CN111807830A - 一种用于骨修复生物磷酸钙陶瓷浆料及其制备方法 - Google Patents
一种用于骨修复生物磷酸钙陶瓷浆料及其制备方法 Download PDFInfo
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- CN111807830A CN111807830A CN202010619285.2A CN202010619285A CN111807830A CN 111807830 A CN111807830 A CN 111807830A CN 202010619285 A CN202010619285 A CN 202010619285A CN 111807830 A CN111807830 A CN 111807830A
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- Prior art keywords
- calcium phosphate
- ceramic slurry
- bone repair
- calcium
- biological
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- 239000002002 slurry Substances 0.000 title claims abstract description 81
- 239000004068 calcium phosphate ceramic Substances 0.000 title claims abstract description 49
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 230000008439 repair process Effects 0.000 title claims abstract description 37
- 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 claims abstract description 81
- 239000002270 dispersing agent Substances 0.000 claims abstract description 29
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 39
- 239000001506 calcium phosphate Substances 0.000 claims description 29
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 29
- 235000011010 calcium phosphates Nutrition 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 26
- -1 N-methylaminocarboxylic acid sodium Chemical compound 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 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 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 11
- 159000000007 calcium salts Chemical class 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 125000004386 diacrylate group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical group CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [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 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000010407 vacuum cleaning Methods 0.000 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- NWWQVENFTIRUMF-UHFFFAOYSA-N diphenylphosphanyl 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=CC(C)=C1C(=O)OP(C=1C=CC=CC=1)C1=CC=CC=C1 NWWQVENFTIRUMF-UHFFFAOYSA-N 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910000392 octacalcium phosphate Inorganic materials 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920001522 polyglycol ester Polymers 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 3
- 239000003462 bioceramic Substances 0.000 claims 3
- 239000011575 calcium Substances 0.000 claims 3
- 229910052791 calcium Inorganic materials 0.000 claims 3
- 150000004683 dihydrates Chemical class 0.000 claims 1
- 150000004682 monohydrates Chemical class 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 29
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000007787 solid Substances 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 26
- 239000002245 particle Substances 0.000 description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 238000004062 sedimentation Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 5
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- HUSUHZRVLBSGBO-UHFFFAOYSA-L calcium;dihydrogen phosphate;hydroxide Chemical compound O.[Ca+2].OP([O-])([O-])=O HUSUHZRVLBSGBO-UHFFFAOYSA-L 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 238000002591 computed tomography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/10—Ceramics or glasses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
- C04B35/6306—Binders based on phosphoric acids or phosphates
- C04B35/6313—Alkali metal or alkaline earth metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
本发明公开了一种用于骨修复生物磷酸钙陶瓷浆料及其制备方法。该陶瓷浆料具有高固含量、低粘度、高分散性，解决现有出现二次团聚导致陶瓷浆料分散不均的问题，其组成成分按照重量百分比划分，由56～88％磷酸钙盐、2～4％亲水性表面活性剂、8～35％活性稀释剂、0～8％低聚物、0.2～4％分散剂、0.1～4％光引发剂、0.1～2％流平助剂、0.1～2％消泡助剂以及0.04～0.4％抗氧化剂组成。
Description
技术领域
本发明属于生物陶瓷领域，设计一种用于骨修复生物磷酸钙陶瓷浆料及其制备方法。
背景技术
磷酸钙陶瓷属于生物活性陶瓷材料，一般表现为在植入体内后，表面会形成羟基碳酸根磷灰石层，与人体骨相连，早在二十世纪七十年代就被报道，并迅速应用于临床。传统磷酸钙陶瓷骨植入物成型的方式有干压成型、湿法成型、挤压成型、注射成型、直接凝固成型等，该方法均不能满足临床个性化需求，比如：复杂的外形、精准的孔隙连通性及孔隙率等。
3D打印技术能够快速高精度成型，通过计算机断层扫描获取人体的DICOM数据，利用逐层叠加方式构造三维实体，可个性化设计。目前陶瓷材料3D打印技术主要有立体光固化成型(SLA)与数字光处理技术(DLP)，打印精度高、后处理力学强度可观。
陶瓷在SLA或DLP成型方式中，浆料的制备为核心技术，需既能满足高固含量又能满足低粘度(分散越均匀，在同一粘度下固含量越高)，陶瓷颗粒的分散性对打印件的性能起着重要作用。陶瓷颗粒在聚合物溶液中形成分散均匀稳定的体系取决于颗粒与颗粒间的作用力，当颗粒间的斥力大于引力时体系稳定，斥力小于引力时颗粒间易产生团聚。为了保证陶瓷颗粒在聚合物溶液中形成稳定体系。目前的研究主要集中于陶瓷颗粒表面，通过增大颗粒间的表面斥力，制备高分散性、高固含量、低粘度的陶瓷浆料，以满足高精度光固化成型方式的需求。
中国专利，CN108706969A提供了一种水基生物陶瓷光固化浆料及其制备方法和应用，该专利解决了水基生物陶瓷光固化浆料的稳定性，改善了浆料的沉降量；
中国专利，CN108658607A提供了一种新型陶瓷浆料及其制备的陶瓷和应用，该专利采用陶瓷粉末与分散剂混合，获得改性陶瓷粉末，解决了陶瓷浆料打印过程中固含量太低以及粘度过高的问题；
文献【Zhen Wang,Chuanzhen Huang,et.al..Development of a Novel AqueousHydroxyapatiteSuspension for Stereolithography Applied to BoneTissueEngineering.Ceramics International,2018】记载了利用聚丙烯酸铵盐修饰羟基磷灰石颗粒表面，获得了固含量为52vol.％的羟基磷灰石浆料。
但是，上述三种方法中均是通过对已成型的陶瓷粉末再次进行表面改性，从而提高陶瓷粉末与聚合物树脂间的融合性，改善浆料的固含量与分散性，但以上方法均忽略了一个问题：这类表面改性法主要是球磨、干燥后研磨，使得陶瓷粉末从出厂方具有较高分散性、高比表面积，经过改性处理后，可能会出现二次团聚的现象，降低了陶瓷粉末在树脂中的分散均匀性。
发明内容
为了解决上述现有技术存在的不足和缺点，提供了一种用于骨修复生物磷酸钙陶瓷浆料及其制备方法。本发明的目的在于采用原位法合成表面改性的磷酸钙盐材料，以其作为原料，配制的陶瓷浆料具有高固含量、低粘度、高分散性，解决现有出现二次团聚导致陶瓷浆料分散不均的问题。
本发明的具体技术方案如下：
本发明提供了一种用于骨修复生物磷酸钙陶瓷浆料，其特征在于，其组成成分按照重量百分比划分，由8～35％活性稀释剂、0～8％低聚物、0.2～4％分散剂、0.1～4％光引发剂、0.1～2％流平助剂、0.1～2％消泡助剂、0.04～0.4％抗氧化剂、56～88％磷酸钙盐以及2～4％亲水性表面活性剂组成。
进一步地，上述磷酸钙陶瓷浆料由75％磷酸钙盐、3％亲水性表面活性剂、11％活性稀释剂、1％低聚物、4％分散剂、3％光引发剂、1.5％流平助剂、1％消泡助剂以及0.5％抗氧化剂组成。
优选地，上述磷酸钙盐为羟基磷灰石或无定型磷酸钙或一水磷酸氢钙或二水磷酸氢钙或无水磷酸氢钙或磷酸八钙。
优选地，上述亲水性表面活性剂为直链烷基磺酸钠或脂肪酸甲酯磺酸钠或Α-烯基磺酸钠或脂肪醇聚氧乙烯醚硫酸钠或N-甲基酰胺羧酸钠。以上亲水性表面活性剂均在水中能发生水解，水解后的阴离子均可与钙离子发生静电吸附，再与磷酸根离子结合，形成改性磷酸钙盐，且上述表面活性剂可与聚合物树脂融合，从而提高粉末的分散性。
优选地，上述活性稀释剂为1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二缩三丙二醇二丙烯酸酯、聚乙二醇(200)二丙烯酸酯、聚乙二醇(400)二丙烯酸酯、聚乙二醇(600)二丙烯酸酯、二丙二醇类二丙烯酸酯、新戊二醇二丙烯酸酯中的一种或多种组合；以上活性稀释剂均具有光敏特性，在光引发剂的激发下发生聚合，达到光固化成型效果；
优选地，上述低聚物为环氧丙烯酸树脂、聚氨酯丙烯酸树脂或聚酯丙烯酸酯；以上低聚物均具有光敏特性，可作为辅助材料添加，提高活性稀释剂的固化时间与固化后强度。
优选地，上述分散剂为德国毕克BYK-110、聚磷酸钠、聚丙烯酸铵、聚丙烯酸钠、三乙基己基磷酸、十二烷硫酸钠、脂肪酸聚乙二醇酯、六偏磷酸钠中的一种或多种组合；以上分散剂均有降低粉末表面能的能力，针对磷酸钙盐陶瓷有较高的分散性。
优选地，上述光引发剂为安息香双甲醚、异丙基硫杂蒽酮、二苯甲酮、三苯基六氟锑酸盐、二苯基-(2,4,6-三甲基苯甲酰)氧磷、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、1-羟基环己基苯基甲酮中的一种或多种组合；以上光引发剂均在紫外光谱范围内使活性稀释剂与低聚物发生聚合，达到光固化成型效果；
优选地，上述抗氧化剂为6-三级丁基-4-甲基苯酚、双(3，5-三级丁基-4-羟基苯基)硫醚或四(β-(3，5-三级丁基-4-羟基苯基)丙酸)季戊四醇酯；以上抗氧化剂均具有空间阻碍的酚类化合物，能延缓或抑制活性稀释剂与低聚物性能发生改变，延长使用寿命；
优选地，上述流平助剂为德国毕克BYK-358N、德国毕克BYK-333、聚醚改性聚二甲基硅氧烷或聚醚改性硅油；以上流平助剂均能降低材料表面张力，且具有湿润效果；
优选地，上述消泡助剂为德国毕克BYK-A530、德国毕克BYK-065或德国毕克BYK-088；以上消泡助剂均含有破泡聚合物,消除浆料中的气泡；
另外，本发明还提供了制备上磷酸钙陶瓷浆料的方法，其具体实施步骤如下：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：将能溶解性钙盐与能溶解性磷酸盐分别溶入去离子水中，得到钙盐溶液与磷酸盐溶液；
步骤1.2：在钙盐溶液中加入亲水性表面活性剂，彻底溶解后，缓慢向该溶液中滴加磷酸盐溶液，首先在恒温的温度下搅拌、之后静置、最后进行真空抽滤清洗、干燥、研磨，制得表面改性的磷酸钙盐粉末；
步骤2：预混液制备
将活性稀释剂、低聚物、流平助剂、消泡助剂、光引发剂、抗氧化剂依次加入恒定温度的水浴锅中混合搅拌；其中，加入过程必须是等待前一个成分完全溶解以后再加入后一个成分，得到预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1获得的表面改性的磷酸钙盐粉末分批次加入所述预混液，每加入一部分磷酸钙盐粉末后加入一部分分散剂，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分进行超声搅拌直至搅拌均匀、再装入盛有氧化锆磨球的不透光罐子中进行球磨、消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料。
优选地，上述步骤1.1中能溶解性钙盐与能溶解性磷酸盐的摩尔比为0.5～1.67：1。
优选地，上述步骤1.2中恒温的温度为37～60℃；搅拌转速为300～600r/min；静置时间为4～24h；干燥方式为冷冻干燥或采用37～80℃鼓风干燥箱干燥；
优选地，上述步骤2中的恒定温度为37～60℃；
优选地，上述步骤3中的超声搅拌时间为4～6h；球磨处理时间为1～3h。
本发明所述步骤A中的能溶解性钙盐为硝酸钙、氯化钙或碳酸氢钙；
与现有技术相比，本发明具有以下有益效果：
1、本发明中以亲水性表面活性剂为模板，通过原位合成法制备的磷酸钙盐分散性较高，工艺简单，相比于对已成型的陶瓷粉末再进行表面改性法，避免二次团聚的产生。
2、本发明以步骤1中合成的磷酸钙盐为原料，配制聚合物光固化陶瓷浆料，有利于陶瓷颗粒在聚合物中的分散，提高颗粒与聚合物溶液的融合性，达到高固含量、低粘度的目的。
3、本发明步骤2中在预混液中加入的抗氧化剂，可通过分解氢过氧化物，中断聚合物自动氧化反应链，从而抑制或缓解聚合物的性能改变，延长浆料存放时间。
具体实施方式
下面结合具体实施例对本发明提供的用于骨修复生物磷酸钙陶瓷浆料做进一步地详细的说明。
实施例1
一种用于骨修复生物磷酸钙陶瓷浆料配方A的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：取摩尔比为1.67：1的硝酸钙与磷酸二氢铵，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在硝酸钙溶液中加入直链烷基磺酸钠(直链烷基磺酸钠作为亲水性表面活性剂加入量为磷酸钙盐理论合成量的4％)，彻底溶解后；在37℃恒温下缓慢向该溶液中滴加磷酸二氢铵溶液，以转速300r/min搅拌、静置4h、真空抽滤清洗、冷冻干燥、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为11％1,6-己二醇二丙烯酸酯(即活性稀释剂)、1％环氧丙烯酸树脂(即低聚物)、1.5％德国毕克BYK-358N(即流平助剂)、1％德国毕克BYK-A530(即消泡助剂)、0.5％6-三级丁基-4-甲基苯酚(即抗氧化剂)、3％安息香双甲醚(即光引发剂)依次加入37℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为78％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，78％表面改性的磷酸钙盐包括亲水性活性剂含量为3％、磷酸钙盐含量为75％)，每加入一批表面改性的磷酸钙盐粉末后均加入德国毕克BYK-110(即分散剂)，超声搅拌至浆料混合均匀，再继续加入表面改性的磷酸钙盐粉末与德国毕克BYK-110(即分散剂)(分散剂总加入量为4％)，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌4h，再装入盛有氧化锆磨球的不透光罐子中球磨处理1h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料；
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方A，分散工艺简便，并且该配方浆料两个月内沉降量约为1.5％，粘度约为23×103cps。
实施例2
一种用于骨修复生物磷酸钙陶瓷浆料配方B的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：取摩尔比为0.5：1的硝酸钙与磷酸二氢铵，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在硝酸钙溶液中加入直链烷基磺酸钠(直链烷基磺酸钠作为亲水性表面活性剂加入量为磷酸钙盐理论合成量的2.3％)，彻底溶解后；在37℃恒温下缓慢向该溶液中滴加磷酸二氢铵溶液，以转速300r/min搅拌、静置4h、真空抽滤清洗、冷冻干燥、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为8％1,6-己二醇二丙烯酸酯(即活性稀释剂)、0.5％环氧丙烯酸树脂(即低聚物)、0.1％德国毕克BYK-358N(即流平助剂)、0.1％德国毕克BYK-065(即消泡助剂)、0.1％6-三级丁基-4-甲基苯酚(即抗氧化剂)、0.1％二苯基-(2,4,6-三甲基苯甲酰)氧磷(即光引发剂)、0.1％安息香双甲醚(即光引发剂)依次加入37℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为90％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，表面改性的磷酸钙盐粉末中亲水性活性剂含量为2％、磷酸钙盐含量为88％)，每加入一批表面改性的磷酸钙盐粉末后均加入德国毕克BYK-110(即分散剂)，超声搅拌至浆料混合均匀，再继续加入一批次表面改性的磷酸钙盐粉末与德国毕克BYK-110(即分散剂)(分散剂总加入量为1％)，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌4h，再装入盛有氧化锆磨球的不透光罐子中球磨处理1h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料；
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方B，分散工艺简便，并且该配方浆料两个月内沉降量约为0.3％，粘度约为30×103cps。
实施例3
一种用于骨修复生物磷酸钙陶瓷浆料配方C的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：称取摩尔比为1.67：1的氯化钙与磷酸氢二铵，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在氯化钙溶液中加入脂肪酸甲酯磺酸钠(脂肪酸甲酯磺酸钠作为亲水性表面活性剂的加入量为磷酸钙盐理论合成量的4.2％)，彻底溶解后；在60℃恒温下缓慢向该溶液中滴加磷酸氢二铵溶液，以转速600r/min搅拌、静置24h、真空抽滤清洗、冷冻干燥、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为29％三羟甲基丙烷三丙烯酸酯(即活性稀释剂)、0.16％聚醚改性聚二甲基硅氧烷(即流平助剂)、0.1％德国毕克BYK-A530(即消泡助剂)、0.04％四(β-(3，5-三级丁基-4-羟基苯基)丙酸)季戊四醇酯(即抗氧化剂)、0.4％1-羟基环己基苯基甲酮(即光引发剂)依次加入60℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为70％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，上述表面改性的磷酸钙盐粉末中亲水性活性剂含量为2.8％、磷酸钙盐含量为67.2％)，每加入一批次表面改性的磷酸钙盐粉末后均加入聚磷酸钠(即分散剂)，超声搅拌至浆料混合均匀，再继续加入一批次表面改性的磷酸钙盐粉末与聚磷酸钠(即分散剂)(分散剂总加入量为0.3％)，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌6h，再装入盛有氧化锆磨球的不透光罐子中球磨处理3h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料；
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方C，分散工艺简便，并且该配方浆料两个月内沉降量约为0.5％，粘度约为30×103cps。
实施例4
一种用于骨修复生物磷酸钙陶瓷浆料配方D的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：称取摩尔比为1：1的碳酸氢钙与磷酸二氢钠，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在碳酸氢钙溶液中加入Α-烯基磺酸钠(Α-烯基磺酸钠作为亲水性表面活性剂加入量为磷酸钙盐理论合成量的5.3％)，彻底溶解后；在50℃恒温下缓慢向该溶液中滴加磷酸二氢钠溶液，以转速400r/min搅拌、静置18h、真空抽滤清洗、冷冻干燥、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为10％聚乙二醇(400)二丙烯酸酯(即活性稀释剂)、3％聚氨酯丙烯酸树脂(即低聚物)、2％聚醚改性硅油(即流平助剂)、0.6％德国毕克BYK-088(即消泡助剂)、0.4％双(3，5-三级丁基-4-羟基苯基)硫醚(即抗氧化剂)、1％三苯基六氟锑酸盐(即光引发剂)依次加入40℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为80％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，上述表面改性的磷酸钙盐粉末中亲水性活性剂含量为4％、磷酸钙盐含量为76％)，每加入一批次表面改性的磷酸钙盐粉末后均加入十二烷硫酸钠(即分散剂)，超声搅拌至浆料混合均匀，再继续加入一批次表面改性的磷酸钙盐粉末与十二烷硫酸钠(即分散剂)(分散剂总加入量为3％)，以此进行，待直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌3h，再装入盛有氧化锆磨球的不透光罐子中球磨处理2h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料；
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方D，分散工艺简便，并且该配方浆料两个月内沉降量约为0.6％，粘度约为27×103cps。
实施例5
一种用于骨修复生物磷酸钙陶瓷浆料配方E的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：称取摩尔比为0.8：1的硝酸钙与磷酸氢二钠，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在硝酸钙溶液中加入脂肪醇聚氧乙烯醚硫酸钠(脂肪醇聚氧乙烯醚硫酸钠作为亲水性表面活性剂加入量为磷酸钙盐理论合成量的5.4％)，彻底溶解后，在40℃恒温下缓慢向该溶液中滴加磷酸氢二钠溶液，以转速450r/min搅拌、静置10h、真空抽滤清洗、80℃烘干、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为20％新戊二醇二丙烯酸酯(即活性稀释剂)、8％1,6-己二醇二丙烯酸酯(即活性稀释剂)、4％聚酯丙烯酸树脂(即低聚物)、0.5％德国毕克BYK-333(即流平助剂)、1.6％德国毕克BYK-088(即消泡助剂)、0.4％四(β-(3，5-三级丁基-4-羟基苯基)丙酸)季戊四醇酯(即抗氧化剂)、2％苯基双(2,4,6-三甲基苯甲酰基)氧化膦(即光引发剂)、1.5％二苯甲酮(即光引发剂)依次加入50℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为59％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，表面改性的磷酸钙盐粉末中亲水性活性剂含量为3％、磷酸钙盐含量为56％)，每加入一批表面改性的磷酸钙盐粉末后均加入十二烷硫酸钠(即分散剂)，超声搅拌至浆料混合均匀，再继续加入一批次表面改性的磷酸钙盐粉末与十二烷硫酸钠(即分散剂)(分散剂总加入量为2％)，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌4h，再装入盛有氧化锆磨球的不透光罐子中球磨处理1h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料；
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方E，分散工艺简便，并且该配方浆料两个月内沉降量约为1.5％，粘度约为21×103cps。
实施例6
一种用于骨修复生物磷酸钙陶瓷浆料配方F的具体制备过程：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：称取摩尔比为1.5：1的碳酸氢钙与磷酸氢二钠，分别溶入去离子水中，得到硝酸钙溶液与磷酸二氢铵溶液；
步骤1.2：在碳酸氢钙溶液中加入N-甲基酰胺羧酸钠(N-甲基酰胺羧酸钠作为亲水性表面活性剂加入量为磷酸钙盐理论合成量的4％)，彻底溶解后；在50℃恒温下缓慢向该溶液中滴加磷酸氢二钠溶液，以转速550r/min搅拌、静置15h、真空抽滤清洗、37℃烘干、研磨，制得表面改性的磷酸钙盐粉末，备用；
步骤2：预混液制备
将重量比为5％二缩三丙二醇二丙烯酸酯(即活性稀释剂)、7％二丙二醇类二丙烯酸酯(即活性稀释剂)、2％聚氨酯丙烯酸树脂(即低聚物)、0.18％德国毕克BYK-358N(即流平助剂)、0.52％德国毕克BYK-065(即消泡助剂)、0.3％6-三级丁基-4-甲基苯酚(即抗氧化剂)、3％安息香双甲醚(即光引发剂)、1％苯基双(2,4,6-三甲基苯甲酰基)氧化膦(即光引发剂)依次加入55℃的水浴锅中混合搅拌(上述加入过程必须是等待前一个成分完全溶解以后再加入后一个成分)，得预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1中制得的重量比为78％表面改性的磷酸钙盐粉末分批次加入上述预混液中(其中，上述表面改性的磷酸钙盐粉末中亲水性活性剂含量为3％、磷酸钙盐含量为75％)，每加入一批次表面改性的磷酸钙盐粉末后均加入三乙基己基磷酸(即分散剂)，超声搅拌至浆料混合均匀，再继续加入一批次表面改性的磷酸钙盐粉末与三乙基己基磷酸(即分散剂)(分散剂总加入量为3％)，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分超声搅拌5h，再装入盛有氧化锆磨球的不透光罐子中球磨处理2h，消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料。
本实施例制备的用于骨修复生物磷酸钙陶瓷浆料的配方F，分散工艺简便，并且该配方浆料两个月内沉降量约为1％，粘度约为26×103cps。
Claims (10)
1.一种用于骨修复生物磷酸钙陶瓷浆料，其特征在于，其组成成分按照重量百分比划分，由56～88％磷酸钙盐、2～4％亲水性表面活性剂、8～35％活性稀释剂、0～8％低聚物、0.2～4％分散剂、0.1～4％光引发剂、0.1～2％流平助剂、0.1～2％消泡助剂以及0.04～0.4％抗氧化剂组成。
2.根据权利要求1所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述磷酸钙陶瓷浆料由75％磷酸钙盐、3％亲水性表面活性剂、11％活性稀释剂、1％低聚物、4％分散剂、3％光引发剂、1.5％流平助剂、1％消泡助剂以及0.5％抗氧化剂组成。
3.根据权利要求1或2所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述磷酸钙盐为羟基磷灰石或无定型磷酸钙或一水磷酸氢钙或二水磷酸氢钙或无水磷酸氢钙或磷酸八钙。
4.根据权利要求1或2所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述亲水性表面活性剂为直链烷基磺酸钠或脂肪酸甲酯磺酸钠或Α-烯基磺酸钠或脂肪醇聚氧乙烯醚硫酸钠或N-甲基酰胺羧酸钠。
5.根据权利要求1或2所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述活性稀释剂为1,6-己二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、二缩三丙二醇二丙烯酸酯、聚乙二醇(200)二丙烯酸酯、聚乙二醇(400)二丙烯酸酯、聚乙二醇(600)二丙烯酸酯、二丙二醇类二丙烯酸酯、新戊二醇二丙烯酸酯中的一种或多种组合。
6.根据权利要求1或2所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述低聚物为环氧丙烯酸树脂、聚氨酯丙烯酸树脂或聚酯丙烯酸酯。
7.根据权利要求1或2所述的用于骨修复生物磷酸钙陶瓷浆料，其特征在于：所述分散剂为德国毕克BYK-110、聚磷酸钠、聚丙烯酸铵、聚丙烯酸钠、三乙基己基磷酸、十二烷硫酸钠、脂肪酸聚乙二醇酯、六偏磷酸钠中的一种或多种组合；
所述光引发剂为安息香双甲醚、异丙基硫杂蒽酮、二苯甲酮、三苯基六氟锑酸盐、二苯基-(2,4,6-三甲基苯甲酰)氧磷、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、1-羟基环己基苯基甲酮中的一种或多种组合；
所述抗氧化剂为6-三级丁基-4-甲基苯酚、双(3，5-三级丁基-4-羟基苯基)硫醚或四(β-(3，5-三级丁基-4-羟基苯基)丙酸)季戊四醇酯；
所述流平助剂为德国毕克BYK-358N、德国毕克BYK-333、聚醚改性聚二甲基硅氧烷(AKN-1131)或聚醚改性硅油(AKN-114)；
所述消泡助剂为德国毕克BYK-A530、德国毕克BYK-065或德国毕克BYK-088。
8.一种制备如权利要求1所述的用于骨修复生物磷酸钙陶瓷浆料的方法，其特征在于，具体实施步骤如下：
步骤1：制备表面改性的磷酸钙盐
步骤1.1：将能溶解性钙盐与能溶解性磷酸盐分别溶入去离子水中，得到钙盐溶液与磷酸盐溶液；
步骤1.2：在钙盐溶液中加入亲水性表面活性剂，彻底溶解后，缓慢向该溶液中滴加磷酸盐溶液，首先在恒温的温度下搅拌、之后静置、最后进行真空抽滤清洗、干燥、研磨，制得表面改性的磷酸钙盐粉末；
步骤2：预混液制备
将活性稀释剂、低聚物、流平助剂、消泡助剂、光引发剂、抗氧化剂依次加入恒定温度的水浴锅中混合搅拌；其中，加入过程必须是等待前一个成分完全溶解以后再加入后一个成分，得到预混液；
步骤3：制备磷酸钙陶瓷浆料
将步骤1获得的表面改性的磷酸钙盐粉末分批次加入所述预混液，每加入一部分磷酸钙盐粉末后加入一部分分散剂，以此进行，直至所有磷酸钙盐粉末全部加完，然后充分进行超声搅拌直至搅拌均匀、再装入盛有氧化锆磨球的不透光罐子中进行球磨、消泡处理，制得用于骨修复生物磷酸钙陶瓷浆料。
9.根据权利要求8所述的制备用于骨修复生物磷酸钙陶瓷浆料的方法，其特征在于：所述步骤1.1中能溶解性钙盐与能溶解性磷酸盐的摩尔比为0.5～1.67：1。
10.根据权利要求8所述的制备用于骨修复生物磷酸钙陶瓷浆料的方法，其特征在于：所述步骤1.2中恒温的温度为37～60℃；搅拌转速为300～600r/min；静置时间为4～24h；干燥方式为冷冻干燥或采用37～80℃鼓风干燥箱干燥；
所述步骤2中的恒定温度为37～60℃；所述步骤3中的超声搅拌时间为4～6h；球磨处理时间为1～3h。
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