics are complicated, and meanwhile, the problem of solubility of the essential oils is not suitable for the aqueous cosmetics, which have high risk of bacterial contamination.
(2) Controlling the usage amount of the nipagin esters. 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 on a user cannot be fundamentally solved by controlling the dosage.
Disclosure of Invention
Accordingly, the present invention provides a preservative adsorption microsphere and a preparation method thereof, wherein the preservative adsorption microsphere can entrap a preservative through specific adsorption.
The invention provides a preparation method of preservative adsorption microspheres, which comprises the following steps:
1) Adding a monomer solution in a reactor, and sequentially adding a cross-linking agent and a solvent containing a stabilizing 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-dimethyl acrylamide and siloxane monomers, cyclohexyl methacrylate, phosphorylcholine and siloxane monomers, hydroxyethyl methacrylate, methacrylic acid, 4-vinyl pyridine and acrylic acid;
2) Introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, adding an initiator, sealing a reactor to isolate oxygen, and performing polymerization reaction under the stirring condition to obtain a suspension;
3) And (3) leading out the suspension from the reactor, centrifuging, cleaning the solid obtained by centrifuging with distilled water, and drying to obtain the preservative adsorption microsphere.
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, in the solvent containing the stabilizer: the stabilizer is polyvinylpyrrolidone, and the solvent is one of water, methanol and ethanol.
Further, the initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenyl-1-propanone, 1-p-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 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 benzoate.
Further, the stirring speed in the step 2) is 350-450 r/min.
Further, the polymerization in step 2) may be a thermal polymerization by heating or a photopolymerization by ultraviolet irradiation, and the polymerization time is 10 to 30 hours.
Further, the speed of centrifugation in the step 3) is 900-1100 r/min, and the time of centrifugation is 8-15 min.
The invention also provides the preservative adsorption microsphere prepared by the preparation method.
The invention also provides application of the preservative adsorption microsphere in removing the nipagin ester preservative in the solution-type or gel-type cosmetics.
Further, the paraben preservative is methyl parahydroxybenzoate or ethyl parahydroxybenzoate.
Compared with the prior art, the preservative adsorption microsphere provided by the invention has specificity and quick adsorption on the parabens preservative in the cosmetics, and has less adsorption on other active substances in the cosmetics. On the basis of not losing the efficacy of the cosmetics, the adverse reaction risk of the cosmetics is reduced, and the cosmetics are particularly suitable for people sensitive to preservatives.
Drawings
FIG. 1 effect of HEMA/VP microspheres on methyl hydroxybenzoate content at different concentrations for different pour times;
FIG. 2 effect of HEMA/VP microspheres on ethyl hydroxybenzoate content at different concentrations for different pour times;
FIG. 3 effect of HEMA/VP microspheres on nicotinamide content at different concentrations for different pour times;
FIG. 4 effect of HEMA/VP microspheres on hyaluronic acid content at different concentrations for different pour times;
FIG. 5 effect of HEMA/VP microspheres on the content of each component of self-made cosmetics at different pouring times;
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The invention provides a preparation method of preservative adsorption microspheres, which comprises the following steps:
1) Adding a monomer solution into a reactor, and sequentially adding a cross-linking agent and a solvent containing a stabilizer 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, sealing a reactor to isolate oxygen, and performing polymerization reaction under the stirring condition to obtain a suspension;
3) And (3) leading out the suspension from the reactor, centrifuging, cleaning the solid obtained by centrifuging with distilled water, and drying to obtain the preservative adsorption microsphere.
Specifically, the invention firstly adds the stabilizer into the solvent to obtain the solvent containing the stabilizer. Wherein the stabilizer is preferably polyvinylpyrrolidone, and the solvent is preferably one selected from water, methanol and ethanol, and more preferably a mixed solution of ethanol and water. Then, after the monomer solution is added into the reactor, the reactor is started to start stirring, the cross-linking agent is added under the stirring condition, and then the solvent containing the stabilizer which is prepared firstly is added, so that the mixed solution is obtained. In the present invention, the monomer solution used is selected from one or more of hydroxyethyl methacrylate, N-vinylpyrrolidone, cyclohexyl methacrylate, N-dimethylacrylamide and siloxane monomer, cyclohexyl methacrylate, phosphorylcholine and siloxane monomer, hydroxyethyl methacrylate, methacrylic acid, 4-vinylpyridine and acrylic acid, more preferably hydroxyethyl methacrylate/4-vinylpyridine; the crosslinking agent is preferably selected from one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and N, N' -methylenebisacrylamide, more preferably polyethylene glycol dimethacrylate.
After the mixed solution is obtained, nitrogen is introduced into the mixed solution to remove dissolved oxygen in the mixed solution, then an initiator is added, then the reactor is sealed to isolate oxygen, and polymerization reaction is carried out under the stirring condition, so as to obtain a suspension. In this process, the initiator used in the present invention is preferably one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenylpropion, 1-p-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholino) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholino) phenyl ] -1-butanone, 2-p-hydroxy-2-methyl-1- [4- (2-p-hydroxyethoxy) phenyl ] -1-propanone and methyl benzoate, more preferably azobisisobutyronitrile or 2-p-hydroxy-2-methyl-1-phenyl-1-propanone; stirring is carried out after the reactor is sealed, wherein the stirring speed is preferably 350-450 r/min, more preferably 400r/min; in the polymerization reaction, it is preferable to carry out the thermal polymerization reaction by heating or the photopolymerization reaction by ultraviolet irradiation, and the polymerization reaction time is preferably 10 to 30 hours, more preferably 12 to 24 hours.
After the polymerization reaction is finished, the suspension is led out from the reactor, the led-out suspension is centrifuged, the solid obtained by the centrifugation is washed by distilled water, and the solid is put into a drying box for drying, so that the preservative adsorption microsphere is obtained. The speed of centrifugation is preferably 900-1100 r/min, more preferably 1000r/min, and the time of centrifugation is preferably 8-15 min, more preferably 10min.
The invention also provides the preservative adsorption microsphere prepared by the preparation method.
The invention also provides an application of the preservative adsorption microsphere prepared by the preparation method in removing the nipagin ester preservative in the solution-type or gel-type cosmetics.
In order to further illustrate the present invention, the following describes in detail the preparation method of the preservative adsorption microsphere provided by the present invention with reference to examples.
Example 1
Preparation of thermally polymerized hydroxyethyl methacrylate/4-vinylpyridine (HEMA/VP) microspheres:
(1) 4g of hydroxyethyl methacrylate and 2g of 4-vinylpyridine are mixed and added into a reactor, then 0.1g of polyethylene glycol dimethacrylate as a crosslinking agent is added while stirring, and then 50mL of an ethanol/water (1:1, V/V) solution containing 4% polyvinylpyrrolidone is added to obtain a mixed solution.
(2) Nitrogen is introduced into the mixed solution to remove dissolved oxygen, then 0.06g of initiator azodiisobutyronitrile is added, then the reactor is sealed to isolate oxygen, and the thermal polymerization reaction is carried out for 24 hours at the temperature of 65 ℃ and the stirring speed of 400r/min, so as to obtain suspension.
(3) And (3) leading out the suspension from the reactor, centrifuging at the speed of 1000r/min for 10min, washing the solid obtained by the centrifuging with distilled water, and drying to obtain the HEMA/VP microsphere.
Example 2
Preparation of photopolymerized hydroxyethyl methacrylate/4-vinylpyridine (HEMA/VP) microspheres:
(1) 4g of hydroxyethyl methacrylate and 2g of 4-vinylpyridine are mixed and added into a reactor, then 0.1g of polyethylene glycol dimethacrylate as a crosslinking agent is added while stirring, and then 50mL of an ethanol/water (1:1, V/V) solution containing 4% polyvinylpyrrolidone is added to obtain a mixed solution.
(2) Introducing nitrogen into the mixed solution to remove dissolved oxygen, adding 0.04g of initiator 2-p-hydroxy-2-methyl-1-phenyl-1-acetone, sealing the reactor to isolate oxygen, and carrying out photopolymerization reaction for 12h at room temperature under 365nm ultraviolet irradiation at a speed of 400r/min under stirring to obtain a suspension.
(3) And (3) leading out the suspension from the reactor, centrifuging at the speed of 1000r/min for 10min, washing the solid obtained by the centrifuging with distilled water, and drying to obtain the HEMA/VP microsphere.
Example 3
Adsorption experiments of HEMA/VP microspheres on methyl parahydroxybenzoate preservative solutions of different concentrations:
50mL of 0.05%, 0.1% and 0.2% methyl parahydroxybenzoate solution are respectively filled into PVC bottles; the 5g HEMA/VP microspheres provided in example 1 were immobilized using a polypropylene filter membrane that fits into the mouth of a PVC bottle, which was then packaged in the PVC bottle mouth. Pouring out the methyl parahydroxybenzoate solution from the inverted light pressure PVC bottle, simulating the using process, repeatedly pouring out 5 times, pouring out about 10mL at a time, and measuring the concentration of the methyl parahydroxybenzoate solution poured out each time by adopting a liquid chromatography method, wherein the measuring conditions are as follows: the chromatographic column is ODS C18 column (250 mm×4.6mm,5 μm), methanol-1% acetic acid solution (60:40) is used as mobile phase, flow rate is 1.0mL/min, column temperature is 35deg.C, and wavelength is 254nm.
The influence of HEMA/VP microspheres on the concentration of methyl parahydroxybenzoate solutions with different concentrations under different pouring times is shown in figure 1, which shows that the microspheres of the invention all show good adsorption effect on methyl parahydroxybenzoate in the maximum allowable concentration range of methyl parahydroxybenzoate in cosmetics regulated by European Union, simulate multiple use, still have good adsorption effect, and realize efficient adsorption and immediate removal of preservative methyl parahydroxybenzoate.
Example 4
Adsorption experiments of HEMA/VP microspheres on ethyl parahydroxybenzoate preservative solutions of different concentrations:
50mL of ethyl parahydroxybenzoate solution with concentration of 0.05%, 0.1% and 0.15% are respectively filled into PVC bottles; the 5g HEMA/VP microspheres provided in example 1 were immobilized using a polypropylene filter membrane that fits into the mouth of a PVC bottle, which was then packaged in the PVC bottle mouth. Pouring out the ethyl p-hydroxybenzoate solution from the inverted light pressure PVC bottle, simulating the using process, repeatedly pouring out 5 times, pouring out about 10mL at a time, and measuring the concentration of the poured ethyl p-hydroxybenzoate solution by adopting a chromatographic column each time, wherein the measuring conditions are as follows: the chromatographic column was a C18 column (250 mm. Times.4.6 mm,5 μm) with acetonitrile-water (25:75) as mobile phase at a flow rate of 1.0mL/min at 35℃and a wavelength of 254nm.
The effect of the microspheres on the concentration of the ethyl p-hydroxybenzoate solution with different concentrations under different pouring times is shown in figure 2, which shows that the microspheres of the invention all show good adsorption effect on the ethyl p-hydroxybenzoate in the maximum allowable concentration range of the ethyl p-hydroxybenzoate in cosmetics regulated by European Union, simulate multiple uses, still have good adsorption effect, and realize efficient adsorption and immediate removal of the preservative ethyl p-hydroxybenzoate.
Example 5
Adsorption experiments of HEMA/VP microspheres on nicotinamide solutions with different concentrations:
in order to verify that the microspheres of the invention can not cause loss of adsorption of micromolecular active ingredients in cosmetics while removing the nipagin ester preservative, the common whitening ingredient nicotinamide of cosmetics is selected as an example.
50mL of 0.05%, 1% and 2% nicotinamide solution are respectively filled into PVC bottles; the 5g HEMA/VP microspheres provided in example 1 were immobilized using a polypropylene filter membrane that fits into the mouth of a PVC bottle, which was then packaged in the PVC bottle mouth. Pouring out nicotinamide solution from the inverted light pressure PVC bottle, simulating the use process, repeating pouring 5 times, pouring about 10mL at a time, and measuring the concentration of the nicotinamide solution poured each time by adopting a chromatographic column, wherein the measuring conditions are as follows: the chromatographic column is a C18 column (250 mm. Times.4.6 mm,5 μm) and takes potassium dihydrogen phosphate solution (0.01 mol/L) -water-methanol-acetonitrile (1/79/15/5) as a mobile phase, the flow rate is 1.0mL/min, the column temperature is 35 ℃, and the wavelength is 262nm.
The effect of the microspheres on the concentration of different concentrations of nicotinamide solution at different pouring times is shown in fig. 3, which shows that the microspheres of the invention show lower adsorption effect on nicotinamide in the common additive concentration range of nicotinamide in cosmetics. The total loss of nicotinamide is lower than 5% when the compound is simulated to be used for multiple times.
Example 6
Adsorption experiments of HEMA/VP microspheres on hyaluronic acid solutions of different concentrations:
in order to verify that the microspheres can not cause loss of adsorption of high polymer active ingredients in cosmetics while removing the nipagin ester preservative, a common moisturizing ingredient, namely hyaluronic acid, is selected for illustration.
Placing 50mL of hyaluronic acid solution with concentration of 0.05%, 0.2% and 0.5% into PVC bottles respectively; the 5g HEMA/VP microspheres provided in example 1 were immobilized using a polypropylene filter membrane that fits into the mouth of a PVC bottle, which was then packaged in the PVC bottle mouth. Inverting the light pressure PVC bottle to pour out the hyaluronic acid solution, simulating the use process, repeatedly pouring 5 times, pouring about 10mL at a time, and then measuring the concentration of the hyaluronic acid solution poured each time by adopting an aliskiren blue color-spectrophotometry, wherein the method comprises the following steps of: taking 1mL of poured hyaluronic acid concentration as a liquid to be detected, adding 6mL of aliskirin blue dye solution, fixing the volume to 10mL, measuring an absorbance value at a wavelength of 510nm, and calculating to obtain the concentration.
The effect of the microspheres on the concentration of hyaluronic acid solutions with different concentrations under different pouring times is shown in fig. 4, which shows that the microspheres of the invention have lower adsorption effect on hyaluronic acid in the common concentration range of hyaluronic acid addition in cosmetics. The total loss of hyaluronic acid is lower than 1% after simulation for multiple use.
Example 7
Testing of the content variation of each component after the self-made cosmetic solution passes through HEMA/VP microspheres:
in order to illustrate whether the microspheres of the invention can cause adsorption loss to typical small molecular active ingredients and large molecular active ingredients in cosmetics while removing the nipagin ester preservative. Selecting a self-made cosmetic solution as an example, wherein the self-made cosmetic solution comprises the following components: 1% nicotinamide, 0.2% hyaluronic acid, 0.2% methylparaben, 0.1% ethylparaben.
50mL of self-made cosmetic solution is filled into a PVC bottle; the 5g HEMA/VP microspheres provided in example 1 were immobilized using a polypropylene filter membrane that fits into the mouth of a PVC bottle, which was then packaged in the PVC bottle mouth. The self-made cosmetic solution was poured out of the inverted light pressure PVC bottle, the use process was simulated, the pouring was repeated 5 times, about 10ml was poured at a time, and then the content of each component in the self-made cosmetic solution poured each time was measured.
The effect of the microspheres on the content of each component in the self-made cosmetic solution at different pouring times is shown in fig. 5, which shows that the content of the preservative methyl parahydroxybenzoate and ethyl parahydroxybenzoate in the poured self-made cosmetic solution is obviously reduced, and the losses of the micromolecular active ingredient nicotinamide and the macromolecule active ingredient hyaluronic acid are less. The microsphere has good effect of removing the nipagin ester preservative, meanwhile, the loss of micromolecular active ingredients and macromolecular active ingredients in the cosmetics is avoided, and the result is unchanged after repeated pouring and simulation.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, 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 may be embodied in 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 understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein 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 method for preparing preservative adsorption microspheres, which is characterized in that the microspheres are used for removing nipagin ester preservatives in solution-type or gel-type cosmetics, the cosmetics contain whitening components nicotinamide and/or moisturizing components hyaluronic acid, and the method comprises the following steps:
1) Adding a monomer solution into a reactor, and sequentially adding a cross-linking agent and a solvent containing a stabilizer while stirring to obtain a mixed solution, wherein the monomer solution is a mixture of hydroxyethyl methacrylate and 4-vinylpyridine;
2) Introducing nitrogen into the mixed solution to remove dissolved oxygen in the mixed solution, adding an initiator, sealing a reactor to isolate oxygen, and performing polymerization reaction under the stirring condition to obtain a suspension;
3) And (3) leading out the suspension from the reactor, centrifuging, cleaning the solid obtained by centrifuging with distilled water, and drying to obtain the preservative adsorption microsphere.
2. The preparation method of claim 1, wherein the cross-linking agent is one or more of polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and N, N' -methylenebisacrylamide.
3. The method according to claim 1, wherein in the solvent containing the stabilizer: the stabilizer is polyvinylpyrrolidone, and the solvent is one of water, methanol and ethanol.
4. The preparation method according to claim 1, wherein the initiator is one or more of azobisisobutyronitrile, azobisisoheptonitrile, 2-p-hydroxy-2-methyl-1-phenyl-1-propanone, 1-p-hydroxycyclohexylphenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyl-phenylphosphonate, 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 benzoate.
5. The method according to claim 1, wherein the stirring speed in step 2) is 350-450 r/min.
6. The method according to claim 1, wherein the polymerization reaction in step 2) is specifically: and carrying out thermal polymerization reaction by heating or photopolymerization reaction by ultraviolet irradiation, wherein the polymerization reaction time is 10-30 h.
7. The method according to claim 1, wherein the centrifugation speed in step 3) is 900-1100 r/min and the centrifugation time is 8-15 min.
8. A preservative adsorption microsphere prepared according to any one of the preparation methods of claims 1 to 7.
9. Use of the preservative adsorption microspheres of claim 8 for removing parabens preservatives in a solution-type or gel-type cosmetic.
10. The use according to claim 9, wherein the paraben preservative is methylparaben or ethylparaben.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011116345.5A CN112316922B (en) | 2020-10-19 | 2020-10-19 | Preservative adsorption microsphere as well as preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011116345.5A CN112316922B (en) | 2020-10-19 | 2020-10-19 | Preservative adsorption microsphere as well as preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN112316922A CN112316922A (en) | 2021-02-05 |
CN112316922B true CN112316922B (en) | 2023-12-12 |
Family
ID=74313968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011116345.5A Active CN112316922B (en) | 2020-10-19 | 2020-10-19 | Preservative adsorption microsphere as well as preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112316922B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102010476A (en) * | 2010-11-02 | 2011-04-13 | 江南大学 | Method for preparing monodisperse polymer microsphere by irradiation polymerization of ultraviolet light |
WO2012110971A2 (en) * | 2011-02-17 | 2012-08-23 | Promed Exports Pvt. Ltd. | Method and composition to retard sorption of preservatives to plastics |
CN102659973A (en) * | 2012-04-28 | 2012-09-12 | 华南理工大学 | Porous composite micro balls for cosmetics and preparation method for porous composite micro balls |
CN104829777A (en) * | 2015-05-14 | 2015-08-12 | 扬州三涧科贸有限公司 | Preparation method of micron-sized highly-crosslinked polymethyl methacrylate (PMMA) microspheres |
WO2015144458A1 (en) * | 2014-03-25 | 2015-10-01 | Basf Se | Preservaton mixtures, and polymer solutions stabilized therewith |
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 |
-
2020
- 2020-10-19 CN CN202011116345.5A patent/CN112316922B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102010476A (en) * | 2010-11-02 | 2011-04-13 | 江南大学 | Method for preparing monodisperse polymer microsphere by irradiation polymerization of ultraviolet light |
WO2012110971A2 (en) * | 2011-02-17 | 2012-08-23 | Promed Exports Pvt. Ltd. | Method and composition to retard sorption of preservatives to plastics |
CN102659973A (en) * | 2012-04-28 | 2012-09-12 | 华南理工大学 | Porous composite micro balls for cosmetics and preparation method for porous composite micro balls |
WO2015144458A1 (en) * | 2014-03-25 | 2015-10-01 | Basf Se | Preservaton mixtures, and polymer solutions stabilized therewith |
CN104829777A (en) * | 2015-05-14 | 2015-08-12 | 扬州三涧科贸有限公司 | Preparation method of micron-sized highly-crosslinked polymethyl methacrylate (PMMA) microspheres |
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 |
Non-Patent Citations (1)
Title |
---|
华丽 ; 张洪权 ; 胡庆兰 ; 张蕾 ; .单分散聚合法制备聚苯乙烯微球.湖北第二师范学院学报.2011,(02),全文. * |
Also Published As
Publication number | Publication date |
---|---|
CN112316922A (en) | 2021-02-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Hiratani et al. | Timolol uptake and release by imprinted soft contact lenses made of N, N-diethylacrylamide and methacrylic acid | |
Brahim et al. | Synthesis and hydration properties of pH-sensitive p (HEMA)-based hydrogels containing 3-(trimethoxysilyl) propyl methacrylate | |
Güven et al. | A review on the radiation synthesis of copolymeric hydrogels for adsorption and separation purposes | |
Alvarez-Lorenzo et al. | Soft contact lenses capable of sustained delivery of timolol | |
US8226934B2 (en) | Hair care compositions and methods of treating hair using same | |
CA2485259A1 (en) | Microcapsules containing biomedical materials | |
Kadłubowski et al. | Hydrogels of polyvinylpyrrolidone (PVP) and poly (acrylic acid)(PAA) synthesized by radiation-induced crosslinking of homopolymers | |
BE904114A (en) | COSMETIC FILTERING COMPOSITION CONTAINING A FILTER ASSOCIATED WITH A POLYMER OBTAINED BY SEQUENTIAL EMULSION POLYMERIZATION AND ITS USE FOR THE PROTECTION OF THE HUMAN SKIN AGAINST ULTRAVIOLET RADIATION. | |
US20180244911A1 (en) | Composition, contact lens coating agent, method for producing contact lens, and contact lens | |
CN101035845A (en) | Stabilisation of aqueous solutions of homopolymers and copolymers of n-vinylpyrrolidones | |
WO2018152395A1 (en) | Ionically modified silicones, compositions, and medical devices formed therefrom | |
EP0580435B1 (en) | Diester monomer, its polymer, water-containing soft contact lens, and processing solution for contact lens | |
CN112316922B (en) | Preservative adsorption microsphere as well as preparation method and application thereof | |
JP2012088525A (en) | Contact lens care formulation and packaging solution | |
US4275183A (en) | Hydrophilic polymers and contact lenses therefrom | |
EP3200754B1 (en) | Cosmetic process for attenuating wrinkles | |
Krezović et al. | Structural, thermal, mechanical, swelling, drug release, antibacterial and cytotoxic properties of P (HEA/IA)/PVP semi-IPN hydrogels | |
CN112337446B (en) | Pellet capable of rapidly removing preservative as well as preparation method and application thereof | |
Brambilla et al. | In vitro Streptococcus mutans biofilm formation on surfaces of chlorhexidine-containing dentin bonding systems | |
CN112220700B (en) | Preservative specific adsorption multi-pore gel and preparation method and application thereof | |
EP2772246A1 (en) | Acidic composition for modifying the internal region of a hair shaft | |
CN112221199B (en) | Antiseptic remove device of cosmetics | |
Xu et al. | Phospholipid based polymer as drug release coating for cardiovascular device | |
Ali et al. | Radiation synthesis of poly (ethylene glycol)/acrylic acid hydrogel as carrier for site specific drug delivery | |
CN105708790B (en) | Preparation and application of macromolecular vesicle hydrogel drug carrier |
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 |