CN114044818B - Gelatin-based surfactant and preparation method and application thereof - Google Patents
Gelatin-based surfactant and preparation method and application thereof Download PDFInfo
- Publication number
- CN114044818B CN114044818B CN202111499794.7A CN202111499794A CN114044818B CN 114044818 B CN114044818 B CN 114044818B CN 202111499794 A CN202111499794 A CN 202111499794A CN 114044818 B CN114044818 B CN 114044818B
- Authority
- CN
- China
- Prior art keywords
- gelatin
- based surfactant
- reaction
- propylene oxide
- ethylene oxide
- 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
- 108010010803 Gelatin Proteins 0.000 title claims abstract description 125
- 239000008273 gelatin Substances 0.000 title claims abstract description 125
- 229920000159 gelatin Polymers 0.000 title claims abstract description 125
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 125
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 125
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 33
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 25
- 239000002453 shampoo Substances 0.000 claims description 20
- 238000002834 transmittance Methods 0.000 claims description 20
- 239000003599 detergent Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 235000001014 amino acid Nutrition 0.000 claims description 9
- 229940024606 amino acid Drugs 0.000 claims description 9
- 150000001413 amino acids Chemical class 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- -1 alkali metal methoxide Chemical class 0.000 claims description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 claims description 4
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 4
- 235000004279 alanine Nutrition 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- 229960000310 isoleucine Drugs 0.000 claims description 4
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 3
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 3
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 3
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 3
- 239000004474 valine Substances 0.000 claims description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 238000005461 lubrication Methods 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 3
- 238000004886 process control Methods 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002994 raw material Substances 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000002292 Radical scavenging effect Effects 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 241000251468 Actinopterygii Species 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000013022 formulation composition Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 241000157835 Gardenia Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005202 decontamination Methods 0.000 description 3
- 230000003588 decontaminative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 210000001185 bone marrow Anatomy 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 2
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 2
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 2
- 229960002216 methylparaben Drugs 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009818 osteogenic differentiation Effects 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920001184 polypeptide Polymers 0.000 description 2
- 239000004302 potassium sorbate Substances 0.000 description 2
- 235000010241 potassium sorbate Nutrition 0.000 description 2
- 229940069338 potassium sorbate Drugs 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 102000004196 processed proteins & peptides Human genes 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- 229940038773 trisodium citrate Drugs 0.000 description 2
- HTCSFFGLRQDZDE-UHFFFAOYSA-N 2-azaniumyl-2-phenylpropanoate Chemical group OC(=O)C(N)(C)C1=CC=CC=C1 HTCSFFGLRQDZDE-UHFFFAOYSA-N 0.000 description 1
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000007059 acute toxicity Effects 0.000 description 1
- 231100000403 acute toxicity Toxicity 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003295 alanine group Chemical group N[C@@H](C)C(=O)* 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229940113120 dipropylene glycol Drugs 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 description 1
- 230000013595 glycosylation Effects 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001909 leucine group Chemical group [H]N(*)C(C(*)=O)C([H])([H])C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000013930 proline Nutrition 0.000 description 1
- 125000001500 prolyl group Chemical group [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 125000002987 valine group Chemical group [H]N([H])C([H])(C(*)=O)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
- C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
- C07K14/78—Connective tissue peptides, e.g. collagen, elastin, laminin, fibronectin, vitronectin or cold insoluble globulin [CIG]
-
- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
- A61K8/65—Collagen; Gelatin; Keratin; Derivatives or degradation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Gastroenterology & Hepatology (AREA)
- Biochemistry (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Zoology (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Biophysics (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a gelatin-based surfactant, a preparation method and application thereof, wherein the gelatin-based surfactant has a structure shown in a formula 1:
Description
Technical Field
The invention relates to a gelatin-based surfactant, a preparation method and application thereof, belonging to the field of anionic-nonionic surfactants.
Background
The surfactant is an indispensable chemical product in daily life, and is named industrial monosodium glutamate. With the pursuit of high life quality, people attach importance to environmental protection and safety to China. High quality, multifunctional, environmentally friendly and degradable surfactants are urgently needed to be developed to meet the market demand.
Gelatin is a natural high molecular polymer with triple helix structure formed by three polypeptide chains through intermolecular hydrogen bonding, and can be obtained by degrading collagen in skin, bone and connective tissue of animals. Because the constituent units of the gelatin are all amino acids, the gelatin has better biocompatibility and biodegradability compared with other natural polymers. However, gelatin is solid at normal temperature, and is insoluble in conventional solvents such as water and ethanol, and melting starts at about 35 ℃.
At present, a part of gelatin is applied to the preparation of polymer cross-linked substances by taking the characteristics of good biological materials and biocompatibility, and is used in the medical field, for example, the research hotspot for promoting bone marrow mesenchymal stem cell osteogenic differentiation by biological scaffold materials, which is issued by orthopedics department of university of Harbin medical science, is used for Chinese tissue engineering research, and the application of the gelatin as a biological scaffold material is taught by the research hotspot for promoting bone marrow mesenchymal stem cell osteogenic differentiation by biological scaffold materials. CN111410917a describes a method for preparing a fish skin gelatin-based surfactant: the fish skin is taken as a raw material, degreased, and modified by high-intensity ultrasonic wave combined with glycosylation to obtain the fish skin gelatin-based surfactant. However, this patent also describes only a method for purifying gelatin from fish skin, the final gelatin of which is still solid gelatin, which does not have the cleaning function of a surfactant.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a gelatin-based surfactant and a preparation method thereof, wherein gelatin and epoxide (EO, PO) are combined to prepare the surfactant, the freezing point of the surfactant is obviously reduced, and the surfactant has better washing property besides the property that the gelatin is easy to degrade and has high biocompatibility.
The polyether block is introduced into the surfactant prepared by combining gelatin and epoxide (EO, PO), so that the surfactant has the characteristic of nonionic surfactant, and meanwhile, the carboxylic acid group part contained in gelatin in the molecular structure of the surfactant also shows the characteristic of anionic surfactant, so that the surfactant has the characteristics of good cleaning and decontamination effects of the anionic surfactant and good formula compatibility of the nonionic surfactant, and in addition, the yellowing property is improved by adopting the preparation method disclosed by the invention, and the surfactant can be widely applied to the fields of paint, textile, home care and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme: the invention provides a gelatin-based surfactant, which has a structure shown in a formula 1:
wherein R is a residue introduced by gelatin;
x is an integer from 20 to 50, preferably from 30 to 40;
m is an integer of 1 to 3;
n is an integer of 1 to 100, preferably 20 to 50.
In the gelatin-based surfactant, gelatin is a polypeptide chain formed by amino acids and contains 18 amino acids required by a human body, and residues R introduced by the gelatin comprise residues of various amino acids in the gelatin composition; the amino acid to which the residue R is introduced in the present invention is preferably any one or a combination of at least two selected from glycine, proline, alanine, glutamic acid, leucine, isoleucine, valine, phenylalanine, more preferably any one or a combination of at least two selected from glycine, proline, alanine, glutamic acid;
preferably, when R is a residue of glycine, proline, alanine, glutamic acid, leucine, isoleucine, valine, phenylalanine, respectively, it may comprise a residue of the following structure, respectively, according to the analysis of the structure of the amino acid itself:
glycine residue R is-H, proline residue R is-CH 2 CH 2 CH 3 + Alanine residue R is-CH 3 Glutamic acid residue R is-CH 3 COOH, leucine residue R is-CH 2 CH(CH 3 ) 2 Isoleucine (Ile)The residue R being-CH (CH) 3 )CH 2 CH 3 Valine residue R is-CH (CH) 3 ) 2 Phenylalanine residue R is-CH 2 Ph。
The average molecular weight of the gelatin-based surfactant of the present invention is 12000 to 410000, more preferably 86000 to 211000.
The gelatin-based surfactant disclosed by the invention has the chromaticity less than or equal to 30Hazen, preferably has the chromaticity less than or equal to 20Hazen, measured by a national standard GB/T9282 method.
The light transmittance of the gelatin-based surfactant measured by the GBT2566-2010 method is more than or equal to 80%, and the preferable light transmittance is more than or equal to 90%.
The viscosity of the gelatin-based surfactant is 300-6000mPa.s, and the acid value is less than or equal to 0.5mgKOH/g.
The invention also provides a preparation method of the gelatin-based surfactant shown in the formula 1, which comprises the step of reacting gelatin serving as an initiator with ethylene oxide and propylene oxide in the presence of an alkaline catalyst to obtain the gelatin-based surfactant.
In the process of the invention, the gelatin material has a water content of less than 500ppm, preferably less than 200ppm; preferably, the gelatin is dehydrated in vacuum before reaction at a dehydration temperature of 100-140 ℃, preferably 100-120 ℃ for a dehydration time of 0.5-4 hours, preferably 1-2 hours, to a water content of less than 500ppm;
preferably, the gelatin is a common commercial raw material and can be prepared from animal skin, bone and other raw materials.
In the method of the present invention, the alkaline catalyst is selected from any one or a combination of at least two of alkali metal hydroxide, alkaline earth metal oxide, phosphazene catalyst, alkali metal methoxide, alkali metal ethoxide, preferably any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, phosphazene;
preferably, the alkaline catalyst is used in an amount of 0.01 to 1%, preferably 0.05 to 0.5% of the total mass of ethylene oxide and propylene oxide.
In the method of the invention, the mass ratio of the gelatin to the ethylene oxide to the propylene oxide is 1:0.4-35:0.4-1.4, preferably 1:6.8-17.1:0.5-1.3.
In the process of the invention, the reaction is carried out at a temperature of from 100 to 180 ℃, preferably from 110 to 160 ℃;
in the reaction process, ethylene oxide and propylene oxide are continuously fed, and the control pressure of the feeding process is 0.1-0.6MPaG, preferably 0.1-0.3MpaG; aging reaction is carried out for 1-4h, preferably 1-2h after feeding is finished, and the reaction reaches the end point;
in the reaction process, the ethylene oxide and propylene oxide are fed in sequence, namely propylene oxide is firstly fed in for reaction, and then ethylene oxide is fed in; preferably, propylene oxide is added in an amount of 1 to 3mol.
As the gelatin contains amino and carboxyl, the amino activity is very high, and the product is easy to deepen and turn yellow when the gelatin reacts with EO, the invention discovers that in the reaction process, PO reaction is introduced in advance to lead 1-3mol PO groups to be polymerized in advance in a molecular chain, and then EO polymerization is carried out, so that the yellowing can be effectively prevented. The analysis is that the secondary hydroxyl is introduced in advance in the reaction to avoid the occurrence of explosion polymerization, meanwhile, the PO quantity which is introduced in advance in the polymerization reaction needs to be strictly controlled, the introduced PO group needs to be proper, if too much PO is introduced, the excessive side reaction can cause the increase of the unsaturation degree of the product, and the increase of the formaldehyde, acetaldehyde and acrolein content can influence the appearance, so that 1-3mol PO is most suitable.
In the method of the invention, the reaction can be carried out in any reactor such as a tubular reactor, a stirred tank, a loop reactor and the like, and after the reaction is finished, acid is added into the reaction liquid for neutralization treatment, and the acid is selected from organic acids such as acetic acid, lactic acid, neodecanoic acid and the like, preferably acetic acid; preferably, the reaction solution is neutralized to a pH of 5 to 7, preferably 6 to 7;
preferably, the neutralized system is further vacuum stripped of unreacted ethylene oxide, propylene oxide and other gaseous impurities.
The invention further provides application of the gelatin-based surfactant shown in the formula 1 in the fields of detergents, pharmacy, textiles, cosmetics, lubrication, defoamers and the like.
In the present invention, the use of the above gelatin-based surfactant in cosmetics is exemplified, and preferably, there is provided a shampoo composition comprising, by weight:
the shampoo composition is prepared by weighing the components in proportion, and stirring and mixing at 30-50 ℃ for 0.5-4h, preferably 1-2h, until the components are fully and uniformly mixed.
The pH value of the shampoo composition is 6.5-7, the viscosity of the shampoo composition is 500-6000 Pa.s at 25 ℃, the light transmittance is more than or equal to 70%, and the chromaticity is less than or equal to 50.
Preferably, there is also provided a laundry detergent composition comprising, in parts by weight:
the preparation method of the liquid laundry detergent composition comprises the steps of weighing the components according to a proportion, stirring and mixing for 0.5-4h, preferably 1-2h at 30-60 ℃ until the components are fully and uniformly mixed.
The pH value of the liquid laundry detergent composition is 6.5-7, the viscosity of the liquid laundry detergent composition is 1000-6000 Pa.s at 25 ℃, the light transmittance is more than or equal to 70%, and the chromaticity is less than or equal to 50.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1) The invention provides a gelatin-based polyether surfactant, wherein the basic constituent unit of gelatin is amino acid, the gelatin has the advantage of wide material sources, and the gelatin is obtained from organisms, compared with chemical raw materials, the biological-based material has the advantages of small skin irritation, good biocompatibility, easy degradation, small acute toxicity of aquatic organisms and the like, and meets the global carbon neutralization requirement.
2) In the gelatin-based surfactant, the part of the amino group and the PO/EO after polymerization is changed into polyether, so that the gelatin-based surfactant can be used as a nonionic surfactant, has the characteristic of good formula compatibility, and carboxylic acid and carboxylate carried by the gelatin-based surfactant have the characteristic of an anionic surfactant, and have the advantages of both anionic and nonionic surfactants.
3) The surfactant disclosed by the invention polymerizes EO/PO on gelatin, and because the PO section contains branched chains, the surfactant has the effect of reducing the solidifying point, the defect of normal-temperature solid of the original gelatin is overcome, meanwhile, the yellowing influence is eliminated by prepolymerization of a certain amount of PO and then polymerization with EO in the preparation process, and the prepared surfactant has good light transmittance and chromaticity, and does not have any adverse influence on the color of a formula.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.
1. The main raw material source information adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
gelatin, chinese medicine reagent, purity is more than or equal to 99%;
sodium methoxide: the purity of the Ara Ding Shiji is more than or equal to 30 percent, and the Ara Ding Shiji is sodium methoxide methanol solution;
potassium methoxide: the purity of the Ara Ding Shiji is more than or equal to 99.5 percent, and the Ara Ding Shiji is in powder form;
phosphazene: the purity of the product is more than or equal to 40 percent and the product is phosphazene ethanol solution;
EO, PO: wanhua chemistry, moisture content < 100ppm;
HX5551A gardenia flavor essence: the purity of Jinan poly Yili chemical industry Co., ltd is more than or equal to 99 percent;
trisodium citrate: the purity of the Western reagent is more than or equal to 99.9%;
lauric acid: zhejiang Qianzin medical science and technology Co., ltd, the purity is more than or equal to 99.5%;
methyl parahydroxybenzoate, dipropylene glycol, potassium sorbate, disodium edetate, triethanolamine, glycerol: the purity of the Ara Ding Shiji is more than or equal to 99%;
sodium fatty alcohol ether sulfate (AESS 70%): in Zanyu science and technology, the purity is 70%, and 30% of water is contained;
sodium chloride: the purity of the Chinese medicine reagent is more than or equal to 99 percent;
fatty alcohol polyoxyethylene ether, the purity of the EOD device is more than or equal to 99.5 percent;
disodium EDTA: the purity of the Suzhou gorgeous industry is more than or equal to 99 percent.
2. The analysis and test method adopted by the embodiment of the invention comprises the following steps:
biodegradability: measured by a GB/T19277 method;
biocompatibility: measured by the method of GB/T16886;
foam volume: measured by a GB/T12579 method;
average molecular weight: measured by GPC;
chromaticity: the method is measured by a national standard GB/T9282 method;
transmittance: measured by GBT 2566-2010;
decontamination ratio: measured by the method of GB/T13174-2021;
radical scavenging rate: the method is used for measuring the cosmetic industry T/SHRH 006-2018;
rinsing times; taking 8 pieces of cloth with the same texture, 50cm and 50cm, respectively immersing the cloth into 2L of mixed liquid of laundry detergent to be detected with the concentration of 1wt% and water, stirring for 5min, taking out, rinsing with 2L of water, spin-drying with a centrifuge, recording for 1 time, repeating rinsing and spin-drying processes until no macroscopic foam exists on the water surface, and recording rinsing times.
Structural characterization: the measurement IS carried out by using a Thermo Fisher IS50 FTIR infrared spectrometer, and the set parameters are as follows: the scanning times are 16 times, and the scanning range is 4000-400cm -1 . The raw material is 3400-3500cm -1 with-NH 2 Is 3300cm -1 Has a stretching vibration peak of-NH. If the characteristic absorption peak of the product in the wave band disappears after the reaction, 1101cm -1 The C-O-C telescopic vibration absorption peak is enhanced, so that the successful synthesis of the product is indicated.
Example 1
Preparation of gelatin-based surfactant:
200g of gelatin and 16.3g of KOH catalyst are added into a reaction vessel, the temperature is raised to 100 ℃, and the vacuum dehydration is carried out for 2 hours until the water content is 400ppm; the reaction temperature is controlled to 140 ℃, 88.2g (1 mol) of propylene oxide is firstly introduced into a reaction vessel, the feeding time is 30min, the pressure is controlled to be 0.1-0.3MPaG, then 1338g of ethylene oxide is continuously added, the feeding time is 5h, the pressure is controlled to be 0.1-0.3MPaG, the aging reaction is carried out for 1h after the ethylene oxide is fed, and then 8.9g of acetic acid is added into the reaction liquid to neutralize to pH 6.8, thus obtaining the gelatin-based surfactant.
The product of example 1 was tested according to the infrared spectrum test method described above: the raw material is 3400-3500cm -1 with-NH 2 Is 3300cm -1 Has a stretching vibration peak of-NH. The characteristic absorption peak of the product in the wave band disappears and is 1101cm -1 The C-O-C stretching vibration absorption peak is enhanced, and the gelatin-based surfactant with the structure shown in the formula 1 is obtained.
The pure gelatin-based surfactant product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The shampoo composition is prepared by adopting the gelatin-based surfactant of the embodiment, and the formula comprises the following components:
trisodium citrate 0.5g, lauric acid 15g, gelatin-based surfactant 2g, methylparaben 0.2g, dipropylene glycol 5g, potassium sorbate 0.3g, disodium edetate 0.3g, gardenia flavor essence 0.2g, deionized water 76.5g.
Weighing the components according to the formula, pouring the components into a stirring kettle, stirring and mixing for 1h at 40 ℃, and completely and uniformly mixing until no visible foreign matters exist, thus obtaining the shampoo composition.
The shampoo composition was measured for pH, viscosity at 25 ℃, light transmittance, and radical scavenging rate according to the methods described above, and the results are shown in table 2.
The gelatin-based surfactant of the embodiment is adopted to prepare a liquid laundry detergent composition, and the formula comprises the following components:
3g of gelatin-based surfactant, 18g of fatty alcohol-polyoxyethylene ether, 12g of fatty alcohol-ether sodium sulfate, 3g of triethanolamine, 0.3g of EDTA disodium, 2g of glycerol, 0.3g of sodium chloride, 0.3g of gardenia flavor essence and 61.1g of deionized water.
Weighing the components according to the formula, pouring the components into a stirring kettle, stirring and mixing for 1h at 40 ℃, and completely and uniformly mixing until no visible foreign matters exist, thus obtaining the liquid laundry detergent composition.
The pH, viscosity at 25℃and transmittance, detergency ratio and the number of rinsing times of the liquid laundry detergent composition were measured according to the above-mentioned methods, and the results are shown in Table 3.
Example 2
Preparation of gelatin-based surfactant:
adding 300g of gelatin and 1.92g of sodium methoxide catalyst into a reaction vessel, heating to 120 ℃, and vacuumizing and dehydrating for 1h until the water content is 300ppm; the reaction temperature is controlled to be 110 ℃, 275g (2 mol) of propylene oxide is firstly introduced into a reaction vessel, the feeding time is 60min, the pressure is controlled to be 0.2-0.3MPaG, then 2084g of ethylene oxide is continuously added, the feeding time is 6h, the pressure is controlled to be 0.2-0.3MPaG, the aging reaction is carried out for 1.5h after the ethylene oxide is fed, then 0.66g of acetic acid is added into the reaction liquid to neutralize to pH 6.7, and the gelatin-based surfactant is obtained.
The product of example 2 was tested according to the infrared spectrum test method described above: the raw material is 3400-3500cm -1 with-NH 2 Is 3300cm -1 Has a stretching vibration peak of-NH. The characteristic absorption peak of the product in the wave band disappears and is 1101cm -1 The C-O-C stretching vibration absorption peak is enhanced, and the gelatin-based surfactant with the structure shown in the formula 1 is obtained.
The pure gelatin-based surfactant product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The shampoo composition was formulated using the gelatin-based surfactant of this example, and the formulation composition and preparation method thereof were as described in reference to example 1, except that the gelatin-based surfactant of this example was replaced, and the other operations were unchanged. The shampoo composition was measured for pH, viscosity at 25 ℃, light transmittance, and radical scavenging rate, and the results are shown in table 2.
The formulation composition and preparation method of the laundry detergent composition prepared by using the gelatin-based surfactant of this example refer to example 1, and the only difference is that the gelatin-based surfactant of this example is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, transmittance, detergency, number of rinses, and results are reported in Table 3.
Example 3
Preparation of gelatin-based surfactant:
200g of gelatin and 72.2g of potassium methoxide catalyst are added into a reaction vessel, the temperature is raised to 140 ℃, and the vacuum dehydration is carried out for 2 hours until the water content is 200ppm; controlling the reaction temperature to 160 ℃, firstly introducing 267g (3 mol) of propylene oxide into a reaction container, feeding for 60min, controlling the pressure to be 0.2-0.3MPaG during the period, then continuously adding 6749g of ethylene oxide, feeding for 5h, controlling the pressure to be 0.2-0.3MPaG during the period, aging for 2h after the ethylene oxide is fed, and then adding 63g of acetic acid into the reaction liquid to neutralize to pH of 6.6, thus obtaining the gelatin-based surfactant.
The product of example 1 was tested according to the infrared spectrum test method described above: the raw material is 3400-3500cm -1 with-NH 2 Is 3300cm -1 Has a stretching vibration peak of-NH. The characteristic absorption peak of the product in the wave band disappears and is 1101cm -1 The C-O-C stretching vibration absorption peak is enhanced, and the gelatin-based surfactant with the structure shown in the formula 1 is obtained.
The pure gelatin-based surfactant product was tested for various performance indexes according to the method of the present invention, and the results are shown in table 1.
The shampoo composition was formulated using the gelatin-based surfactant of this example, and the formulation composition and preparation method thereof were as described in reference to example 1, except that the gelatin-based surfactant of this example was replaced, and the other operations were unchanged. The shampoo composition was measured for pH, viscosity at 25 ℃, light transmittance, and radical scavenging rate, and the results are shown in table 2.
The formulation composition and preparation method of the laundry detergent composition prepared by using the gelatin-based surfactant of this example refer to example 1, and the only difference is that the gelatin-based surfactant of this example is replaced, and other operations are unchanged. The pH, viscosity at 25 ℃, transmittance, detergency, number of rinses, and results are reported in Table 3.
Comparative example 1
A gelatin-based surfactant was prepared according to the method of example 1, except that: a gelatin-based surfactant was prepared by replacing the starting material with a 5000g/mol average molecular weight of x=37 with a 60 g/mol average molecular weight of 8000g/mol starting material, and replacing 88.2g (1 mol) of propylene oxide, and 1338g of ethylene oxide, all with 1342g of ethylene oxide, with the other procedure unchanged.
The performance index of each surfactant was measured according to the method of example 1, and the results are shown in Table 1.
The shampoo composition, the formulation of the laundry detergent composition and the preparation method are all referred to in example 1, except that the gelatin-based surfactant of this comparative example is replaced, and other operations are unchanged. The performance indexes were measured according to the method of example 1, and the results are shown in tables 2 and 3, respectively.
Comparative example 2
A gelatin-based surfactant was prepared according to the method of example 1, except that: a gelatin-based polyether (m value 20, n value 120) was prepared by substituting 88.2g (1 mol) of propylene oxide and 1338g of ethylene oxide with 1764g (20 mol) of propylene oxide and 25344g of ethylene oxide.
The performance index of each surfactant was measured according to the method of example 1, and the results are shown in Table 1.
The shampoo composition, the formulation of the laundry detergent composition and the preparation method are all referred to in example 1, except that the gelatin-based surfactant of this comparative example is replaced, and other operations are unchanged. The performance indexes were measured according to the method of example 1, and the results are shown in tables 2 and 3, respectively.
Comparative example 3
A gelatin-based surfactant was prepared according to the method of example 1, except that: the gelatin-based butane polyether was prepared by replacing 88.2g (1 mol) of propylene oxide and 1338g of ethylene oxide with butylene oxide, the sum of the molar amounts of both.
The performance index of each surfactant was measured according to the method of example 1, and the results are shown in Table 1.
The shampoo composition, the formulation of the laundry detergent composition and the preparation method are all referred to in example 1, except that the gelatin-based surfactant of this comparative example is replaced, and other operations are unchanged. The performance indexes were measured according to the method of example 1, and the results are shown in tables 2 and 3, respectively.
Comparative example 4
Referring to the shampoo formulation of example 1, the gelatin surfactant was replaced with equal mass gelatin.
The shampoo composition, the formulation of the laundry detergent composition and the preparation method are all referred to in example 1, except that the gelatin-based surfactant is replaced with equal mass gelatin, and the other operations are unchanged. The performance indexes were measured according to the method of example 1, and the results are shown in tables 2 and 3, respectively.
TABLE 1 gelatin-based surfactant characterization data
Table 2 results of shampoo composition performance testing
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| pH | 6.6 | 6.8 | 6.9 | 6.7 | 6.9 | 6.8 | 6.6 |
| Viscosity mPas | 1000 | 1200 | 2000 | 1600 | 3000 | 1200 | 5000 |
| Transmittance% | 98 | 99 | 97 | 70 | 56 | 62 | 60 |
| Chroma, hazon | 20 | 10 | 15 | 82 | 60 | 68 | 80 |
| Radical scavenging% | 100 | 99 | 100 | 80 | 65 | 10 | 20 |
Table 3 results of performance testing of liquid laundry compositions
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| pH | 6.5 | 6.5 | 6.6 | 6.6 | 6.4 | 6.3 | 6.5 |
| Viscosity mPas | 1200 | 1500 | 1000 | 1600 | 3000 | 300 | 2000 |
| Transmittance% | 98 | 99 | 97 | 98 | 90 | 90 | 96 |
| Chroma, hazon | 20 | 10 | 15 | 12 | 30 | 35 | 30 |
| Decontamination rate% | 99 | 99 | 98 | 82 | 88 | 30 | 40 |
| Number of rinses | 2 | 2 | 2 | 6 | 6 | 5 | 5 |
As can be seen from the data in Table 1 above, the gelatin-based surfactants within the scope of the present invention all have excellent light transmittance, biocompatibility, degradability, chromaticity and detergency. And the gelatin-based polyether prepared in the scope of the invention has excellent formula compatibility and light transmittance in shampoo and liquid laundry detergent. Comparative example 1 shows that when EO is directly polymerized without polymerizing PO, and x > 50, the prepared gelatin polyether has extremely high chromaticity and extremely low light transmittance. Comparative example 2 shows that the gelatin-based polyether prepared when m > 3 and n exceeds 100 is also high in color and low in light transmittance. Comparative example 3 it can be seen that the butylene oxide polymerized gelatin-based polyether does not possess surfactant-related cleaning and foam properties. It can also be seen from comparative example 4 that the pure gelatin starting material also has poor performance in the surfactant field.
The gelatin surfactants of the present invention are more easily rinsed by experiments on the number of rinses.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (34)
1. A gelatin-based surfactant having a structure represented by formula (1):
wherein R is a residue introduced by gelatin;
x is an integer of 20 to 50;
m is an integer of 1 to 3;
n is an integer of 1 to 100.
2. The gelatin-based surfactant of claim 1, wherein x is an integer from 30 to 40.
3. The gelatin-based surfactant of claim 1, wherein n is an integer from 20 to 50.
4. The gelatin-based surfactant of claim 1, wherein the gelatin-introduced residues R comprise residues of various amino acids in the gelatin composition.
5. The gelatin-based surfactant according to claim 4, wherein the amino acid is selected from any one or a combination of at least two of glycine, proline, alanine, glutamic acid, leucine, isoleucine, valine, phenylalanine.
6. The gelatin-based surfactant according to claim 1, wherein the gelatin-based surfactant has an average molecular weight of 12000-410000, a chromaticity of 30Hazen or less, and a light transmittance of 80% or more;
the viscosity of the gelatin-based surfactant is 300-6000 Pa.s, and the acid value is less than or equal to 0.5mgKOH/g.
7. The gelatin-based surfactant of claim 6, wherein the average molecular weight is 86000-211000.
8. The gelatin-based surfactant of claim 6, wherein the chroma is 20Hazen or less.
9. The gelatin-based surfactant according to claim 6, wherein the light transmittance is not less than 90%.
10. A process for the preparation of a gelatin-based surfactant according to any one of claims 1 to 9, characterized in that gelatin is used as an initiator and reacted with ethylene oxide and propylene oxide in the presence of an alkaline catalyst to give a gelatin-based surfactant;
the mass ratio of the gelatin to the ethylene oxide to the propylene oxide is 1:0.4-35:0.4-1.4;
in the reaction process, the feeding sequence of the ethylene oxide and the propylene oxide is that the propylene oxide is firstly introduced to react, then the ethylene oxide is introduced, and the ageing reaction is carried out for 1-4 hours after the feeding is finished.
11. The method of claim 10, wherein the gelatin has a water content of less than 500ppm.
12. The method of claim 11, wherein the gelatin has a water content of less than 200ppm.
13. The method according to claim 11, wherein the gelatin is dehydrated in vacuum at a dehydration temperature of 100 to 140 ℃ for a dehydration time of 0.5 to 4 hours before the reaction.
14. The method according to claim 13, wherein the dehydration temperature is 100 to 120 ℃ and the dehydration time is 1 to 2 hours.
15. The preparation method according to claim 10, wherein the mass ratio of the gelatin to the ethylene oxide and the propylene oxide is 1:6.8-17.1:0.5-1.3.
16. The method according to claim 10, wherein the basic catalyst is selected from any one or a combination of at least two of alkali metal hydroxide, alkaline earth metal oxide, phosphazene catalyst, alkali metal methoxide, alkali metal ethoxide.
17. The method according to claim 16, wherein the basic catalyst is selected from any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, and phosphazene.
18. The preparation method according to claim 10, wherein the amount of the basic catalyst is 0.01-1% of the total mass of ethylene oxide and propylene oxide.
19. The preparation method according to claim 18, wherein the amount of the basic catalyst is 0.05-0.5% of the total mass of ethylene oxide and propylene oxide.
20. The method of claim 10, wherein the reaction is at a temperature of 100-180 ℃;
in the reaction process, ethylene oxide and propylene oxide are fed continuously, and the pressure is controlled to be 0.1-0.6MPaG in the feeding process.
21. The method of claim 20, wherein the reaction is at a temperature of 110-160 ℃.
22. The method of claim 20, wherein the feed process control pressure is 0.1-0.6MPaG.
23. The method of claim 10, wherein the aging reaction is 1-2 hours after completion of the feeding.
24. The process according to claim 10, wherein propylene oxide is added in an amount of 1 to 3mol.
25. The method according to claim 10, wherein the reaction is completed, and the reaction mixture is neutralized by adding an acid selected from the group consisting of organic acids.
26. The method of claim 25, wherein the organic acid is selected from acetic acid, lactic acid, neodecanoic acid.
27. The process of claim 25 wherein the reaction mixture is neutralized to a pH of from 5 to 7.
28. The process of claim 27 wherein the reaction mixture is neutralized to a pH of from 6 to 7.
29. The method of claim 25, wherein the neutralized system further removes unreacted ethylene oxide and propylene oxide gas impurities in vacuum.
30. Use of a gelatin-based surfactant as claimed in any of claims 1 to 9 or as prepared by a process as claimed in any of claims 10 to 29 in the fields of detergents, pharmaceuticals, textiles, cosmetics, lubrication, defoamers.
31. A shampoo composition comprising the gelatin-based surfactant of any one of claims 1-9 or prepared by the method of any one of claims 10-29, the composition comprising in parts by weight:
32. the shampoo composition of claim 31, wherein the composition comprises in parts by weight:
33. a laundry detergent composition comprising the gelatin-based surfactant of any one of claims 1-9 or prepared by the process of any one of claims 10-29, in parts by weight comprising:
34. the liquid laundry detergent composition of claim 33, comprising in parts by weight:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111499794.7A CN114044818B (en) | 2021-12-09 | 2021-12-09 | Gelatin-based surfactant and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111499794.7A CN114044818B (en) | 2021-12-09 | 2021-12-09 | Gelatin-based surfactant and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114044818A CN114044818A (en) | 2022-02-15 |
| CN114044818B true CN114044818B (en) | 2023-05-26 |
Family
ID=80212584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111499794.7A Active CN114044818B (en) | 2021-12-09 | 2021-12-09 | Gelatin-based surfactant and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114044818B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888797A (en) * | 1970-08-04 | 1975-06-10 | Carapus Company Limited | Detergent composition |
| CN109762159A (en) * | 2018-12-19 | 2019-05-17 | 万华化学集团股份有限公司 | One kind surfactant containing selenium and preparation method thereof |
| CN111454784A (en) * | 2020-04-30 | 2020-07-28 | 中山榄菊日化实业有限公司 | Floor cleaning agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3486303A1 (en) * | 2017-11-21 | 2019-05-22 | Henkel IP & Holding GmbH | Laundry composition having broad spectrum stain removal |
-
2021
- 2021-12-09 CN CN202111499794.7A patent/CN114044818B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888797A (en) * | 1970-08-04 | 1975-06-10 | Carapus Company Limited | Detergent composition |
| CN109762159A (en) * | 2018-12-19 | 2019-05-17 | 万华化学集团股份有限公司 | One kind surfactant containing selenium and preparation method thereof |
| CN111454784A (en) * | 2020-04-30 | 2020-07-28 | 中山榄菊日化实业有限公司 | Floor cleaning agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Poly(ethylene oxide) surfactant polymers;KATANCHALEE VACHEETHASANEE et al.;《J Biomater Sci Polym Ed》;第15卷(第1期);第95–110页 * |
| 多链型高分子表面活性剂的合成及其对水煤浆的作用效果;张树军 等;《齐齐哈尔轻工学院学报》;第8卷(第4期);第44-48页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114044818A (en) | 2022-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112513237B (en) | Process for preparing alkoxylated polyethyleneimines | |
| JP5652691B2 (en) | Polyalkylene glycol derivative and method for producing the same | |
| CN1049244C (en) | Detergent gels | |
| CN104559213A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyethylene glycol | |
| AU2011219566A1 (en) | Associative acrylic emulsion containing a monomer based on oxo alcohol, production method thereof, and method for thickening an aqueous formulation produced from said emulsion | |
| CA1177096A (en) | Low-foaming nonionic surfactants | |
| CN107057052B (en) | Castor oil group polyether glycol and its polyurethane soft foamed plastics of preparation | |
| CN114044818B (en) | Gelatin-based surfactant and preparation method and application thereof | |
| NO180164B (en) | Liquid, concentrated aqueous solutions of salts of alkyl ether carboxylic acid and a process for their preparation | |
| CN111620780B (en) | Simple, low-cost and high-hydrophilicity polyglycerol ester preparation method | |
| CN116926958B (en) | Amphoteric aliphatic super-hydrophilic liquid softener and preparation method thereof | |
| CN100410304C (en) | Synthetic method for crosslinking agent-pentaerythritol allyl ether for high molecular polymerization | |
| CN108130214B (en) | Functional surfactant for cleaning and preparation method thereof | |
| CN106336502A (en) | Method for preparing semi-dull and full-dull titanium polyester through adding titanium dioxide | |
| EP0358263A2 (en) | Thickening agents for aqueous systems | |
| JP4252192B2 (en) | Fatty acid polyoxyalkylene alkyl ether and method for producing the same | |
| CN114085373B (en) | Hyaluronic acid polyether polyol and preparation method and application thereof | |
| WO2016053212A1 (en) | Process for preparation of concentrated gelling free aqueous solution of betaine | |
| CN102892798A (en) | Low-profile additives on the basis of renewable resources | |
| CN113214077A (en) | Method for degrading thermoplastic polyethylene terephthalate | |
| JP2834551B2 (en) | Polyether carboxylate | |
| JP5864413B2 (en) | Method for producing monohydroxypolyalkylene oxide | |
| CN113831527B (en) | Preparation method of methallyl alcohol polyoxyethylene ether | |
| RU2205191C1 (en) | Method of synthesis of amorphouzed polyvinyl alcohol | |
| CN101659725A (en) | Preparation method of copolymer of hydroxybutyl vinyl ether and maleic anhydride |
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 |