CN113045698A - Zwitterionic polymer and preparation method and application thereof - Google Patents
Zwitterionic polymer and preparation method and application thereof Download PDFInfo
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- CN113045698A CN113045698A CN201911388184.2A CN201911388184A CN113045698A CN 113045698 A CN113045698 A CN 113045698A CN 201911388184 A CN201911388184 A CN 201911388184A CN 113045698 A CN113045698 A CN 113045698A
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- Prior art keywords
- zwitterionic polymer
- sulfobetaine
- acrylic acid
- polymer
- zwitterionic
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- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000001179 sorption measurement Methods 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 35
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229940117986 sulfobetaine Drugs 0.000 claims abstract description 35
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 28
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 28
- -1 methacryloyl ethyl sulfobetaine Chemical compound 0.000 claims abstract description 26
- 241000894006 Bacteria Species 0.000 claims abstract description 15
- 239000008375 oral care agent Substances 0.000 claims abstract description 13
- 229920006254 polymer film Polymers 0.000 claims abstract description 8
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 229920001577 copolymer Polymers 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 9
- 239000002244 precipitate 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
- 239000000843 powder Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000000499 gel Substances 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
- 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
- 238000010186 staining Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 210000003296 saliva Anatomy 0.000 abstract description 5
- 210000004400 mucous membrane Anatomy 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 201000002170 dentin sensitivity Diseases 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 230000036347 tooth sensitivity Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 51
- 229910021641 deionized water Inorganic materials 0.000 description 50
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 44
- 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 44
- 239000000243 solution Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 20
- 102000034287 fluorescent proteins Human genes 0.000 description 15
- 108091006047 fluorescent proteins Proteins 0.000 description 15
- 210000004268 dentin Anatomy 0.000 description 10
- 239000012460 protein solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 8
- 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 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 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000002904 solvent Substances 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
- 230000015572 biosynthetic process Effects 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
- 150000001875 compounds Chemical class 0.000 description 4
- 235000011180 diphosphates Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000007794 irritation Effects 0.000 description 4
- 210000000214 mouth Anatomy 0.000 description 4
- 229940048084 pyrophosphate Drugs 0.000 description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 description 4
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 235000006468 Thea sinensis Nutrition 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 235000020279 black tea Nutrition 0.000 description 3
- 229910001424 calcium ion Inorganic materials 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
- 239000007858 starting material Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 235000013616 tea Nutrition 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 208000002064 Dental Plaque Diseases 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229940078916 carbamide peroxide Drugs 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000006378 damage Effects 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
- 210000002200 mouth mucosa Anatomy 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
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000007995 HEPES buffer Substances 0.000 description 1
- 239000007836 KH2PO4 Substances 0.000 description 1
- 206010044029 Tooth deposit Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012660 binary copolymerization Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 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
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect 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
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 239000002052 molecular layer Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003826 tablet 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
- 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
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
Abstract
The invention relates to the field of high molecular materials, and discloses a zwitterionic polymer, and a preparation method and application thereof. The zwitterionic polymer is formed by copolymerizing acrylic acid and a zwitterionic monomer, namely methacryloyl ethyl sulfobetaine, and can form a compact polymer film on the surface of teeth, so that proteins and bacteria in saliva can be prevented from being adsorbed on the surface of the teeth, and the effect of protecting the teeth is achieved. The invention applies the zwitterionic polymer to the oral care agent for the first time as an active ingredient for resisting exogenous stains, bacteria and protein adsorption. The zwitterionic polymer disclosed by the invention is free from biotoxicity and good in safety, and does not stimulate mucous membranes to cause tooth sensitivity; secondly, the color spot resistance and the timeliness are good; thirdly, the material which is harmful to the environment, such as phosphorus, is not contained, and the material belongs to an environment-friendly material.
Description
Technical Field
The invention relates to the field of high molecular materials, in particular to a zwitterionic polymer and a preparation method and application thereof.
Background
The formation process of dental plaque is that nutrient substances in saliva are adsorbed on the surface of teeth to form a base suitable for the growth of bacteria, and the bacteria are adsorbed to absorb nutrient substances and proliferate to expand, so that the dental plaque is formed after reaching a certain amount.
At present, in the field of tooth anti-stain whitening, the main approaches for chemical whitening can be divided into bleaching agents and pyrophosphate systems. The bleaching agent is most widely applied to hydrogen peroxide and carbamide peroxide, the mechanisms of the action of the hydrogen peroxide and the carbamide peroxide are similar, and both the hydrogen peroxide and the carbamide peroxide form superoxide radicals to generate redox action with a colored matrix, so that the pigment is faded or decomposed into small molecules to achieve the whitening effect. The pyrophosphate system compound can chelate with metal ions in the oral cavity, allowing the tartar seeds to attack and thereby avoid the formation of tartar. Among them, the first solution has the disadvantages of poor mouth feel of hydrogen peroxide in oral cavity, irritation to oral mucosa, influence on enamel surface after long-term use, tooth sensitivity and the like. The second proposal has the defects that the phosphorus-containing substances in the compounds of the pyrophosphoric acid system easily cause eutrophication and have great harm to the environment, and the substitution and elimination are trending.
In the two schemes, no polymer is adopted, and the polymer composition applied to the field of tooth whitening at present is an oral care composition formed by compounding vinyl methyl ether/maleic anhydride copolymer and other oral care substances. Vinyl methyl ether/maleic anhydride (PVM/MA) is a raw material with relatively high monomer price, and is introduced into the oral care field as a thickening agent and an adhesive in recent years. Meanwhile, a plurality of documents report the prevention effect of PVM/MA on exogenous color spots, for example, the oral care composition formed by compounding PVM/MA with zinc citrate and tetrasodium pyrophosphate is applied to oral care products in Weimeizi. However, PVM/MA is expensive and has limited ability to resist protein adsorption, and mainly depends on the compound of zinc citrate and pyrophosphate system to play the role. However, the problem of oral mucosa destruction of the pyrophosphate system still 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 the teeth, and plays a role in protecting the teeth. The invention applies the zwitterionic polymer to the oral care agent for the first time as an active ingredient for resisting exogenous stains, bacteria and protein adsorption. Compared with the bleaching agent and the pyrophosphoric acid system used for whitening teeth in the prior art, the zwitterionic polymer disclosed by the invention has the advantages of no biotoxicity, good safety and no irritation to mucous membrane, so that teeth are sensitive; on the other hand, the polymer has outstanding ability to resist protein adsorption on the tooth surface; in addition, the material has no influence on the environment and is an environment-friendly material.
The specific technical scheme of the invention is as follows:
the invention provides a zwitterionic polymer with protein non-specific 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 strong ionic solvation, if harmful substances such as protein, bacteria and the like are adsorbed on the surface of the teeth, the barrier of the hydration layer on the surface needs to be broken firstly, the free energy barrier caused by dehydration entropy change is overcome, and the replacement of the water molecular layer on the surface is an essential step, so that the nutrient substances and bacteria in saliva cannot be adsorbed on the surface of the teeth coated 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 the formation of extrinsic stains and dental calculus in teeth. 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 the bleaching agent and the pyrophosphoric acid system used for whitening teeth in the prior art, the zwitterionic polymer disclosed by the invention has the advantages of no biotoxicity, good safety and no irritation to mucous membrane, so that teeth are sensitive; on the other hand, the polymer has outstanding ability to resist protein adsorption on the tooth surface; in addition, the material has no influence on the environment and is an environment-friendly material.
It is emphasized that not any zwitterionic polymers have similar effects, and the mechanism of action of the zwitterionic polymers of the invention at the molecular structure level is specifically: the amphoteric ionic polymer is prepared by binary copolymerization of acrylic acid and a zwitterionic monomer, namely methacryloyl ethyl sulfobetaine. Carboxyl in the copolymer can be tightly combined with calcium ions on the surface of the tooth, so that the bonding strength of the polymer film adsorbed on the surface of the tooth is increased, and brush-shaped side chains on the zwitterionic monomer methacryloylethyl sulphobetaine 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 and n2 < 300.
The invention also provides a preparation method of the zwitterionic polymer, which comprises the following steps:
1) dissolving methacrylethyl sulfobetaine in water to obtain a methacrylethyl sulfobetaine aqueous solution.
2) Stirring, adding acrylic acid into the methacrylethyl sulfobetaine aqueous solution, adding an initiator, and heating for reaction.
3) After the reaction is finished, the product is dropped into absolute ethyl alcohol for precipitation, centrifugal treatment is carried out, and the precipitate is frozen and dried to obtain the target product.
Preferably, the mole ratio of the methacrylethyl sulfobetaine to acrylic acid is 1: (0.5-2).
The reason why the ratio of the two monomers is controlled within the above range in the present invention is that: as described above, the adsorption of the polymer of the present invention on the tooth surface depends mainly on carboxyl groups, and therefore, it is necessary to control the density of carboxyl groups on the molecular chain within a reasonable range. Within the above range, the bonding strength of the polymer to the tooth surface is highest.
Preferably, in step 1), the concentration of the methacrylethyl sulfobetaine aqueous solution is 50 to 100 mg/mL.
Preferably, in the step 2), the temperature of the reaction is raised to 65-75 ℃, and the reaction time is 10-12 h.
Preferably, in the step 2), the mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1 to (15-20).
Preferably, in the step 3), the volume ratio of the product in the step 2) to the absolute ethyl alcohol is 1: 1-5.
Preferably, in the step 3), the centrifugation time is 5-10min, and the centrifugation rotating speed is 3000-.
Preferably, in the step 3), the freeze drying time is 18-24 h.
The present inventors have discovered that the above zwitterionic polymers can be used as active ingredients against extrinsic stains, bacteria and protein adsorption in the preparation of oral care agents.
Preferably, the zwitterionic polymer is used in combination with an acrylic acid/maleic anhydride copolymer in the oral care agent.
The carboxyl groups in the acrylic acid/maleic anhydride copolymer are also effective in adhering 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, and the generation of tartar particles such as calcium phosphate is prevented. Meanwhile, the copolymer has large molecular weight, is not easy to be absorbed by human body, and can avoid causing some recessive toxic and side effects.
The effect of singly adopting the acrylic acid/maleic anhydride copolymer is not ideal, but the inventor finds that the acrylic acid/methacrylic acyl ethyl sulfobetaine copolymer and the acrylic acid/maleic anhydride copolymer have good cooperativity through research, and the acrylic acid/maleic anhydride copolymer and the acrylic acid/methacrylic acyl ethyl sulfobetaine copolymer are compounded for use, so that compared with a solution in which the acrylic acid/methacrylic acyl ethyl sulfobetaine copolymer is singly added, the compound composition can effectively increase the resistance of teeth to exogenous color spots. The reason for this is that the two copolymers differ in molecular weight, and the small copolymer (polymer of the invention) can be made to complement the position in the large copolymer (acrylic acid/maleic anhydride copolymer, molecular weight), thus making the polymer film on the tooth surface denser. Preferably, the molecular weight of the acrylic acid/methacryloyl ethyl sulfobetaine copolymer is 20000-50000, and the molecular weight of the acrylic acid/maleic anhydride copolymer is 2000-10000.
Preferably, the oral care agent is a toothpaste, gel, mouthwash, powder, confection, 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 the teeth, and plays a role in protecting the teeth. The invention applies the zwitterionic polymer to the oral care agent for the first time as an active ingredient for resisting exogenous stains, bacteria and protein adsorption. Compared with the bleaching agent and the pyrophosphoric acid system used for whitening teeth in the prior art, the zwitterionic polymer disclosed by the invention has the advantages of no biotoxicity, good safety and no irritation to mucous membrane, so that teeth are sensitive; on the other hand, the polymer has outstanding ability to resist protein adsorption on the tooth surface; in addition, the material has no influence on the environment and is an environment-friendly material.
(2) The preparation process of the zwitterionic polymer is simple to operate and suitable for large-scale mass production.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A zwitterionic polymer having the following formula:
wherein n1 and n2 are less than 500.
Preferably, n1 and n2 < 300.
The preparation method of the zwitterionic polymer comprises the following steps:
1) dissolving methacryloylethyl sulfobetaine in water to obtain a methacryloylethyl sulfobetaine aqueous solution with the concentration of 50-100 mg/mL.
2) Stirring, adding acrylic acid into the methacrylethyl sulfobetaine aqueous solution, adding an initiator, and heating to 65-75 ℃ for reaction for 10-12 h. The mol ratio of the methacryl ethyl sulfobetaine to the acrylic acid is 1 to (0.5-2). The mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1: 15-20.
3) After the reaction is finished, the product is dropped into absolute ethyl alcohol according to the volume ratio of 1: 1-5 for precipitation, centrifugal treatment is carried out, the centrifugal time is 5-10min, the centrifugal rotating speed is 3000-.
The above zwitterionic polymers can be used as active ingredients against extrinsic stains, bacteria and protein adsorption in the preparation of oral care agents.
Preferably, the zwitterionic polymer is used in combination with an acrylic acid/maleic anhydride copolymer in the oral care agent. Preferably, the molecular weight of the acrylic acid/methacryloyl ethyl sulfobetaine copolymer is 20000-50000 and the molecular weight of the acrylic acid/maleic anhydride copolymer is 2000-10000.
Preferably, the oral care agent is a toothpaste, gel, mouthwash, powder, confection, lozenge, or the like.
Example 1
A zwitterionic polymer prepared by the following method:
1) firstly, 2.79g of white powder of methacryloyl ethyl sulfobetaine is weighed and added into a single-neck flask, 35ml of deionized water is weighed and added into the flask, and the mixture is stirred for 10min at the same time, so that the methacryloyl ethyl sulfobetaine is dissolved in the deionized water.
2) 0.36g of acrylic acid (molar ratio of the two starting materials 1: 0.5) was weighed out and dissolved in 10ml of deionized water, and the solution was added to a flask of 1).
3) Weighing 30mg of initiator ammonium persulfate to dissolve in 5ml of deionized water, adding into the flask in 1) after completely dissolving, stirring, heating to 65 ℃, and reacting for 12 hours.
4) And dripping the mixed liquid obtained after the reaction is finished into a centrifugal tube filled with 80mL of absolute ethyl alcohol for precipitation, putting the centrifugal tube into a centrifugal machine, centrifuging the centrifugal tube at the rotating speed of 3500r/min for 10min, pouring out the supernatant, completely freezing the precipitate by using liquid nitrogen, and then putting the precipitate into a freeze dryer for freeze drying for 24h to obtain the product.
The product was weighed to give 2.98g, 94.6% yield; the product was characterized by gel permeation chromatography to have a molecular weight of 1.9W.
The bovine serum albumin marked by fluorescence is taken as protein for adsorption, the round hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of the hydroxyapatite sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after an experiment. The fluorescence intensity is low when the adsorption resistance is strong, and the fluorescence intensity is high when the adsorption resistance is weak.
1) A fluorescent protein solution was prepared at a concentration of 1mg/ml, and the solvent was artificial saliva (Table 1).
Two round hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water and put into an ultrasonic oscillator to be oscillated for 10 minutes to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloylethyl 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 a copolymer composition solution with a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two pieces of hydroxyapatite A, B were placed in the copolymer solution and deionized water, respectively, and placed in a shaker for 10 minutes at 200 rpm.
4) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and placed in a shaker to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were respectively put into 30ml of deionized water and shaken for 30 times to wash the fluorescent protein physically adhered to the surface.
7) Taking out from water, placing into a watch glass, and measuring fluorescence intensity of hydroxyapatite sheet surface with fluorescence microscope to obtain AAt 2s exposure time, the fluorescence intensity P is 2218. B fluorescence intensity P2590 at 200ms exposure time. After conversion to equal exposure time, PA＝2330，PB25900, the anti-protein adsorption effect was (PB-PA)/PB 91.00%.
Example 2
A zwitterionic polymer prepared by the following method:
1) firstly, 2.79g of white powder of methacryloyl ethyl sulfobetaine is weighed and added into a single-neck flask, 35ml of deionized water is weighed and added into the flask, and the mixture is stirred for 10min at the same time, so that the methacryloyl ethyl sulfobetaine is dissolved in the deionized water.
0.72g of acrylic acid (molar ratio of the two starting materials 1: 1) was weighed out and dissolved in 10ml of deionized water, and the solution was added to the flask 1).
3) Weighing 35mg of initiator ammonium persulfate to dissolve in 5ml of deionized water, adding into the flask in 1) after completely dissolving, stirring, heating to 72 ℃, and reacting for 10 hours.
4) And dripping the mixed liquid obtained after the reaction is finished into a centrifugal tube filled with 100mL of absolute ethyl alcohol for precipitation, putting the centrifugal tube into a centrifugal machine for centrifugation at 4000r/min for 10min, pouring out supernatant, completely freezing the precipitate with liquid nitrogen, and then putting the precipitate into a freeze dryer for freeze drying for 24 hours to obtain a product.
The product was weighed to give 3.30g, 94% yield; the product was characterized by gel permeation chromatography to have a molecular weight of 2.3W.
The bovine serum albumin marked by fluorescence is taken as protein for adsorption, the round hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of the hydroxyapatite sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after an experiment. The fluorescence intensity is low when the adsorption resistance is strong, and the fluorescence intensity is high when the adsorption resistance is weak.
1) Fluorescent protein solution is prepared with the concentration of 1mg/ml, and the solvent is artificial saliva.
Two round hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water and put into an ultrasonic oscillator to be oscillated for 10 minutes to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloylethyl sulfobetaine (molecular weight 2.3w, molar ratio of the two monomers 1: 1) was dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution with a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two pieces of hydroxyapatite A, B were placed in the copolymer solution and deionized water, respectively, and placed in a shaker for 10 minutes at 200 rpm.
4) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and placed in a shaker to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were respectively put into 30ml of deionized water and shaken for 30 times to wash the fluorescent protein physically adhered to the surface.
7) After being taken out of the water, the plate was placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite plate was measured by a fluorescence microscope, whereby the fluorescence intensity P of a was 2480 at 20s exposure time. B, under the exposure time of 200ms, the fluorescence intensity P is 2108. After conversion to equal exposure time, PA＝2480，PB210800, the effect of anti-protein adsorption is (PB-PA)/PB 98.82%.
Example 3
A zwitterionic polymer prepared by the following method:
1) firstly, 2.79g of white powder of methacryloyl ethyl sulfobetaine is weighed and added into a single-neck flask, 35ml of deionized water is weighed and added into the flask, and the mixture is stirred for 10min at the same time, so that the methacryloyl ethyl sulfobetaine is dissolved in the deionized water.
1.44g of acrylic acid (molar ratio of the two starting materials: 1: 2) were weighed out and dissolved in 10ml of deionized water, and the solution was added to the flask of 1).
3) Weighing 40mg of initiator ammonium persulfate to dissolve in 5ml of deionized water, adding into the flask in 1) after completely dissolving, stirring, heating to 72 ℃, and reacting for 10 hours.
4) And dripping the mixed liquid obtained after the reaction is finished into a centrifugal tube filled with 150mL of absolute ethyl alcohol for precipitation, putting the centrifugal tube into a centrifugal machine for centrifugation at 4000r/min for 10min, pouring out supernatant, completely freezing the precipitate with liquid nitrogen, and then putting the precipitate into a freeze dryer for freeze drying for 24 hours to obtain a product.
The product was weighed to give 3.75g, 88.6% yield; the product was characterized by gel permeation chromatography to have a molecular weight of 2.8W.
The bovine serum albumin marked by fluorescence is taken as protein for adsorption, the round hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of the hydroxyapatite sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after an experiment. The fluorescence intensity is low when the adsorption resistance is strong, and the fluorescence intensity is high when the adsorption resistance is weak.
1) Fluorescent protein solution is prepared with the concentration of 1mg/ml, and the solvent is artificial saliva.
Two round hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water and put into an ultrasonic oscillator to be oscillated for 10 minutes to remove small bubbles in the dental sheets.
2) 0.5g of acrylic acid/methacryloylethyl sulfobetaine (molecular weight 2.8w, molar ratio of the two monomers 1: 2) was dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution with a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two pieces of hydroxyapatite A, B were placed in the copolymer solution and deionized water, respectively, and placed in a shaker for 10 minutes at 200 rpm.
4) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and placed in a shaker to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were respectively put into 30ml of deionized water and shaken for 30 times to wash the fluorescent protein physically adhered to the surface.
7) After being taken out of the water, the plate was placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite plate was measured by a fluorescence microscope, so that the fluorescence intensity P of A at 2s exposure time was 1988. B, under the exposure time of 150ms, the fluorescence intensity P is 2365. Scaling to equal ExposureAfter light time, PA＝1988，PB31533, the protein adsorption resistance 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 with the concentration of 1mg/ml, and the solvent is artificial saliva.
Two round hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water and put into an ultrasonic oscillator to be oscillated for 10 minutes 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 give 10ml of a copolymer composition solution at a concentration of 5%, and 10ml of deionized water was used as a control.
3) Two pieces of hydroxyapatite sheet A, B were placed in cocamidopropyl betaine solution and deionized water, respectively, and placed in a shaker for 10 minutes at 200 rpm.
4) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and placed in a shaker to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were respectively put into 30ml of deionized water and shaken for 30 times to wash the fluorescent protein physically adhered to the surface.
7) The plate was taken out of the water and placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite plate was measured by a fluorescence microscope, whereby the fluorescence intensity P of a was 2218 at an exposure time of 200 ms. B fluorescence intensity P2250 at 200ms exposure time. After conversion to equal exposure time, PA＝2250，PB2250, the anti-protein adsorption effect was 1.4% for (PB-PA)/PB.
It can therefore be concluded that cocamidopropyl betaine does not have efficacy against protein adsorption, and it merely acts as a surfactant. From this, it is clear that not any zwitterionic polymer can exert technical effects similar to those of the polymer of the present invention.
Example 4 (composition)
Selecting black tea from Litton yellow brand as exogenous color spot source, measuring hydroxyapatite with color difference meter to show brightness change of the stone, and finally representing the ability of resisting exogenous color spot by using brightness change of soaked black tea. The brightness change is low when the color spot resistance is strong, and the brightness change is high when the color spot resistance is weak.
1) A bag of black tea is soaked in 100ml of deionized water at 90 ℃, and the tea bag is taken out after natural cooling.
2) 0.33g of acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of the two monomers 1: 1) and 0.17g of acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of the two monomers 1: 1) were dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution with a concentration of 5%, and 10ml of deionized water was taken as a control.
3) Taking two round hydroxyapatite sheets A, B with same specification to simulate dentin, soaking in deionized water, placing in an ultrasonic oscillator, shaking for 10min to remove small bubbles in the dental sheets, taking out from the water, and immediately measuring whiteness L with a color difference meterA1＝90.24、LB1＝90.19。
4) Two hydroxyapatite sheets were placed in the copolymer solution and deionized water, respectively, and placed in a shaker at 200rpm for 5 minutes.
5) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
6) The two hydroxyapatite tablets were placed in 10ml of tea water, respectively, and placed in a shaker for 3 minutes at 120 rpm.
7) The two hydroxyapatite sheets were respectively put into 30ml of deionized water and shaken for 30 times to wash the tea stains physically adhered to the surfaces.
8) Immediately after taking out from the water, L was measured by a color difference meterA2＝88.59、LB276.76. The adsorbed stain quantification is obtained as Δ LA＝1.65、ΔLB＝13.43。
As can be seen from the above results, in this example, the effect of resisting extrinsic stain in the composition solution was (Δ L) as compared with deionized waterB-ΔLA)/ΔLB＝87.71％。
Example 5 (composition)
The bovine serum albumin marked by fluorescence is taken as protein for adsorption, the round hydroxyapatite sheet is used for simulating dentin, and the average fluorescence intensity of the hydroxyapatite sheet observed by a fluorescence microscope is used for representing the amount of protein adsorption after an experiment. The fluorescence intensity is low when the adsorption resistance is strong, and the fluorescence intensity is high when the adsorption resistance is weak.
1) A fluorescent protein solution was prepared at a concentration of 1mg/ml, and the solvent was artificial saliva (Table 1).
Two round hydroxyapatite sheets A, B with the same specification are taken to simulate dentin, soaked in deionized water and put into an ultrasonic oscillator to be oscillated for 10 minutes to remove small bubbles in the dental sheets.
2) 0.33g of acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of the two monomers 1: 1) and 0.17g of acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of the two monomers 1: 1) were dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution with a concentration of 5%, and 10ml of deionized water was taken as a control.
3) Two pieces of hydroxyapatite A, B were placed in the copolymer solution and deionized water, respectively, and placed in a shaker for 10 minutes at 200 rpm.
4) Two pieces of hydroxyapatite were put into 30ml of deionized water, respectively, and shaken 30 times to wash the physically adhered polymer on the surface.
5) Two pieces of hydroxyapatite were placed in 10ml of fluorescent protein solution, respectively, and placed in a shaker to shake at 120rpm for 5 minutes.
6) Two pieces of hydroxyapatite were respectively put into 30ml of deionized water and shaken for 30 times to wash the fluorescent protein physically adhered to the surface.
7) The plate was taken out of the water and placed in a petri dish, and the fluorescence intensity of the surface of the hydroxyapatite plate was measured by a fluorescence microscope, whereby the fluorescence intensity P of a was 2090 at 8s exposure time. B exposure at 100msThe fluorescence intensity P was 2688 over time. After conversion to equal exposure time, PA＝2090，PB215040, the effect of anti-protein adsorption is (PB-PA)/PB 99.03%.
TABLE 1 Artificial saliva formula
| Substance(s) | Concentration of |
| CaCl2 | 0.001mol/L |
| KH2PO4 | 0.004mol/L |
| HEPES | 0.02mol/L |
| KCl | 0.016mol/L |
| NH4Cl | 0.0046mol/L |
| MgCl2 | 0.0002mol/L |
| KOH | 0.0118mol/L |
Example 6 (composition)
1) 0.33g of acrylic acid/maleic anhydride copolymer (molecular weight 5332, molar ratio of the two monomers 1: 1) and 0.17g of acrylic acid/methacryloyl ethyl sulfobetaine copolymer (molecular weight 35300, molar ratio of the two monomers 1: 1) were dissolved in 10ml of deionized water to form 10ml of a copolymer composition solution with a concentration of 5%, and a 5% tetrasodium pyrophosphate solution was taken as a control.
2) To 10ml of the copolymer solution and 10ml of the tetrasodium pyrophosphate solution were added 0.1g of CaCl, respectively2And (4) chelating. After the state is stabilized, the copolymer solution is clear. The tetrasodium pyrophosphate solution was uniformly turbid.
Then 0.1g of Na was added to each of the above solutions2HPO4After the powder is stabilized, the copolymer solution is clear, the tetrasodium pyrophosphate solution is uniform and turbid, and tiny flocculent precipitates appear.
Calcium pyrophosphate being poorly soluble in water, the composition and Ca2+The formed complex is easy to dissolve in water, and free Ca is not released2+The composition and Ca2+The complex formed is easier to clean and therefore the copolymer prevents calculus formation better than tetrasodium pyrophosphate.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A zwitterionic polymer characterized by the following structural formula:
wherein n1 and n2 are less than 500.
2. The zwitterionic polymer of claim 1, where n1, n2 < 300.
3. A process for the preparation of the zwitterionic polymer of claim 1 or 2, characterised by the steps of:
1) dissolving methacrylethyl sulfobetaine in water to obtain a methacrylethyl sulfobetaine aqueous solution;
2) stirring, adding acrylic acid into the methacrylethyl sulfobetaine aqueous solution, adding an initiator, and heating for reaction;
3) after the reaction is finished, the product is dropped into absolute ethyl alcohol for precipitation, centrifugal treatment is carried out, and the precipitate is frozen and dried to obtain the target product.
4. The process of claim 3, wherein the molar ratio of methacryloylethylsulfobetaine to acrylic acid is 1: 0.5-2.
5. The method according to claim 3, wherein the concentration of the methacrylethyl sulfobetaine aqueous solution in the step 1) is 50 to 100 mg/mL.
6. The method of claim 3, wherein in step 2):
the temperature of the reaction is increased to 65-75 ℃, and the reaction time is 10-12 h; and/or
The mass ratio of the initiator to the methacryloyl ethyl sulfobetaine is 1: 15-20.
7. The method of 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; and/or
The centrifugation time is 5-10min, and the centrifugation rotating speed is 3000-; and/or
The freeze drying time is 18-24 h.
8. Use of the zwitterionic polymer of claim 1 or 2 or of the zwitterionic polymer obtained by the process of any one of claims 3 to 7 in the preparation of an oral care agent as an active ingredient against extrinsic staining, bacteria and protein adsorption, characterised in that the zwitterionic polymer forms a dense polymer film on the tooth surface.
9. The use of claim 8, wherein the zwitterionic polymer is formulated with an acrylic acid/maleic anhydride copolymer in the oral care agent.
10. The use of claim 8 or 9, wherein the oral care agent is a toothpaste, gel, mouthwash, powder, confectionary, or lozenge.
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