CN113045698B - Zwitterionic polymer and preparation method and application thereof - Google Patents
Zwitterionic polymer and preparation method and application thereof Download PDFInfo
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- CN113045698B CN113045698B CN201911388184.2A CN201911388184A CN113045698B CN 113045698 B CN113045698 B CN 113045698B CN 201911388184 A CN201911388184 A CN 201911388184A CN 113045698 B CN113045698 B CN 113045698B
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- acrylic acid
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- methacryloyl ethyl
- zwitterionic
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 38
- 229940117986 sulfobetaine Drugs 0.000 claims abstract description 38
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 methacryloyl ethyl sulfobetaine Chemical compound 0.000 claims abstract description 30
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 26
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 241000894006 Bacteria Species 0.000 claims abstract description 15
- 239000008375 oral care agent Substances 0.000 claims abstract description 12
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 229920001577 copolymer Polymers 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007937 lozenge Substances 0.000 claims description 3
- 239000002324 mouth wash Substances 0.000 claims description 3
- 229940051866 mouthwash Drugs 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000606 toothpaste Substances 0.000 claims description 3
- 229940034610 toothpaste Drugs 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 14
- 229920006254 polymer film Polymers 0.000 abstract description 7
- 230000007794 irritation Effects 0.000 abstract description 5
- 210000004400 mucous membrane Anatomy 0.000 abstract description 5
- 210000003296 saliva Anatomy 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 50
- 229910021641 deionized water Inorganic materials 0.000 description 50
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 40
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 40
- 239000000243 solution Substances 0.000 description 27
- 102000034287 fluorescent proteins Human genes 0.000 description 15
- 108091006047 fluorescent proteins Proteins 0.000 description 15
- 210000004268 dentin Anatomy 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000012460 protein solution Substances 0.000 description 10
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- 239000000120 Artificial Saliva Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 244000269722 Thea sinensis Species 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 229940005657 pyrophosphoric acid Drugs 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 4
- QCZAWDGAVJMPTA-RNFRBKRXSA-N ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C Chemical compound ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C QCZAWDGAVJMPTA-RNFRBKRXSA-N 0.000 description 4
- 208000006558 Dental Calculus Diseases 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229940098773 bovine serum albumin Drugs 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 4
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 4
- 201000002170 dentin sensitivity Diseases 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 210000000214 mouth Anatomy 0.000 description 4
- 230000036347 tooth sensitivity Effects 0.000 description 4
- 235000006468 Thea sinensis Nutrition 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 235000020279 black tea Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 235000013616 tea Nutrition 0.000 description 3
- 206010044029 Tooth deposit Diseases 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 2
- 229940068475 zinc citrate Drugs 0.000 description 2
- 235000006076 zinc citrate Nutrition 0.000 description 2
- 239000011746 zinc citrate Substances 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007995 HEPES buffer Substances 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
- 241001440840 Mikania micrantha Species 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 229940078916 carbamide peroxide Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000001516 effect on protein Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000002200 mouth mucosa Anatomy 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000007505 plaque formation Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 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
- C08F220/38—Esters containing sulfur
-
- 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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dermatology (AREA)
- Dental Preparations (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to the field of high polymer materials, and discloses a zwitterionic polymer, a preparation method and application thereof. The zwitterionic polymer is formed by copolymerizing acrylic acid and a zwitterionic monomer, namely methacryloyl ethyl sulfobetaine, can form a layer of compact polymer film on the surface of teeth, can prevent protein and bacteria in saliva from being adsorbed on the surface of teeth, and plays a role in protecting teeth. The present invention applies zwitterionic polymers for the first time to oral care agents as active ingredients against exogenous stains, bacteria and protein adsorption. The amphoteric ion polymer has no biological toxicity, good safety and no irritation to mucous membrane, and is sensitive to teeth; secondly, the stain resistance timeliness is good; thirdly, the material does not contain substances harmful to the environment such as phosphorus, and the like, and belongs to environment-friendly substances.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a zwitterionic polymer and a preparation method and application thereof.
Background
The plaque formation process is that nutrient substances in saliva are adsorbed on the tooth surface to form a base suitable for bacterial growth, and bacteria absorb nutrients to proliferate and expand after being adhered, so that the plaque is formed after a certain amount of bacteria are reached.
Currently in the field of tooth stain resistance whitening, the main chemical whitening approaches can be divided into bleaching agents and pyrophosphoric acid systems. The most widely used bleaching agent is hydrogen peroxide and carbamide peroxide, which have similar mechanisms of action, and the peroxide and carbamide peroxide form superoxide radicals to have oxidation-reduction action with colored matrix, so that the pigment is discolored or decomposed into small molecules, and the whitening effect is achieved. The pyrophosphate system compound may sequester metal ions in the oral cavity so that the tartar seed is attacked to avoid tartar formation. Among them, the first solution has the disadvantage that the hydrogen peroxide has poor taste in the oral cavity, has irritation to the mucous membrane of the oral cavity, and can also affect the enamel surface to cause a series of problems such as tooth sensitivity and the like after long-term use. The second solution has the disadvantage that phosphorus-containing substances in the compound of the pyrophosphoric acid system are easy to cause eutrophication, and have great environmental hazards and become increasingly popular as alternatives.
In both of the above solutions, no polymer is used, and the polymer composition currently used in the field of tooth whitening is an oral care composition formed by compounding a vinyl methyl ether/maleic anhydride copolymer with other oral care substances. Vinyl methyl ether/maleic anhydride, PVM/MA for short, is a relatively expensive raw material for monomers, and has been introduced into the field of oral care in recent years as a thickener and binder. Meanwhile, some documents report the prevention effect of PVM/MA on exogenous color spots, such as mikania micrantha, and an oral care composition formed by compounding PVM/MA with zinc citrate and tetrasodium pyrophosphate is applied to oral care products. However, PVM/MA is expensive and has limited resistance to protein adsorption, and is mainly dependent on zinc citrate and pyrophosphoric acid compounds. The problem of oral mucosa destruction with pyrophosphate systems remains.
Disclosure of Invention
In order to solve the technical problems, the invention provides a zwitterionic polymer and a preparation method and application thereof. The zwitterionic polymer can form a layer of compact polymer film on the surface of teeth, can prevent protein and bacteria in saliva from being adsorbed on the surface of teeth, and plays a role in protecting teeth. The present invention applies zwitterionic polymers for the first time to oral care agents as active ingredients against exogenous stains, bacteria and protein adsorption. Compared with bleaching agents and pyrophosphoric acid systems for tooth whitening in the prior art, the zwitterionic polymer disclosed by the invention has the advantages that on one hand, the zwitterionic polymer is free of biotoxicity, good in safety, and free of irritation to mucous membrane and tooth sensitivity; on the other hand, the polymer is distinguished by its ability to resist adsorption of proteins on tooth surfaces; in addition, the method does not influence the environment and belongs to environment-friendly substances.
The specific technical scheme of the invention is as follows:
the invention provides a zwitterionic polymer with protein nonspecific adsorption resistance, which has the following structural formula:
wherein n1 and n2 are less than 500.
When the zwitterionic polymer is applied to an oral care agent, a compact hydration layer can be formed on the surface of teeth through the stronger ion solvation action, if harmful substances such as protein, bacteria and the like want to be adsorbed on the surface of the teeth, firstly, the barrier of the hydration layer on the surface needs to be broken, the free energy barrier caused by dehydration entropy change is overcome, and the water molecule layer on the surface is replaced by the essential step, so that nutrient substances and bacteria in saliva cannot be adsorbed on the surface of the teeth wrapped by the polymer film. It is known that the adsorption of harmful substances such as proteins and bacteria on the tooth surface is a source of diseases such as tooth extrinsic stains and calculus. The invention can effectively protect teeth by forming a layer of protective film on the surface of the teeth to resist the adsorption of protein and bacteria on the surface of the teeth. Compared with bleaching agents and pyrophosphoric acid systems for tooth whitening in the prior art, the zwitterionic polymer disclosed by the invention has the advantages that on one hand, the zwitterionic polymer is free of biotoxicity, good in safety, and free of irritation to mucous membrane and tooth sensitivity; on the other hand, the polymer is distinguished by its ability to resist adsorption of proteins on tooth surfaces; in addition, the method does not influence the environment and belongs to environment-friendly substances.
It should be emphasized that not all zwitterionic polymers have similar efficacy, and the mechanism of action of the zwitterionic polymers of the present invention on the molecular structure level is specifically: the zwitterionic polymer is prepared by binary copolymerization of acrylic acid and a zwitterionic monomer, namely methacryloyl ethyl sulfobetaine. The carboxyl in the copolymer can be tightly combined with calcium ions on the tooth surface, so that the bonding strength of the polymer film adsorbed on the tooth surface is increased, and the brush-shaped side chains on the zwitterionic monomer methacryloyl ethyl sulfobetaine are used for forming a hydration layer to resist the adsorption of protein molecules, so that the long-acting antibacterial effect is achieved.
Preferably, n1, n2<300.
The invention also provides a preparation method of the zwitterionic polymer, which comprises the following steps:
1) Dissolving the methacryloyl ethyl sulfobetaine in water to obtain a methacryloyl ethyl sulfobetaine aqueous solution.
2) Stirring, adding acrylic acid into the methacryloyl ethyl sulfobetaine aqueous solution, adding an initiator, and heating to react.
3) And after the reaction is finished, dripping the product into absolute ethyl alcohol for precipitation, centrifuging, and freeze-drying the precipitate to obtain the target product.
Preferably, the molar ratio of the methacryloyl ethyl sulfobetaine to the acrylic acid is 1: (0.5-2).
The reason why the present invention controls the ratio of the above two monomers in the above range is that: as mentioned above, the adsorption of the polymer of the present invention on the tooth surface is mainly dependent on carboxyl groups, and thus it is necessary to control the density of carboxyl groups on the molecular chain to a reasonable extent. Within the above range, the bonding strength of the polymer to the tooth surface is highest.
Preferably, in step 1), the concentration of the methacryloyl ethyl sulfobetaine aqueous solution is 50 to 100mg/mL.
Preferably, in the step 2), the reaction temperature is raised to 65-75 ℃ and the reaction time is 10-12h.
Preferably, in the step 2), the mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1:15-20.
Preferably, in step 3), the volume ratio of the product in step 2) to absolute ethanol is 1:1-5.
Preferably, in the step 3), the centrifugation time is 5-10min, and the centrifugation rotating speed is 3000-5000r/min.
Preferably, in step 3), the freeze-drying time is 18 to 24 hours.
The present invention has found that the zwitterionic polymers described above can be used as active ingredients against exogenous stains, bacteria and protein adsorption in the preparation of oral care agents.
Preferably, the zwitterionic polymer is formulated with an acrylic acid/maleic anhydride copolymer in the oral care agent.
The carboxyl groups in the acrylic acid/maleic anhydride copolymer can be effectively adhered to the tooth surface to form a polymer film on the tooth surface. Meanwhile, when the copolymer exists in the oral cavity, the copolymer can form a complex with metal ions, so that dental calculus particles such as calcium phosphate and the like are prevented. Meanwhile, the copolymer has large molecular weight, is not easy to be absorbed by human body, and can avoid causing some hidden toxic and side effects.
The effect of singly adopting the acrylic acid/maleic anhydride copolymer is not ideal, but the inventor discovers that the acrylic acid/methyl propionyl ethyl sulfobetaine copolymer and the acrylic acid/maleic anhydride copolymer have good cooperativity when being compounded, and the acrylic acid/maleic anhydride copolymer and the acrylic acid/methyl propionyl ethyl sulfobetaine copolymer are compounded for use, and compared with the solution of singly adding the acrylic acid/methyl propionyl ethyl sulfobetaine copolymer, the compound composition can effectively increase the resistance of teeth to exogenous stains. The reason for this is that the two copolymers have different molecular weights, and the small molecular copolymer (the polymer of the invention) can be repaired in the large molecular copolymer (the acrylic acid/maleic anhydride copolymer, the molecular weight is the same), so that the polymer film on the tooth surface is more compact. Preferably, the molecular weight of the acrylic acid/methyl acrylic ethyl sulfobetaine copolymer ranges from 20000 to 50000, and the molecular weight of the acrylic acid/maleic anhydride copolymer ranges from 2000 to 10000.
Preferably, the oral care agent is a toothpaste, gel, mouthwash, powder, confectionery, lozenge or the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) The zwitterionic polymer can form a layer of compact polymer film on the surface of teeth, can prevent protein and bacteria in saliva from being adsorbed on the surface of teeth, and plays a role in protecting teeth. The present invention applies zwitterionic polymers for the first time to oral care agents as active ingredients against exogenous stains, bacteria and protein adsorption. Compared with bleaching agents and pyrophosphoric acid systems for tooth whitening in the prior art, the zwitterionic polymer disclosed by the invention has the advantages that on one hand, the zwitterionic polymer is free of biotoxicity, good in safety, and free of irritation to mucous membrane and tooth sensitivity; on the other hand, the polymer is distinguished by its ability to resist adsorption of proteins on tooth surfaces; in addition, the method does not influence the environment and belongs to environment-friendly substances.
(2) The preparation process of the amphoteric ion polymer is simple to operate and is suitable for large-scale mass production.
Detailed Description
The invention is further described below with reference to examples.
General examples
A zwitterionic polymer having the structural formula:
wherein n1 and n2 are less than 500.
Preferably, n1, n2<300.
The preparation method of the zwitterionic polymer comprises the following steps:
1) The methacryloyl ethyl sulfobetaine is dissolved in water to obtain a methacryloyl ethyl sulfobetaine aqueous solution with the concentration of 50-100mg/mL.
2) Stirring, adding acrylic acid into the methacryloyl ethyl sulfobetaine aqueous solution, adding an initiator, and heating to 65-75 ℃ for reaction for 10-12h. The mol ratio of the methacryloyl ethyl sulfobetaine to the acrylic acid is 1: (0.5-2). The mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1:15-20.
3) After the reaction is finished, dripping the product into absolute ethyl alcohol according to the volume ratio of 1:1-5 for precipitation, centrifuging for 5-10min at the centrifugal speed of 3000-5000r/min, and freeze-drying the precipitate for 18-24 h to obtain the target product.
The zwitterionic polymers described above can be used as active ingredients against exogenous stains, bacteria and protein adsorption in the preparation of oral care agents.
Preferably, the zwitterionic polymer is formulated with an acrylic acid/maleic anhydride copolymer in the oral care agent. Preferably, the molecular weight of the acrylic acid/methyl acrylic acyl ethyl sulfobetaine copolymer ranges from 20000 to 50000, and the molecular weight of the acrylic acid/maleic anhydride copolymer ranges from 2000 to 10000.
Preferably, the oral care agent is a toothpaste, gel, mouthwash, powder, confectionery, lozenge or the like.
Example 1
A zwitterionic polymer prepared by the method comprising:
1) Firstly, weighing 2.79g of white powder of the methacryloyl ethyl sulfobetaine, adding the white powder into a single-neck flask, weighing 35ml of deionized water into the flask, and stirring for 10 minutes simultaneously to enable the methacryloyl ethyl sulfobetaine to be dissolved in the deionized water.
2) 0.36g of acrylic acid (molar ratio of the two materials 1:0.5) was weighed into 10ml of deionized water and added to the flask of 1) after complete dissolution.
3) 30mg of initiator ammonium persulfate is weighed and dissolved in 5ml of deionized water, added into a flask in the step 1) after complete dissolution, stirred, heated to 65 ℃ and reacted for 12 hours.
4) Dripping the obtained mixed liquid after the reaction into a centrifuge tube filled with 80mL of absolute ethyl alcohol to precipitate, putting the mixture into a centrifuge for centrifugation at 3500r/min for 10min, pouring out supernatant, completely freezing the precipitate by liquid nitrogen, and then sending the precipitate into a freeze dryer for freeze drying for 24 hours to obtain the product.
The product was weighed to give 2.98g, yield 94.6%; the product was characterized by gel permeation chromatography as having a molecular weight of 1.9W.
The fluorescence-labeled bovine serum albumin is used as an adsorption protein, a circular hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of a stone sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after experiments. The fluorescence intensity is low when the anti-adsorption capability is strong, and the fluorescence intensity is high when the anti-adsorption capability is weak.
1) Fluorescent protein solutions were prepared at a concentration of 1mg/ml, with the solvent being artificial saliva (Table 1).
Two circular hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water, and put into an ultrasonic oscillator to oscillate for 10 minutes so as to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloyl ethyl sulfobetaine (molecular weight 1.9w, molar ratio of the two monomers 1:0.5) was dissolved in 10ml of deionized water to form 10ml of copolymer composition solution with a concentration of 5%, and another 10ml of deionized water was taken as a control.
3) Two hydroxyapatite sheets A, B were placed in the copolymer solution and deionized water, respectively, and put into a shaker to shake at 200rpm for 10 minutes.
4) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and put into a shaking table to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to wash out surface physically adhered fluorescent proteins.
7) After being taken out of the water, the mixture was placed in a dish, and the fluorescence intensity of the surface of the hydroxyapatite sheet was measured by a fluorescence microscope, to obtain a fluorescence intensity p=2218 at 2s exposure time. B at 200ms exposure time, fluorescence intensity p=2590. Converted to equal exposure time, P A ＝2330，P B =25900, the anti-protein adsorption effect was (PB-PA)/pb=91.00%.
Example 2
A zwitterionic polymer prepared by the method comprising:
1) Firstly, weighing 2.79g of white powder of the methacryloyl ethyl sulfobetaine, adding the white powder into a single-neck flask, weighing 35ml of deionized water into the flask, and stirring for 10 minutes simultaneously to enable the methacryloyl ethyl sulfobetaine to be dissolved in the deionized water.
0.72g of acrylic acid (molar ratio of the two materials 1:1) was weighed into 10ml of deionized water and added to the flask of 1) after complete dissolution.
3) 35mg of initiator ammonium persulfate is weighed and dissolved in 5ml of deionized water, and added into a flask in the step 1) after complete dissolution, stirring is carried out, the temperature is raised to 72 ℃, and the reaction is carried out for 10 hours.
4) Dripping the obtained mixed liquid after the reaction is completed into a centrifuge tube filled with 100mL of absolute ethyl alcohol to precipitate, putting the mixed liquid into a centrifuge for centrifugation at 4000r/min for 10min, pouring out supernatant, completely freezing the precipitate by liquid nitrogen, and then sending the precipitate into a freeze dryer for freeze drying for 24 hours to obtain the product.
The product was weighed to give 3.30g with a yield of 94%; the product was characterized by gel permeation chromatography as having a molecular weight of 2.3W.
The fluorescence-labeled bovine serum albumin is used as an adsorption protein, a circular hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of a stone sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after experiments. The fluorescence intensity is low when the anti-adsorption capability is strong, and the fluorescence intensity is high when the anti-adsorption capability is weak.
1) Fluorescent protein solution is prepared at a concentration of 1mg/ml, and the solvent is artificial saliva.
Two circular hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water, and put into an ultrasonic oscillator to oscillate for 10 minutes so as to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloyl ethyl sulfobetaine (molecular weight 2.3w, molar ratio of the two monomers 1:1) was dissolved in 10ml of deionized water to form 10ml of copolymer composition solution with a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two hydroxyapatite sheets A, B were placed in the copolymer solution and deionized water, respectively, and put into a shaker to shake at 200rpm for 10 minutes.
4) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and put into a shaking table to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to wash out surface physically adhered fluorescent proteins.
7) After being taken out of the water, the mixture was placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite sheet was measured by a fluorescence microscope, to obtain a fluorescence intensity p=2480 at an exposure time of 20 s. B at 200ms exposure time, fluorescence intensity p=2108. Converted to equal exposure time, P A ＝2480，P B = 210800, the anti-protein adsorption effect was (PB-PA)/pb= 98.82%.
Example 3
A zwitterionic polymer prepared by the method comprising:
1) Firstly, weighing 2.79g of white powder of the methacryloyl ethyl sulfobetaine, adding the white powder into a single-neck flask, weighing 35ml of deionized water into the flask, and stirring for 10 minutes simultaneously to enable the methacryloyl ethyl sulfobetaine to be dissolved in the deionized water.
1.44g of acrylic acid (molar ratio of the two materials 1:2) was weighed into 10ml of deionized water and added to the flask of 1) after complete dissolution.
3) 40mg of initiator ammonium persulfate is weighed and dissolved in 5ml of deionized water, added into a flask in the step 1) after complete dissolution, stirred, heated to 72 ℃ and reacted for 10 hours.
4) Dripping the obtained mixed liquid after the reaction is completed into a centrifuge tube filled with 150mL of absolute ethyl alcohol to precipitate, putting the mixture into a centrifuge to centrifuge for 10min at 4000r/min, pouring out supernatant, completely freezing the precipitate by liquid nitrogen, and then sending the precipitate into a freeze dryer to freeze for 24 hours to obtain the product.
The product was weighed to give 3.75g with a yield of 88.6%; the product was characterized by gel permeation chromatography as having a molecular weight of 2.8W.
The fluorescence-labeled bovine serum albumin is used as an adsorption protein, a circular hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of a stone sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after experiments. The fluorescence intensity is low when the anti-adsorption capability is strong, and the fluorescence intensity is high when the anti-adsorption capability is weak.
1) Fluorescent protein solution is prepared at a concentration of 1mg/ml, and the solvent is artificial saliva.
Two circular hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water, and put into an ultrasonic oscillator to oscillate for 10 minutes so as to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloyl ethyl sulfobetaine (molecular weight 2.8w, molar ratio of the two monomers 1:2) was dissolved in 10ml of deionized water to form 10ml of copolymer composition solution with a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two hydroxyapatite sheets A, B were placed in the copolymer solution and deionized water, respectively, and put into a shaker to shake at 200rpm for 10 minutes.
4) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and put into a shaking table to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to wash out surface physically adhered fluorescent proteins.
7) After removal from water, the resulting mixture was placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite sheet was measured by a fluorescence microscope, to obtain a fluorescence intensity p=1988 at 2s exposure time. B at 150ms exposure time, fluorescence intensity p=2365. Converted to equal exposure time, P A ＝1988，P B 31533, the anti-protein adsorption effect was (PB-PA)/pb=93.70%.
Comparative example 1
A zwitterionic surfactant: cocamidopropyl betaine (molecular weight 342.52).
The zwitterionic surfactant was tested for anti-protein adsorption:
1) Fluorescent protein solution is prepared at a concentration of 1mg/ml, and the solvent is artificial saliva.
Two circular hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water, and put into an ultrasonic oscillator to oscillate for 10 minutes so as to remove small bubbles in the dental sheets.
2) 0.5g of cocamidopropyl betaine (molecular weight 342.52) was dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution at a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two hydroxyapatite sheets A, B were placed in cocamidopropyl betaine solution and deionized water, respectively, and placed in a shaker to shake at 200rpm for 10 minutes.
4) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and put into a shaking table to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to wash out surface physically adhered fluorescent proteins.
7) After being taken out of the water, the mixture was placed in a dish, and the fluorescence intensity of the surface of the hydroxyapatite sheet was measured by a fluorescence microscope, to obtain a fluorescence intensity p=2218 at 200ms exposure time. B at 200ms exposure time, fluorescence intensity p=2250. Converted to equal exposure time, P A ＝2250，P B 2250, the anti-protein adsorption effect was (PB-PA)/pb=1.4%.
It can thus be concluded that cocamidopropyl betaine has no effect on protein adsorption, and it only acts as a surfactant. It is clear that not any zwitterionic polymer can exert similar technical effects as the polymer according to the invention.
Example 4 (composition)
The Liton yellow brand carefully chosen black tea is used as an exogenous color spot source, the color difference meter is used for measuring the change of the brightness of the hydroxyapatite sheet representing stone sheet, and finally the exogenous color spot resistance is represented by the brightness change amount of the black tea after soaking. The brightness change is low when the anti-stain capability is strong, and the brightness change is high when the anti-stain capability is weak.
1) Soaking a bag of black tea in 100ml deionized water at 90 ℃, and taking out the tea bag after natural cooling.
2) 0.33g of acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of two monomers 1:1) and 0.17g of acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of two monomers 1:1) were dissolved in 10ml of deionized water to form 10ml of copolymer composition solution at a concentration of 5%, and another 10ml of deionized water was taken as a control.
3) Taking two round equal-specification hydroxyapatite sheets A, B to simulate dentin, soaking in deionized water, placing into an ultrasonic oscillator, vibrating for 10min to remove small bubbles in the dental sheets, taking out from water, and immediately measuring brightness L by using a color difference meter A1 ＝90.24、L B1 ＝90.19。
4) Two pieces of hydroxyapatite were placed in the copolymer solution and deionized water, respectively, and put into a shaking table to shake at 200rpm for 5 minutes.
5) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
6) Two pieces of hydroxyapatite were placed in 10ml of tea respectively, and put into a shaking table to shake at 120rpm for 3 minutes.
7) Two pieces of hydroxyapatite were each placed in 30ml of deionized water and shaken for 30 times to clean the tea stain physically adhered to the surface.
8) Immediately after removal from the water, L was measured with a color difference meter A2 ＝88.59、L B2 =76.76. Obtaining the adsorbed stain quantization DeltaL A ＝1.65、ΔL B ＝13.43。
From the above results, it was found that in this example, the composition solution had an anti-exogenous stain effect of (. DELTA.L) B -ΔL A )/ΔL B ＝87.71％。
Example 5 (composition)
The fluorescence-labeled bovine serum albumin is used as an adsorption protein, a circular hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of a stone sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after experiments. The fluorescence intensity is low when the anti-adsorption capability is strong, and the fluorescence intensity is high when the anti-adsorption capability is weak.
1) Fluorescent protein solutions were prepared at a concentration of 1mg/ml, with the solvent being artificial saliva (Table 1).
Two circular hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water, and put into an ultrasonic oscillator to oscillate for 10 minutes so as to remove small bubbles in the dental sheets.
2) 0.33g of acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of two monomers 1:1) and 0.17g of acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of two monomers 1:1) were dissolved in 10ml of deionized water to form 10ml of copolymer composition solution at a concentration of 5%, and another 10ml of deionized water was taken as a control.
3) Two hydroxyapatite sheets A, B were placed in the copolymer solution and deionized water, respectively, and put into a shaker to shake at 200rpm for 10 minutes.
4) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to clean the polymer physically adhered to the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and put into a shaking table to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were separately put into 30ml of deionized water and shaken 30 times to wash out surface physically adhered fluorescent proteins.
7) After being taken out of the water, the mixture was placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite sheet was measured by a fluorescence microscope, to obtain a fluorescence intensity p=2090 at an 8s exposure time. B at 100ms exposure time, fluorescence intensity p=2688. Converted to equal exposure time, P A ＝2090，P B = 215040, the anti-protein adsorption effect was (PB-PA)/pb= 99.03%.
Table 1 artificial saliva formulations
| Substance (B) | Concentration of |
| CaCl 2 | 0.001mol/L |
| KH 2 PO 4 | 0.004mol/L |
| HEPES | 0.02mol/L |
| KCl | 0.016mol/L |
| NH 4 Cl | 0.0046mol/L |
| MgCl 2 | 0.0002mol/L |
| KOH | 0.0118mol/L |
Example 6 (composition)
1) 0.33g of an acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of two monomers 1:1) and 0.17g of an acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of two monomers 1:1) were dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution at a concentration of 5%, and a 5% tetrasodium pyrophosphate solution was used as a control.
2) To 10ml of copolymer solution and 10ml of tetrasodium pyrophosphate solution were added 0.1g of CaCl, respectively 2 And (5) chelating. After the state was stable, the copolymer solution was clear. The tetrasodium pyrophosphate solution is in a uniform turbidity state.
Then 0.1g of Na was added to the above solution, respectively 2 HPO 4 After the powder is stable in state, the copolymer solution is clear, and the pyrophosphoric acid is tetra-phosphateThe sodium solution was uniformly cloudy and had a slightly flocculent precipitate.
Calcium pyrophosphate is poorly soluble in water, the present composition is in combination with Ca 2+ The complex formed is easily soluble in water and does not release free Ca 2+ The composition and Ca 2+ The complex formed is easier to clean, so the copolymer can prevent dental calculus better than tetrasodium pyrophosphate.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. Use of a composition of a zwitterionic polymer and an acrylic acid/maleic anhydride copolymer as an active ingredient against exogenous stains, bacteria and protein adsorption in the preparation of an oral care agent, characterized in that the zwitterionic polymer is a methacryloyl ethyl sulfobetaine/acrylic acid copolymer having the following structural formula:
wherein n1, n2<500;
the molecular weight of the zwitterionic polymer is 20000-50000, the mol ratio of the methacryloyl ethyl sulfobetaine monomer to the acrylic acid monomer is 1:0.5-2;
the molecular weight of the acrylic acid/maleic anhydride copolymer is 2000-10000.
2. The use according to claim 1, wherein n1, n2<300.
3. Use according to claim 1 or 2, characterized in that: the preparation method of the zwitterionic polymer comprises the following steps:
1) Dissolving methacryloyl ethyl sulfobetaine in water to obtain methacryloyl ethyl sulfobetaine aqueous solution;
2) Stirring, adding acrylic acid into the methacryloyl ethyl sulfobetaine aqueous solution, adding an initiator, and heating to react;
3) And after the reaction is finished, dripping the product into absolute ethyl alcohol for precipitation, centrifuging, and freeze-drying the precipitate to obtain the target product.
4. The use according to claim 3, wherein in step 1) the concentration of the aqueous solution of methacryloyl ethyl sulfobetaine is 50 to 100mg/mL.
5. The use according to claim 3, characterized in that in step 2): the reaction temperature is raised to 65-75 ℃ and the reaction time is 10-12h.
6. The use according to claim 3, characterized in that in step 2): the mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1:15-20.
7. The use according to claim 3, wherein in step 3): the volume ratio of the product in the step 2) to the absolute ethyl alcohol is 1:1-5.
8. The use according to claim 3, wherein in step 3): the centrifugation time is 5-10min, and the centrifugation rotating speed is 3000-5000r/min.
9. The use according to claim 3, wherein in step 3): the freeze drying time is 18-24 h.
10. The use according to claim 1, wherein the oral care agent is a toothpaste, gel, mouthwash, powder, confectionery or lozenge.
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| CN108192020A (en) * | 2018-01-03 | 2018-06-22 | 兰州石化职业技术学院 | A kind of preparation method of intelligent amphoteric ion polymer material |
| CN110028614A (en) * | 2019-04-16 | 2019-07-19 | 东华大学 | The micro-nano gel of antibacterial and fiber with protein adsorption function and preparation method thereof |
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| CN108192020A (en) * | 2018-01-03 | 2018-06-22 | 兰州石化职业技术学院 | A kind of preparation method of intelligent amphoteric ion polymer material |
| JP2019178200A (en) * | 2018-03-30 | 2019-10-17 | 東洋インキＳｃホールディングス株式会社 | Biofilm formation inhibiting coating agent and biofilm formation inhibiting laminate |
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