CN85101839A - Inorganic-organic filler, its preparation method and the application in polymeric composition thereof - Google Patents
Inorganic-organic filler, its preparation method and the application in polymeric composition thereof Download PDFInfo
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- CN85101839A CN85101839A CN85101839A CN85101839A CN85101839A CN 85101839 A CN85101839 A CN 85101839A CN 85101839 A CN85101839 A CN 85101839A CN 85101839 A CN85101839 A CN 85101839A CN 85101839 A CN85101839 A CN 85101839A
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- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000012766 organic filler Substances 0.000 title claims description 4
- 239000000945 filler Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002444 silanisation Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920006222 acrylic ester polymer Polymers 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 238000001694 spray drying Methods 0.000 claims 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 19
- 235000013312 flour Nutrition 0.000 description 14
- -1 acyloxy silanes Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000005548 dental material Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012764 mineral filler Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NGMNTLCQDNNBNT-UHFFFAOYSA-N C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O NGMNTLCQDNNBNT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- UNBDCVXGGDKSCP-UHFFFAOYSA-N methyl 2-methylidenetetradecanoate Chemical compound CCCCCCCCCCCCC(=C)C(=O)OC UNBDCVXGGDKSCP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Polymerisation Methods In General (AREA)
Abstract
It is 10 to 500 millimicrons inorganic core grains, polyethylene-silane first cladding and poly-(methyl) acrylate second cladding that the filler that polymeric composition is used contains granularity.This filler is used for preparing acrylate tooth moulded product with traditional method.This moulded product is very hard and wear-resisting.
Description
The invention relates to the filler that polymeric composition is used, dental material specifically, this filler is made up of the particle of inorganic core grains, polyvinyl silane first coating layer and poly-(methyl) acrylate second coating layer.
Tie up in the dental material with the polymeric acceptor of Inorganic Fillers Filled and to be widely used.Therefore, the general packing material of using the mineral filler of (methyl) acrylate (making polymerizable binder uses) and particulate as the plastics tooth.
These fillers can be divided into " coarse stuff " and " flour filler " two classes by their granularity.The granularity of " coarse stuff " is about 1 micron to 50 microns, is preferably about 30 microns; The granularity of " flour filler " is about 5 millimicrons to 500 millimicrons.Based on the existing at present report of the dental material of " coarse stuff ", for example United States Patent (USP) 3,066, and 112; United States Patent (USP) 3,926,906; DE-OS(Germany prospectus) 2,357,324; And DE-OS(Germany prospectus) 2,419,887.
DE-OS 2,403, and 211 and DE-OS 2,462,271 disclosed dental materials, it contains thin especially silicon-dioxide as mineral filler, and its granularity is 5 millimicrons to 700 millimicrons.Compare with " coarse stuff product ", the polishing of " flour filler product " is much easier, but its compactedness is lower usually, and this is to some physicals, and for example the shrinkability of polyreaction, thermal expansivity and water-absorbent have adverse influence.And processing performance is poor when making " flour filler " with the polymerizable binder preparation because their binding property is high.People once taked various approach to go to overcome " flour filler " and joined the difficulty of going in the monomeric cement.Possible method is to replace all or part of " flour filler particle " with the polymers fragment that gives that contains " flour filler ".Further improved method is to contain filler and polymers with what " flour filler particle " was incorporated into that (European patent A-001,190) in the bead polymer use shred or pearl, obtain filler content on be limited to 50%(by weight) " flour filler product ".Higher compactedness can and be worn into the particulate method with condensation product by cohesion " flour filler " before using and reach, but this will inevitably incur loss concerning the easiness of the homogeneity of dental material and polishing (PCT/EP80/00135).
Coat " coarse stuff " to reach easily and dental material blended purpose is well-known with organic polymer.Therefore, DE-OS(Germany prospectus) 1,937,871 disclose a kind of finely divided silicon-dioxide or silicate filler, bag one deck vinyl silanes coats one deck acrylate copolymer again as basic unit.And European patent A-0,047,971 discloses the inorganic particle of coating plastic.From Japanese Patent A74-042, as can be known, making the filler that the greasy composition of tooth uses is the glass granules that has coated synthetic polymer in 905.
But these known cladding process can not be used in " flour filler ", because " flour filler " in last handling process, because their granularity is too thin, specific surface area is too big, and condenses easily.This has just equaled to lose the high-performance of " flour filler ".
The purpose of this invention is to provide a kind of filler based on " flour filler " as dental material, the compactedness height of this filler, and make material easily polished, physical strength is also high.
The invention relates to a kind of be core with the inorganics, be the first layer with the polyethylene-silane, be the particulate filler of the second layer with (methyl) acrylate copolymer, it is characterized in that inorganic core is that the particle of 10 to 500 millimicrons high dispersing is formed by granularity.
Filler of the present invention is to be dispersed in the organic solvent by the particle with high fineness, the first step makes this particle silanization with the mixture of vinyl silanes, water and acid earlier, and second step was the particle that clads this silanization by polyreaction with (methyl) acrylate copolymer.
Suitable polymolecularity packing material is the mineral filler of using always, and granularity is the 10-500 millimicron, and 10-100 millimicron particularly is preferably based on aluminum oxide, silicon-dioxide and silicate.Silicon-dioxide and aluminium dioxide preferably obtain with flame hydrolysis, and granularity is that 10 to 40 millimicrons, BET(cloth Shandong Nao E-Ai Meite-Taylor's method is measured) surface-area is 30 to 300 meters
2/ gram is preferably 40 to 200 meters
2/ gram.
Vinyl silanes itself is known in the above-mentioned disclosed publication.The vinyl silanes of using as the first layer has: for example, vinyltriethoxysilane, vinyltrimethoxy silane, r-methacrylic acid oxygen propyl trimethoxy silicane, r-methacrylic acid oxygen propyl group-three (2-methoxyl group)-silane or vinyl three acyloxy silanes.The most handy r-methacrylic acid oxygen propyl trimethoxy silicane.The consumption of silane compound is advisable with 2-40% by the weight of high degree of dispersion filler, and 5-25% is better.
Prepare filler of the present invention, must keep the silanization condition of regulation.In first step of reaction, silane is changed into active state by reacting with water.In this primary reaction, alkoxyl group that reactive behavior is low or acyloxy water are situated between into the high group of reactive behavior.This reaction mixture is instability when storing, thereby at every turn all must existing preparation before carrying out Silanization reaction.Silane-needed time of water generation primary reaction is depended on temperature of reaction, and the time that general provision at room temperature reacts is 15 minutes to 2 hours.If, then can obtain the good especially product of performance with the water and the silane of weight much at one.The optimum response activity of silane appears at initial water/silane two-phase mixture system and has just become monophasic the time.Mineral acid or organic acid all can be used as catalyzer.For example, very suitable with vinylformic acid and methacrylic acid.The consumption of acid by silane weight, is advisable with 0.1 to 5%, and 0.5 to 2% be the best.
Silanization reaction preferably carries out in the presence of inert organic solvents, such a organic solvent, for example, acetone, vinyl acetate, chloroform or methylene dichloride.It is 5-40% particularly in the organic solvent of 15-25% that the polymolecularity granular filling material preferably is dispersed in weight concentration, and by means of high-speed stirring, adds the reactive silane/water mixture that has prepared simultaneously.Silanization reaction can carry out between 0 to 100 ℃, for example carries out under the room temperature.But the raising temperature of reaction is for example carried out this reaction under the boiling point of solvent, then more favourable.
Reaction times was generally several hours.The viscosity of dispersion descends gradually in the Silanization reaction process, therefore can determine the terminal point of reaction by the continuously measured method of viscosity.
(methyl) Acrylic Acid Monomer and initiators for polymerization are added in the dispersion of silanization filler in inert organic solvents, begin to generate the polyreaction of second cladding.Monomer can once all add when the reaction beginning.But it is, then more favourable if in the long time, monomer and polymerization starter metering are added in the reaction mixture in batches.
Suitable (methyl) Acrylic Acid Monomer is single functionality (methyl) acrylate, two-(methyl) acrylate or three-(methyl) acrylate.In concrete enforcement of the present invention, it is two or three (methyl) acrylate that (methyl) acrylate that can add has a part at least, and therefore second cladding is crosslinked.
The example of single (methyl) acrylate energy usefulness is: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) dodecylacrylate, cyclohexyl (methyl) acrylate and dihydro dicyclopentadienyl (methyl) acrylate.
Two (methyl) acrylate can propose following example: ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dimethyltrimethylene glycol two (methyl) acrylate, 1,12-dodecane two (methyl) acrylate, and by the further again derived compounds of dihydroxyphenyl propane, for example 2,2-is two-4(2-hydroxy-3-methyl acryloyl-oxy propyl group)-phenyl-propane (two GMA) and as United States Patent (USP) 3,425,988,3,709,866 and 3, urethanum two (methyl) vinylformic acid that is proposed in 629,187.
Three (methyl) acrylate available example has: glycerol three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and tetramethylolmethane three (methyl) acrylate.
The meaning of the such word of (methyl) acrylate be meant methacrylic ester and acrylate the two.Concerning preparing granular filling material of the present invention, preferably use methacrylic ester.Except (methyl) acrylate, also available as many as 20% is by other vinyl or the di-vinyl monomers of (methyl) acrylate gross weight, this monomer for example, vinylbenzene, alpha-methyl styrene, vinyl cyanide, or vinyl acetate.The consumption of (methyl) acrylate monomer is advisable with 3-100% by polymolecularity granular filling material weight, and 10-50% is better.(methyl) acrylate monomer is that the service requirements of the granular filling material according to the present invention is selected for use.Therefore, in order to reach enough tolerances, for being used on the tooth of being made by poly methyl methacrylate plastic, advantageous method is to make at least a portion methyl methacrylate carry out copolymerization on second cladding.
The solvent of generation radical commonly used can be used for initiated polymerization, can enumerate superoxide and even oxygen compound is example, and they are as dibenzoyl peroxide, dilauroyl peroxide, cyclohexyl SPC-D and even cyanogen isobutyl dintrile.Initiator mixture with different decomposition temperature also is suitable for polyreaction especially.Polyreaction and is carried out adding to depress when being heated to the decomposition of initiator temperature.For example depress and carry out at the nitrogen of 2 to 6 crust.The most handy high speed agitator stirred reaction mixture in the polymerization process.
Solvent evaporated can obtain filler of the present invention from the polymeric dispersion.Also can flocculate polymkeric substance out, for example add the methyl alcohol flocculation, then it be leached.Especially advantageously adopt spray-dired method, this method can obtain the free-pouring product of particulate.
Filler of the present invention, especially isolated filler helps using in polymeric composition with spraying drying, particularly uses in preparation plastics tooth.This filler is easy to wetting and disperses, and can be added in the monomeric cement with high filling ratio and go.The moulded products that contains filler of the present invention, for example artificial tooth or dental filling putty, with high mechanical strength, particularly high-wearing feature is famous.
The content of polymerisable monomer is 20 to 65% by weight in the polymeric composition of the present invention, preferably 20 to 50%, particularly 25 to 45%.Filler content of the present invention is 10 to 75% by weight, preferably 20 to 75%, particularly 30 to 70%.In addition, also suitably contain inorganic or organic filler, initiators for polymerization, inhibitor, tinting material and other additive, these itself all are known substances.If the consumption of polyfunctionality monomer (linking agent) is big,, in order to reduce fragility, adds softening agent in the composition and be good in of the present invention gathering for some predetermined purposes.Those known high molecular weight plasticizers, particularly those softening agent based on polyurethane, polycarbonate, polyester and polyethers are all suitable especially.German patent application book P3316851,2 polyester of being addressed and polyester-carbonic ether are best softening agent.The example of polymerisable monomer and polymerization starter is the compound that the preparation of second cladding of above-mentioned and filler interrelates.Can gather the dental articles that composition is particularly useful for making shaping, also be suitable for as rigidity cement and other orthopedic surface.
Example 1
(about 20 millimicrons of granularity, the BET surface-area is 50 meters with 19.8 kilograms of methylene dichloride and 3.8 kilograms of polymolecularity silicon-dioxide
2/ gram) weighing joins 40 liter bands and stirs in the autoclave that can heat, and stirring velocity is adjusted to 400 rev/mins.760 gram r-methacrylic oxygen propyl trimethoxy silicanes, 980 gram deionized waters and 10.4 gram methacrylic acids are mixed in a separatory Glass Containers.That this mixed system one becomes is single-phase (under the room temperature after about 40 minutes) is added to its part in the autoclave of stirring immediately.Temperature remains on 40 ℃ in the still, reacted 20 hours, add 0.38 kilogram of methyl methacrylate, 0.38 kilogram of Propenoic acid, 2-methyl, isobutyl ester, 8 gram EDMA ethylene dimethacrylates and 20 gram azo isobutyl dintrile then, adopting pressure is the nitrogen of 5 crust, temperature remain on 70 ℃ 3 hours, then 80 ℃ 3 hours again.Cooling.With carrying out spraying drying after 10 kilograms of these dispersions of methylene dichloride elution.Obtain 5.1 kilograms particulate filler.
Example 2
By following consumption repeat 1: 19.8 kilogram of methylene dichloride of example, (about 20 millimicrons of granularity, the BET surface-area is 50 meters to 3.8 kilograms of polymolecularity silicon-dioxide
2/ gram), 456 gram r-methacrylic oxygen propyl trimethoxy silicanes, 588 gram deionized waters, 6 gram methacrylic acids, 550 gram methyl methacrylates, 11 gram EDMA ethylene dimethacrylates and the even helium isobutyl dintrile of 20 grams.Obtain 4.8 kilograms of particulate fillers.
Example 3
The common pigments of the particulate fillers of 65 gram dihydroxyphenyl propane diepoxy propyl-dimethyl acrylate, 35 gram triethylene glycol dimethacrylates, 318 gram examples 1,2 gram dibenzoyl peroxide and a small amount of (＜0.1 gram) is kneaded form slurry when doing tooth in kneading machine, this slurry is pressed into mould, hardened 6 minutes down at 30 ℃.The tooth of making like this has the high and high outstanding advantage of wear resistance of hardness.
Example 4
With the polyester of 75 gram methyl methacrylates, 20 gram EDMA ethylene dimethacrylates, 5 gram carbonate-containing bases (DE-OS2, the example 3 in 732,718), 20 gram benzoyl peroxides, 30 gram polymethylmethacrylate bead polymer (d
50Be 45 microns, (η) in the trichloromethane is 1.8 liters/gram) and 220 restrain the particulate filler derive from example 2 and be placed on the pulp composition of kneading in the kneading machine.Activate this composition with 2 gram dibenzoyl peroxide, into the color of tooth with pigment commonly used.After the slaking in 30 minutes, said composition is pressed into the tooth mould, hardened 8 minutes down at 120 ℃.The gained tooth has hard and excellent properties highly abrasion-resistant.
Errata
CPCH856162
Claims (10)
1, the filler used of polymeric composition is made up of inorganics core, polyvinyl silane first cladding and poly-(methyl) acrylate second cladding, it is characterized in that the inorganics core is made up of by 10 to 500 millimicrons particle granularity.
2, the filler of claim 1 is characterized in that, the weight of first cladding accounts for 2-40%, and preferably 5-25%(is a benchmark with the weight of inorganics core).
3, claim 1 or 2 filler is characterized in that the weight of second cladding accounts for 3-100%, and preferably 10-50%(is a benchmark with the weight of inorganics core).
4, the filler of claim 1 to 3 is characterized in that, the inorganics core is made up of silicon-dioxide, silicate or aluminum oxide.
5, the filler of claim 4 is characterized in that, the inorganics core is silicon-dioxide or aluminum oxide, and granularity is 10 to 40 millimicrons, is with flame-hydrolytically produced.
6, the filler of claim 1 to 5 is characterized in that, the BET surface-area of inorganics core is 30 to 300 meters
2/ gram, preferably 40 to 200 meters
2/ gram.
7, the filler of claim 1 to 6 is characterized in that, second cladding is crosslinked.
8, the filler preparation method of claim 1 to 7, it is characterized in that, with granularity is that 10 to 500 millimicrons inorganics pellet is dispersed in the organic solvent, with the reaction mixture silanization of vinyl silanes and water, by polyreaction with (methyl) acrylic ester polymer wrap the product of silanization earlier by second step for the first step.
9, the method for claim 8 is characterized in that, filler is to separate from solvent with spray drying process.
10, polymeric composition, contain 20 to 65% by weight polymerization single polymerization monomer, 10 to 75% by weight inorganic-organic filler and suitable additives known, it is characterized in that at least a portion filler is the filler of claim 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101839A CN85101839B (en) | 1985-04-01 | 1985-04-01 | Organic-inorganic filler, its preparation and use in polymer composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101839A CN85101839B (en) | 1985-04-01 | 1985-04-01 | Organic-inorganic filler, its preparation and use in polymer composites |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101839A true CN85101839A (en) | 1987-01-10 |
| CN85101839B CN85101839B (en) | 1988-07-13 |
Family
ID=4792093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101839A Expired CN85101839B (en) | 1985-04-01 | 1985-04-01 | Organic-inorganic filler, its preparation and use in polymer composites |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85101839B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597360B (en) * | 2009-07-10 | 2010-10-20 | 王猛 | Method for preparing gas barrier material by sol-gel method |
| CN103273713A (en) * | 2013-06-13 | 2013-09-04 | 日照沪鸽齿科工业有限公司 | Four-layer-color synthetic resin block and preparation method thereof |
| CN103998008A (en) * | 2011-12-15 | 2014-08-20 | 登特斯普伊德特雷有限公司 | Composite filler particles and process for the preparation thereof |
| CN105860364A (en) * | 2016-05-25 | 2016-08-17 | 青海大学 | Surface treatment method for novel crystal whiskers applied to PVC |
| CN109281172A (en) * | 2018-08-15 | 2019-01-29 | 浙江理工大学 | Hud typed free-floride water-proof aagent and its preparation method and application |
-
1985
- 1985-04-01 CN CN85101839A patent/CN85101839B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101597360B (en) * | 2009-07-10 | 2010-10-20 | 王猛 | Method for preparing gas barrier material by sol-gel method |
| CN103998008A (en) * | 2011-12-15 | 2014-08-20 | 登特斯普伊德特雷有限公司 | Composite filler particles and process for the preparation thereof |
| CN103998008B (en) * | 2011-12-15 | 2017-08-18 | 登特斯普伊德特雷有限公司 | Compounded mix particle and preparation method thereof |
| CN103273713A (en) * | 2013-06-13 | 2013-09-04 | 日照沪鸽齿科工业有限公司 | Four-layer-color synthetic resin block and preparation method thereof |
| CN103273713B (en) * | 2013-06-13 | 2015-12-09 | 山东沪鸽口腔材料股份有限公司 | Four layers of look synthetic resin block and preparation method thereof |
| CN105860364A (en) * | 2016-05-25 | 2016-08-17 | 青海大学 | Surface treatment method for novel crystal whiskers applied to PVC |
| CN109281172A (en) * | 2018-08-15 | 2019-01-29 | 浙江理工大学 | Hud typed free-floride water-proof aagent and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101839B (en) | 1988-07-13 |
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