CN116655847B - Preparation method of temperature-sensitive macromolecular dye, mascara containing temperature-sensitive macromolecular dye and preparation method of mascara - Google Patents
Preparation method of temperature-sensitive macromolecular dye, mascara containing temperature-sensitive macromolecular dye and preparation method of mascara Download PDFInfo
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- CN116655847B CN116655847B CN202310648673.7A CN202310648673A CN116655847B CN 116655847 B CN116655847 B CN 116655847B CN 202310648673 A CN202310648673 A CN 202310648673A CN 116655847 B CN116655847 B CN 116655847B
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- dye
- temperature
- reaction
- sulfuric acid
- mascara
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 83
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 abstract description 19
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- -1 neopentyl alcohol isostearyl ester Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 7
- 235000013869 carnauba wax Nutrition 0.000 claims abstract description 7
- 239000004203 carnauba wax Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229940075507 glyceryl monostearate Drugs 0.000 claims abstract description 7
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims abstract description 7
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Substances CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 7
- 239000000600 sorbitol Substances 0.000 claims abstract description 7
- 239000012185 ceresin wax Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 claims abstract description 5
- 239000003755 preservative agent Substances 0.000 claims abstract description 5
- 230000002335 preservative effect Effects 0.000 claims abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 4
- 235000013871 bee wax Nutrition 0.000 claims abstract description 4
- 239000012166 beeswax Substances 0.000 claims abstract description 4
- 239000000975 dye Substances 0.000 claims description 128
- 238000006243 chemical reaction Methods 0.000 claims description 75
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 26
- URUIKGRSOJEVQG-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanylacetonitrile Chemical compound CCCCCCCCCCCCSC(=S)SCC#N URUIKGRSOJEVQG-UHFFFAOYSA-N 0.000 claims description 18
- 239000012954 diazonium Substances 0.000 claims description 18
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 150000001989 diazonium salts Chemical class 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- ZTUKGBOUHWYFGC-UHFFFAOYSA-N 1,3,3-trimethyl-2-methylideneindole Chemical compound C1=CC=C2N(C)C(=C)C(C)(C)C2=C1 ZTUKGBOUHWYFGC-UHFFFAOYSA-N 0.000 claims description 9
- AHOIGFLSEXUWNV-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazole Chemical compound COC1=CC=C2N=CSC2=C1 AHOIGFLSEXUWNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000001045 blue dye Substances 0.000 claims description 9
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 claims description 6
- IVKILQAPNDCUNJ-UHFFFAOYSA-N 6-methyl-1,3-benzothiazole Chemical compound CC1=CC=C2N=CSC2=C1 IVKILQAPNDCUNJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009935 nitrosation Effects 0.000 claims description 6
- 238000007034 nitrosation reaction Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000006193 diazotization reaction Methods 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- 239000000851 basic yellow dye Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000001044 red dye Substances 0.000 claims description 4
- 239000007766 cera flava Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005185 salting out Methods 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- HZMXJTJBSWOCQB-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl prop-2-enoate Chemical compound COCCOCCOC(=O)C=C HZMXJTJBSWOCQB-UHFFFAOYSA-N 0.000 claims 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N meta-toluidine Natural products CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims 1
- 235000010356 sorbitol Nutrition 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 abstract description 11
- 230000003670 easy-to-clean Effects 0.000 abstract description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 210000000720 eyelash Anatomy 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GCECACVNILMTRD-XYOKQWHBSA-N (2e)-2-(1,3,3-trimethylindol-2-ylidene)acetaldehyde Chemical compound C1=CC=C2N(C)\C(=C\C=O)C(C)(C)C2=C1 GCECACVNILMTRD-XYOKQWHBSA-N 0.000 description 1
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical compound CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 1
- KLLOEOPUXBJSOW-UHFFFAOYSA-N 3-(methylamino)phenol Chemical compound CNC1=CC=CC(O)=C1 KLLOEOPUXBJSOW-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8188—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bonds, and at least one being terminated by a bond to sulfur or by a hertocyclic ring containing sulfur; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/105—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a methine or polymethine dye
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/106—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an azo dye
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/42—Colour properties
- A61K2800/43—Pigments; Dyes
- A61K2800/432—Direct dyes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Cosmetics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a temperature-sensitive macromolecular dye, mascara containing the temperature-sensitive macromolecular dye and a preparation method of the mascara. The temperature sensitive macromolecular dye is prepared by using AIBN as initiator, CMDT as RAFT chain transfer agent and DMSO as solvent, and mixing with OEGA and MEO via double bond-containing dye monomer 2 And (3) polymerizing the A, dissolving the polymer in tetrahydrofuran, precipitating in n-hexane, filtering and drying to obtain the polymer. The mascara is prepared by dissolving beeswax, ceresin and carnauba wax, adding white oil, neopentyl alcohol isostearyl ester, polyvinyl alcohol, glyceryl monostearate and triethanolamine, uniformly mixing to form an oil phase, dissolving sorbitol, EDTA-2Na and sodium carboxymethyl cellulose in deionized water to form a water phase, mixing the water phase and the oil phase, and adding a temperature-sensitive macromolecular dye, a preservative and essence. The mascara prepared by the invention has temperature-sensitive property, can hold makeup for a long time and is easy to clean by warm water.
Description
Technical Field
The invention relates to the technical field of mascaras, in particular to a preparation method of a thermo-sensitive macromolecular dye, a mascaras containing the thermo-sensitive macromolecular dye and a preparation method of the mascaras.
Background
Mascara is a cosmetic applied to the surface of eyelashes, and is increasingly favored and paid attention to by people who are loving beauty as the economic and living standard increases. In the prior art, most of mascaras are added with a film forming agent, a coloring agent and an auxiliary agent to achieve the effect of coloring eyelashes, and although the mascaras can achieve long-term makeup holding required by consumers, the mascaras are difficult to clean, especially cannot be cleaned with water, and can be removed only by using an organic solvent type makeup remover, but the makeup removers are easy to damage protective barriers of eyes and facial skin and can cause irritation and damage. Therefore, there is a need to develop a mascara that is long lasting and easy to clean with water.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a temperature-sensitive macromolecular dye, a mascara containing the temperature-sensitive macromolecular dye and a preparation method of the mascara.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing temperature-sensitive macromolecular dye comprises using AIBN as initiator, CMDT as RAFT chain transfer agent, and DMSO as solvent to make double bond-containing dye monomer and non-dye monomer OEGA, MEO 2 A is subjected to polymerization reaction; after stopping the reaction, dissolving the polymer in tetrahydrofuran, adding the tetrahydrofuran into normal hexane for precipitation, removing unreacted monomers, filtering and drying to obtain temperature-sensitive macromolecular dye solid powder;
the dye monomer containing double bonds is selected from one of structural formulas shown in formulas (A) - (F):
the specific steps of the polymerization reaction are as follows: in a reaction vessel, a double bond-containing dye monomer, a non-dye monomer OEGA and MEO 2 A. Dissolving initiator AIBN and RAFT chain transfer agent CMDT in solvent DMSO, degassing through three freeze-thawing cycles, and then placing in an oil bath kettle at 70-80 ℃ under the protection of nitrogen for reaction;double bond-containing dye monomer and non-dye monomer OEGA and MEO 2 A. AIBN, CMDT, DMSO has a mass ratio of 1: (6-15): (5-14): 0.09:0.12.
the compound represented by the formula (A) is prepared by the following method: adding N-ethyl-N-allylaniline, 1, 3-trimethyl-indoline-omega-aldehyde and sulfuric acid into a reaction container, reacting at 26-30 ℃ to obtain crude dye, and refining to obtain basic yellow dye monomer; the concentration of sulfuric acid is 20wt%, and the mass ratio of N-ethyl-N-allylaniline to 1, 3-trimethylindoleacetaldehyde to sulfuric acid is 23:30:137.
the compound represented by the formula (B) is prepared by the following method: adding 1, 3-trimethyl-2-methylene indoline, phosphoric acid, oxalic acid and N-ethyl-N- (allyl) amino benzaldehyde into a reaction vessel, and stirring for reaction to obtain a basic red dye monomer; the phosphoric acid concentration is 85wt%, and the mass ratio of the 1, 3-trimethyl-2-methylene indoline to phosphoric acid, oxalic acid and N-ethyl-N- (allyl) amino benzaldehyde is 42.2:30.5:5.5:41.4.
the compound represented by the formula (C) or (D) is produced by the following method: step a1, adding sulfuric acid with the concentration of 20wt percent, nitrosylsulfuric acid and 6-substituted benzothiazole into a reaction vessel for diazotization reaction to obtain diazonium salt; step a2, adding N-ethyl-N-allylaniline or N-ethyl-N-allylm-toluidine, ice water and sulfuric acid with the concentration of 20wt% into another reaction container, dripping diazonium salt at the temperature of 0-5 ℃, filtering after adding, obtaining a dye matrix and drying; step a3, adding chlorobenzene into a dye matrix to dissolve, cooling to 80 ℃, then dropwise adding dimethyl sulfate, reacting at a constant temperature to a terminal point, cooling, and filtering to obtain an alkaline violet or alkaline blue dye monomer; wherein the 6-substituted benzothiazole is 6-methylbenzothiazole or 6-methoxybenzothiazole, the mass ratio of sulfuric acid to nitrosylsulfuric acid added in the step a1 to 6-substituted benzothiazole, N-ethyl-N-allylaniline or N-ethyl-N-allylm-toluidine to ice water, and sulfuric acid, chlorobenzene and dimethyl sulfate added in the step a2 is 40:35: (16.4-18): 17.5:200:20:200:18.
the compound represented by the formula (E) is prepared by the following method: step b1, adding sulfuric acid with the concentration of 20wt percent, nitrosylsulfuric acid and 6-methoxybenzothiazole into a reaction vessel for diazotization reaction to obtain diazonium salt; step b2, adding N-ethyl-N-allylaniline, ice water and sulfuric acid with the concentration of 20wt% into another reaction container, dripping diazonium salt at the temperature of 0-5 ℃, filtering after the addition is finished to obtain a dye matrix, and drying; step b3, adding chlorobenzene into the dye matrix to dissolve, cooling to 80 ℃, then dropwise adding dimethyl sulfate, reacting at a constant temperature to a terminal point, cooling, and filtering to obtain a basic blue dye monomer; wherein, the mass ratio of sulfuric acid, nitrosylsulfuric acid, 6-methoxybenzothiazole, N-ethyl-N-allylaniline, ice water added in the step b1 to sulfuric acid, chlorobenzene and dimethyl sulfate added in the step b2 is 40:35:18:17:200:20:200:18.
the compound represented by the formula (F) is prepared by the following method: step c1, adding 3-hydroxy-N-methyl-N-allylaniline, water and 30wt% of liquid alkali into a reaction vessel, heating to 75 ℃, adding dimethyl sulfate, heating to 100 ℃ after the addition, preserving heat until the reaction is finished, discharging a lower layer of water layer, adding 15wt% of hydrochloric acid into an upper layer of oily substance, adding 30wt% of sodium nitrite solution at the temperature of less than or equal to 5 ℃ under control, and carrying out heat preservation reaction at 0-5 ℃ after the addition, so as to obtain nitrosation liquid; step c2, adding 3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride and water into another reaction container, heating to 90-95 ℃, stirring for a period of time, dropwise adding nitrosation liquid, and salting out after the addition is finished and keeping the reaction to a terminal point to obtain a basic black dye monomer; wherein, the mass ratio of 3-hydroxy-N-methyl-N-allylaniline, water added in step c1, 30wt% liquid alkali, dimethyl sulfate, 15wt% hydrochloric acid, 30wt% sodium nitrite solution, 3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride and water added in step c2 is 16.2:200:25:25:40:23:35:100.
a mascara, based on 100% of the total mass of the mascara, is made up of the following raw materials: 8wt% of temperature-sensitive macromolecular dye, 8wt% of beeswax, 4wt% of ceresin wax, 4wt% of carnauba wax, 5wt% of white oil, 1wt% of neopentyl alcohol isostearyl ester, 2wt% of polyvinyl alcohol, 1wt% of glyceryl monostearate, 2wt% of triethanolamine, 3wt% of sorbitol, 0.1-0.3wt% of EDTA-2Na, 1wt% of sodium carboxymethyl cellulose, 0.1-0.15wt% of preservative, 1-3wt% of essence and the balance of deionized water.
A method for preparing mascara comprises dissolving Cera flava, ceresin and carnauba wax at 80deg.C, adding white oil, neopentyl alcohol isostearyl ester, polyvinyl alcohol, glyceryl monostearate and triethanolamine, and stirring to form oil phase; dissolving sorbitol, EDTA-2Na and sodium carboxymethyl cellulose in deionized water to form a water phase; mixing the water phase and the oil phase to obtain emulsion, and adding temperature-sensitive macromolecular dye, antiseptic and essence to obtain mascara.
The beneficial effects of the invention are as follows: the USTC (dissolution temperature) of the synthesized temperature-sensitive macromolecular dye is adjusted by adjusting the type and the addition amount of the dye monomer, so that the optimal temperature change temperature is achieved; the mascara is prepared by using UCST temperature-sensitive macromolecular dye at 44-46 ℃ as a colorant, so that the effect of keeping makeup clean for 12 hours is realized, the mascara can be easily removed by hot water at 46 ℃ or above, the makeup removing process is free from irritation to eyes and facial skin, and the safety problem caused by using organic solvent type makeup remover is avoided.
Drawings
FIG. 1 is a synthetic reaction equation of a temperature-sensitive macromolecular dye according to the present invention (in the figure, dye represents a portion other than a carbon-carbon double bond in the dye monomer structure shown in formulas (A) - (F));
FIG. 2 is a temperature-sensitive test chart of the temperature-sensitive macromolecular dye prepared in example 9;
FIG. 3 is a nuclear magnetic resonance spectrum of the blue dye monomer prepared in example 4.
FIG. 4 is a nuclear magnetic resonance spectrum of the temperature-sensitive macromolecular dye prepared in example 4.
Detailed Description
The invention is further described with reference to the drawings and detailed description which follow:
example 1: preparation of temperature-sensitive yellow macromolecular dye
S1, preparing a basic yellow dye monomer: in a three-port reaction flask, 137g of 20wt% sulfuric acid was added with stirring, and 23g N-ethyl-N-allylaniline and 30g of 1, 3-trimethyl-indole were added at room temperatureAnd (3) a pino-omega-aldehyde. Reacting at 26-30deg.C for 16 hr, filtering, and obtaining filter cake as crude dye. Preparing for the next refining step. In a reaction flask, 1800g of water was added under stirring, the above crude dye was added, heated to 75℃to dissolve it completely, 3.6g of activated carbon was added, stirred for half an hour, and then filtered. To the filtrate, 140g of purified salt (sodium chloride) was added, and the mixture was filtered at room temperature. Drying at 70deg.C to obtain 43.6g of basic yellow dye monomer with structural formula ofStructure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,CDCl 3 )δ8.80-9.00(d,1H),8.00-8.05(t,1H),7.30-7.40(b,5H),6.60-6.70(m,2H),5.87(t,1H),5.18-5.40(m,2H),4.60-4.80(m,1H),4.20-4.40(s,3H),4.02-4.04(m,3H),3.40-3.42(d,2H),1.40-1.50(s,6H)。
N-ethyl-N-allylaniline (N-all-N-ethyllaniline, CAS number 16078-91-4) has the formula
1, 3-Trimethyl-indoline-omega-aldehyde, also known as 1, 3-Trimethyl-2-methyleneindoline acetaldehyde (1, 3-Trimethyl-2- (formylethylene) in-line, CAS: 84-83-3) of formula
S2: 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN (azodiisobutyronitrile) and 120mg of RAFT chain transfer agent CMDT (cyanomethyl dodecyl trithiocarbonate) are dissolved in solvent DMSO (dimethyl sulfoxide), added into a three-port bottle, degassed through three freeze-thaw cycles, then introduced with nitrogen, and the reactants are placed in an oil bath pot at 70-80 ℃ for reaction for 12 hours, and then the reaction is stopped. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane to eliminate unreacted monomer, filtering to collect solid, vacuum drying to obtain temperature sensitive yellow macromolecular dye No. 1, and the product has the structure as shown 1 H NMR spectra confirm: 1 H NMR(400MHz,CDCl 3 )δ4.8-9.0(H on benzene ring of dye monomer), 4.00-4.50 (Polymer backbone, COOCH) 2, -C＝C-NH-,-N + -CH 3 ),3.30-3.40(polymer backbone,-OCH 3 ,-CH 2 N-CH 2- ),3.50-3.80(polymer backbone,-CH 2 OCH 2 CH 2 O),1.40-1.80(polymer backbone,-CH 2 -,CH 3 CCH 3 ),1.00-1.20(polymer backbone,-CH 3 )。
The structural formula of the non-dye monomer OEGA (methoxy polyethylene glycol monoacrylate) isMEO 2 A is of the formula->
N-ethyl-N-allylaniline, 1, 3-trimethyl-indoline-omega-aldehyde, non-dye monomers OEGA, MEO2A were purchased from Michelin reagent company.
Example 2: preparation of temperature-sensitive red macromolecular dye
S1, preparing basic red dye monomers: 42.2g of 1, 3-trimethyl-2-methylene indoline is firstly added into a reaction bottle, and stirring is started for 10 minutes; then 30.5g of 85wt% phosphoric acid and 5.5g of oxalic acid are added and stirred for 10 minutes; adding 41.4g N-ethyl-N- (allyl) amino benzaldehyde, stirring to the end of the reaction, and drying to obtain 100g of basic red dye monomer with the structural formula ofStructure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,CDCl 3 )δ8.80-9.00(d,1H),8.00-8.05(t,1H),7.70-7.74(t,2H),7.30-7.40(b,2H),6.88-6.90(m,1H),6.60-6.72(m,2H),5.80-5.90(t,1H),5.60-5.70(m,1H),5.18-5.22(m,2H),4.20-4.40(s,3H),4.02-4.04(m,2H),3.40-3.42(d,2H),1.48-1.50(s,6H),1.12-1.16(t,3H)。
1, 3-Trimethyl-2-methyleneindoline (1, 3-Trimethyl-2-methylethylendoline, CAS 118-12-7) has the structural formula
N-ethyl-N- (allyl) aminobenzaldehyde (N-ethyli-N-all-p-aminobenzaldyd, CAS number 1079-75-0) of formula
1, 3-trimethyl-2-methyleneindoline, N-ethyl-N- (allyl) aminobenzaldehyde were purchased from Michelin reagent company.
S2: 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane to eliminate unreacted monomer, filtering to collect solid, and vacuum drying to obtain temperature sensitive red macromolecular dye No. 2 with the product structure 1 HNMR spectroscopy confirmed: 1 H NMR(400MHz,CDCl 3 ) Delta 5.6-8.5 (H on benzene ring of dye monomer), 4.1-4.5 (Polymer backbone, -COOCH) 2 -,-N + -CH 3 ),3.3-3.4(polymer backbone,-OCH 3 ,-CH 2 N-CH 2 -),3.5-3.8(polymer backbone,-CH 2 OCH 2 CH 2 O-),1.5-1.8(polymer backbone,-CH 2 -，-CH 3 CCH 3 -)，1.00-1.20(polymer backbone,-CH 3 )。
Example 3: preparation of temperature-sensitive purple macromolecular dye
S1, preparing an alkaline violet dye monomer: adding 40g of 20wt% sulfuric acid, 35g of nitrosylsulfuric acid and 16.4g of 6-methylbenzothiazole at a controlled temperature of 0-3 ℃ into a reaction bottle, and carrying out heat preservation for 3-4h by using diazonium, thereby obtaining diazonium salt after heat preservation; another reaction flask was taken and added with 17.5g of N-ethyl-N-allylm-toluidine, 200g of ice water and 20g of 20wt% sulfuric acid, and after stirring and complete dissolution, the temperature was controlled between 0 and 5 ℃ to drop the diazonium salt, and after the addition, the dye matrix was obtained and dried. Adding 20 to the dye matrixDissolving 0g of chlorobenzene, cooling to 80 ℃, dropwise adding 18g of dimethyl sulfate at the temperature, then preserving heat for reaction to a terminal point, cooling, and suction-filtering to obtain 40g of basic violet dye monomer, wherein the structural formula isStructure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,DMSO)δ7.72-7.76(m,1H),7.00-7.30(t,3H),6.50-6.70(b,2H),5.87(t,1H),5.18-5.22(m,2H),4.20-4.40(s,3H),4.02-4.04(m,2H),3.40-3.42(d,2H),2.30-2.40(s,6H),1.10-1.20(t,3H)。
the structural formula of the 6-methylbenzothiazole isN-ethyl-N-allyl-m-toluidine (N-ethyl-Nn-all-m-tolucin, CAS number 16078-92-5) of the formula->6-methylbenzothiazole, N-ethyl-N-allylm-toluidine were purchased from Michelin reagent company.
S2: 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane to eliminate unreacted monomer, filtering to collect solid, and vacuum drying to obtain temperature sensitive purple macromolecular dye No. 3 with the product structure 1 HNMR spectroscopy confirmed: 1 H NMR(400MHz,CDCl 3 )δ6.5-8.5(aromatic H),4.1-4.5(polymer backbone,-COOCH 2 -,-N + -CH 3 ),3.3-3.4(polymer backbone,-OCH 3 ,-CH 2 NCH 2 -),3.5-3.8(polymer backbone,-CH 2 OCH 2 CH 2 O),2.0-2.5(aromatic CH 3 )，1.10-1.20(-CH 3 -)。
example 4: preparation of temperature-sensitive blue macromolecular dye
S1, preparing a basic blue dye monomer: adding 20wt% sulfuric acid 40g, nitrosylsulfuric acid 35g, and 6-methoxybenzothiazole at 0-3deg.C into a reaction bottle18g, and carrying out diazonium heat preservation for 3-4h, and obtaining diazonium salt after heat preservation; another reaction flask was taken and added with 17.5g of N-ethyl-N-allylaniline, 200g of ice water and 20g of 20wt% sulfuric acid, and after stirring and complete dissolution, the temperature was controlled at 0-5℃to drop the diazonium salt, and after the addition, the dye matrix was obtained by filtration and oven drying. Dissolving 200g of chlorobenzene in a dye matrix, cooling to 80 ℃, dropwise adding 18g of dimethyl sulfate at the temperature, then carrying out heat preservation reaction to the end point, cooling, and carrying out suction filtration to obtain 40.5g of basic blue dye monomer, wherein the structural formula is->Structure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,DMSO)δ7.90-7.92(m,1H),7.83-7.85(m,2H),7.60-7.70(t,1H),7.10-7.12(t,1H),6.98-7.00(m,2H),5.87(t,1H),5.18-5.22(m,2H),4.10-4.30(s,3H),4.02-4.04(m,2H),3.86(s,3H),3.53-3.58(d,2H),1.20-1.23(t,3H)。
s2: 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, the polymer is dissolved in tetrahydrofuran solvent, precipitated in normal hexane, unreacted monomers are removed, the solid is collected by filtration, and the temperature-sensitive purple macromolecular dye No. 4 is obtained by vacuum drying. Structure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,CDCl 3 )δ6.90-8.00(aromatic H),4.1-4.5(polymer backbone,-COOCH 2 -，-N + CH 3 -)，3.3-3.4(polymer backbone,-OCH 3 ,CH 2 N-CH 2 ),3.5-3.8(polymer backbone,-CH 2 OCH 2 CH 2 O-),1.0-1.2(polymer backbone,-CH 3 -)。
example 5: preparation of temperature-sensitive blue macromolecular dye
S1, preparing a basic blue dye monomer: adding 40g of 20wt% sulfuric acid, 35g of nitrosylsulfuric acid and 18g of 6-methoxybenzothiazole at a controlled temperature of 0-3 ℃ into a reaction bottle, and carrying out heat preservation for 3-4h by using diazonium, thereby obtaining diazonium salt after heat preservation; another reaction flask was added with 17.0g of N-ethyl-N-allylaniline, 200g of ice water and 20g of 20wt% sulfuric acid, and after stirring and complete dissolution, the nitrogen salt was added dropwise at a temperature of 0-5 ℃, and the dye matrix was obtained by filtration and oven-dried. Dissolving parent dye in 200g of chlorobenzene, cooling to 80 ℃, dropwise adding 18g of dimethyl sulfate, reacting to the end point under heat preservation, cooling, and suction filtering to obtain 40.7g of blue dye, wherein the structural formula isStructure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,DMSO)δ8.90-9.00(m,1H),7.90-7.94(d,1H),7.10-7.15(t,1H),6.74-6.77(t,2H),5.85-5.88(m,1H)5.19-5.22(m,2H),4.83(s,1H),4.00-4.03(d,2H),3.05-3.10(m,8H),1.10-1.20(t,3H)。
s2, 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane to eliminate unreacted monomer, filtering to collect solid, vacuum drying to obtain temperature sensitive blue macromolecular dye No. 5, and final product structure 1 HNMR spectroscopy confirmed: 1 H NMR(400MHz,CDCl 3 )δ4.8-9.0(aromatic H),4.1-4.5(polymer backbone,-COOCH 2 -)3.5-3.8(polymer backbone,-CH 2 OCH 2 CH 2 O-),3.0-3.2(polymer backbone,CH 3 NCH 3 )3.2-3.4(polymer backbone,-OCH 3 ,-CH 2 N-CH 2 -),1.0-1.2(polymer backbone,CCH 3 )。
example 6: preparation of temperature-sensitive black macromolecular dye
S1, a synthetic method of 3-hydroxy-N-methyl-N-allylaniline comprises the following steps: taking 20g of 3-hydroxy N methylaniline, 200g of water and 16.5g of baking soda in a 500mL reaction bottle, dropwise adding 35g of bromopropene at room temperature, heating to 40 ℃ after the dripping is finished, keeping the reaction until the end, layering, taking an oil layer for later use, and obtaining 21g of oily matter. 3-hydroxy-N-methyl-N-allylaniline structure 1 HNMR spectroscopy confirmed: 1 H NMR(400MHz,DMSO)δ7.22-7.16(m,2H),7.01(t,J＝8.0Hz,1H),6.68(t,J＝2.3Hz,1H),5.90(d,J＝9.6Hz,1H),5.29(s,1H),5.10-5.04(m,2H),3.85(dd,J＝3.0,1.5Hz,2H),1.09(t,3H)。
s2, preparing a basic black dye monomer: adding 16.2g of 3-hydroxy-N-methyl-N-allylaniline, 200g of water and 25g of 30wt% liquid alkali into a reaction bottle, heating to 75 ℃, adding 25g of dimethyl sulfate, heating to 100 ℃, preserving heat until the reaction is finished, discharging a lower water layer, adding 40g of 15wt% hydrochloric acid into an upper oily substance, adding 23g of 30wt% sodium nitrite solution at the temperature of less than or equal to 5 ℃, and carrying out heat preservation reaction for 3 hours at the temperature of 0-5 ℃ to obtain nitrosation liquid; adding 35g of 3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride and 100g of water into a reaction bottle, heating to 90-95 ℃, stirring for 1h, then dripping nitrosation liquid, keeping the reaction to a terminal point after the addition, adding salt to separate out 40.02g of temperature-sensitive black dye, wherein the structural formula is that3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride was purchased from Michael reagent company. Structure of the product 1 H NMR spectra confirm: 1 H NMR(400MHz,DMSO)δ8.90-9.20(d,3H),δ8.05-8.20(m,2H),δ7.91-7.94(d,1H),7.30-7.35(m,1H)7.10-7.15(t,1H),6.74-6.77(t,2H),6.00-6.10(s,2H),5.85-5.88(m,1H),5.17-5.20(m,2H),4.81(s,1H),4.00-4.03(d,2H),3.00-3.20(s,9H)。
s3, mixing 1g of dye monomer, 10g of non-dye monomer OEGA and 10g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reactants are placed in an oil bath pot at 70-80 ℃ to react for 12H,the reaction was stopped. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane to eliminate unreacted monomer, filtering to collect solid, vacuum drying to obtain temperature sensitive black macromolecular dye No. 6, and final product structure 1 H NMR spectra confirm:
1 H NMR(400MHz,CDCl 3 )δ4.8-9.2(aromatic H),4.0-4.5(polymer backbone,-COOCH 2 -,)δ3.2-3.4(polymer backbone,-OCH 3 -,-CH 2 N-CH 2 -),3.5-3.8(polymer backbone,-CH 2 OCH 2 CH 2 O-),3.0-3.2(polymer backbone,CH 3 NCH 3 )
example 7: preparation of temperature-sensitive black macromolecular dye
1g of dye monomer (basic black dye monomer prepared in example 6), 9g of non-dye monomer OEGA, 11g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane, removing unreacted monomer, filtering and collecting solid, and vacuum drying to obtain the temperature-sensitive black macromolecular dye No. 7.
Example 8: preparation of temperature-sensitive black macromolecular dye
1g of dye monomer (basic black dye monomer prepared in example 6), 8g of non-dye monomer OEGA, 12g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane, removing unreacted monomer, filtering and collecting solid, and vacuum drying to obtain the temperature-sensitive black macromolecular dye No. 8.
Example 9: preparation of temperature-sensitive black macromolecular dye
1g of dye monomer(basic Black dye monomer prepared in example 6), 7g of non-dye monomer OEGA, 13g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane, removing unreacted monomer, filtering and collecting solid, and vacuum drying to obtain the temperature-sensitive black macromolecular dye No. 9.
Example 10: preparation of temperature-sensitive black macromolecular dye
1g of dye monomer (basic black dye monomer prepared in example 6), 6g of non-dye monomer OEGA, 14g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane, removing unreacted monomer, filtering and collecting solid, and vacuum drying to obtain the temperature-sensitive black macromolecular dye No. 10.
Example 11: preparation of temperature-sensitive black macromolecular dye
1g of dye monomer (basic black dye monomer prepared in example 6), 5g of non-dye monomer OEGA, 15g of MEO 2 A. 90mg of initiator AIBN, 120mg of RAFT chain transfer agent CMDT are dissolved in solvent DMSO, added to a three-necked flask, degassed by three freeze-thaw cycles, and then purged with nitrogen. The reaction is put into an oil bath pot with the temperature of 70-80 ℃ and stopped after reacting for 12 hours. After stopping the reaction, dissolving the polymer in tetrahydrofuran solvent, precipitating in n-hexane, removing unreacted monomer, filtering and collecting solid, and vacuum drying to obtain the temperature-sensitive black macromolecular dye No. 11.
The macromolecular dyes prepared in examples 1 to 11 were prepared into dispersion liquid by a micelle self-assembly mode, the temperature sensitivity of each macromolecular dye micelle was detected by ultraviolet equipment, and the test results are shown in table 1.
TABLE 1
Application examples:
examples 12-22 preparation of mascaras
Dissolving Cera flava, ceresin and carnauba wax at 80deg.C, adding white oil, neopentyl alcohol isostearyl ester, polyvinyl alcohol, glyceryl monostearate, and triethanolamine, and dispersing at 600rpm for 10 min to obtain oil phase; dissolving sorbitol, EDTA-2Na and sodium carboxymethylcellulose in deionized water to obtain a water phase, increasing the rotating speed, and adding the dissolved water phase into an oil phase to emulsify to obtain an emulsion; and (3) adding the temperature-sensitive macromolecular dye to color after the rotating speed is reduced, and adding essence and preservative to obtain the mascara.
Based on 100% of the total mascara mass, the mascara is made up of the following materials: the mascara is prepared from the following raw materials: 8wt% of temperature-sensitive macromolecular dye, 8wt% of beeswax, 4wt% of ceresin wax, 4wt% of carnauba wax, 5wt% of white oil, 1wt% of neopentyl alcohol isostearyl ester, 2wt% of polyvinyl alcohol, 1wt% of glyceryl monostearate, 2wt% of triethanolamine, 3wt% of sorbitol, 0.1-0.3wt% of EDTA-2Na, 1wt% of sodium carboxymethyl cellulose, 0.1-0.15wt% of preservative, 1-3wt% of essence and the balance of deionized water.
The material ratios of examples 12 to 22 are specifically shown in table 2, and the temperature-sensitive macromolecular dyes adopted in each application example are prepared in sequence in examples 1 to 11 (i.e. example 12 is prepared in example 1, example 13 is prepared in example 2, and so on).
TABLE 2
The makeup-holding properties and makeup-removing cleansing properties of the mascaras prepared in examples 12 to 22 were examined, and the results are shown in Table 3. Experiments show that the mascara prepared from the thermo-sensitive macromolecular dye can keep long-acting makeup effect within 12 hours, has good water resistance at 20-30 ℃, has good water solubility at 46 ℃ and above, and is easy to clean.
TABLE 3 Table 3
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A preparation method of a temperature-sensitive macromolecular dye is characterized by comprising the following steps: azo diisobutyronitrile is used as an initiator, cyano methyl dodecyl trithiocarbonate is used as a RAFT chain transfer agent, dimethyl sulfoxide is used as a solvent, and a double-bond-containing dye monomer and a non-dye monomer methoxy polyethylene glycol monoacrylate and 2- (2-methoxyethoxy) ethyl acrylate are subjected to polymerization reaction; after stopping the reaction, dissolving the polymer in tetrahydrofuran, adding the tetrahydrofuran into normal hexane for precipitation, removing unreacted monomers, filtering and drying to obtain temperature-sensitive macromolecular dye solid powder;
the structural formula of the methoxy polyethylene glycol monoacrylate is
The structural formula of the 2- (2-methoxyethoxy) ethyl acrylate isThe dye monomer containing double bonds is selected from one of structural formulas shown in formulas (A) - (F):
2. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the specific steps of the polymerization reaction are as follows: in a reaction vessel, double bond-containing dye monomers, non-dye monomers methoxy polyethylene glycol monoacrylate, 2- (2-methoxyethoxy) ethyl acrylate, an initiator azo-diisobutyronitrile, RAFT chain transfer agent cyano methyl dodecyl trithiocarbonate are dissolved in a solvent dimethyl sulfoxide, and are degassed through three freeze-thawing cycles, and then are placed in an oil bath kettle at 70-80 ℃ for reaction under the protection of nitrogen; the mass ratio of the double bond-containing dye monomer to the non-dye monomer methoxy polyethylene glycol monoacrylate, 2- (2-methoxyethoxy) ethyl acrylate, azodiisobutyronitrile, cyano methyl dodecyl trithiocarbonate and dimethyl sulfoxide is 1: (6-15): (5-14): 0.09:0.12.
3. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the compound represented by the formula (A) is prepared by the following method: adding N-ethyl-N-allylaniline, 1, 3-trimethyl-indoline-omega-aldehyde and sulfuric acid into a reaction container, reacting at 26-30 ℃ to obtain crude dye, and refining to obtain basic yellow dye monomer; the concentration of sulfuric acid is 20wt%, and the mass ratio of N-ethyl-N-allylaniline to 1, 3-trimethylindoleacetaldehyde to sulfuric acid is 23:30:137.
4. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the compound represented by the formula (B) is prepared by the following method: adding 1, 3-trimethyl-2-methylene indoline, phosphoric acid, oxalic acid and N-ethyl-N- (allyl) amino benzaldehyde into a reaction vessel, and stirring for reaction to obtain a basic red dye monomer; the phosphoric acid concentration is 85wt%, and the mass ratio of the 1, 3-trimethyl-2-methylene indoline to phosphoric acid, oxalic acid and N-ethyl-N- (allyl) amino benzaldehyde is 42.2:30.5:5.5:41.4.
5. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the compound represented by the formula (C) is prepared by the following method: step a1, adding sulfuric acid with the concentration of 20wt percent, nitrosylsulfuric acid and 6-methylbenzothiazole into a reaction vessel for diazotization reaction to obtain diazonium salt; step a2, adding N-ethyl-N-allyl m-toluidine, ice water and sulfuric acid with the concentration of 20wt% into another reaction container, dropwise adding diazonium salt at the temperature of 0-5 ℃, filtering after adding, obtaining a dye matrix and drying; step a3, adding chlorobenzene into a dye matrix to dissolve, cooling to 80 ℃, then dropwise adding dimethyl sulfate, reacting at a constant temperature to a terminal point, cooling, and filtering to obtain an alkaline violet dye monomer; the mass ratio of sulfuric acid to nitrosylsulfuric acid, 6-methylbenzothiazole, N-ethyl-N-allylm-toluidine and ice water added in the step a1 to sulfuric acid, chlorobenzene and dimethyl sulfate added in the step a2 is 40:35:16.4:17.5:200:20:200:18;
the compound represented by the formula (D) is prepared by the following method: step a1, adding sulfuric acid with the concentration of 20wt percent, nitrosylsulfuric acid and 6-methoxybenzothiazole into a reaction vessel for diazotization reaction to obtain diazonium salt; step a2, adding N-ethyl-N-allylaniline, ice water and sulfuric acid with the concentration of 20wt% into another reaction container, dripping diazonium salt at the temperature of 0-5 ℃, filtering after the addition is finished to obtain a dye matrix, and drying; step a3, adding chlorobenzene into a dye matrix to dissolve, cooling to 80 ℃, then dropwise adding dimethyl sulfate, reacting at a constant temperature to a terminal point, cooling, and filtering to obtain a basic blue dye monomer; the mass ratio of sulfuric acid to nitrosylsulfuric acid added in the step a1 to 6-methoxybenzothiazole to N-ethyl-N-allylaniline to ice water to sulfuric acid, chlorobenzene to dimethyl sulfate added in the step a2 is 40:35:18:17.5:200:20:200:18.
6. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the compound represented by the formula (E) is prepared by the following method: step b1, adding sulfuric acid with the concentration of 20wt percent, nitrosylsulfuric acid and 6-methoxybenzothiazole into a reaction vessel for diazotization reaction to obtain diazonium salt; step b2, adding N-ethyl-N-allylaniline, ice water and sulfuric acid with the concentration of 20wt% into another reaction container, dripping diazonium salt at the temperature of 0-5 ℃, filtering after the addition is finished to obtain a dye matrix, and drying; step b3, adding chlorobenzene into the dye matrix to dissolve, cooling to 80 ℃, then dropwise adding dimethyl sulfate, reacting at a constant temperature to a terminal point, cooling, and filtering to obtain a basic blue dye monomer; wherein, the mass ratio of sulfuric acid, nitrosylsulfuric acid, 6-methoxybenzothiazole, N-ethyl-N-allylaniline, ice water added in the step b1 to sulfuric acid, chlorobenzene and dimethyl sulfate added in the step b2 is 40:35:18:17:200:20:200:18.
7. the method for preparing the temperature-sensitive macromolecular dye according to claim 1, wherein the method comprises the following steps: the compound represented by the formula (F) is prepared by the following method: step c1, adding 3-hydroxy-N-methyl-N-allylaniline, water and 30wt% of liquid alkali into a reaction vessel, heating to 75 ℃, adding dimethyl sulfate, heating to 100 ℃ after the addition, preserving heat until the reaction is finished, discharging a lower layer of water layer, adding 15wt% of hydrochloric acid into an upper layer of oily substance, adding 30wt% of sodium nitrite solution at the temperature of less than or equal to 5 ℃ under control, and carrying out heat preservation reaction at 0-5 ℃ after the addition, so as to obtain nitrosation liquid; step c2, adding 3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride and water into another reaction container, heating to 90-95 ℃, stirring for a period of time, dropwise adding nitrosation liquid, and salting out after the addition is finished and keeping the reaction to a terminal point to obtain a basic black dye monomer; wherein, the mass ratio of 3-hydroxy-N-methyl-N-allylaniline, water added in step c1, 30wt% liquid alkali, dimethyl sulfate, 15wt% hydrochloric acid, 30wt% sodium nitrite solution, 3- (N-N-dimethyl) amino-7-hydroxy-5-phenylphenazine chloride and water added in step c2 is 16.2:200:25:25:40:23:35:100.
8. a mascara, characterized by: based on 100% of the total mass of the mascara, the mascara is prepared from the following raw materials: 8wt% of the temperature-sensitive macromolecular dye prepared by the method according to any one of claims 1 to 7, 8wt% of beeswax, 4wt% of ceresin, 4wt% of carnauba wax, 5wt% of white oil, 1wt% of neopentyl alcohol isostearyl ester, 2wt% of polyvinyl alcohol, 1wt% of glyceryl monostearate, 2wt% of triethanolamine, 3wt% of sorbitol, 0.1 to 0.3wt% of disodium ethylenediamine tetraacetate, 1wt% of sodium carboxymethyl cellulose, 0.1 to 0.15wt% of preservative, 1 to 3wt% of essence, and the balance of deionized water.
9. A method of preparing mascara according to claim 8, wherein: dissolving Cera flava, ceresin and carnauba wax at 80deg.C, adding white oil, neopentyl alcohol isostearyl ester, polyvinyl alcohol, glyceryl monostearate and triethanolamine, and stirring to form oil phase; dissolving sorbitol, disodium ethylenediamine tetraacetate and sodium carboxymethylcellulose in deionized water to form a water phase; mixing the water phase and the oil phase to obtain emulsion, and adding temperature-sensitive macromolecular dye, antiseptic and essence to obtain mascara.
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