CN105315478A - Copolymer using nano calcium phosphate coated polymethyl methacrylate as substrate and coating method thereof - Google Patents
Copolymer using nano calcium phosphate coated polymethyl methacrylate as substrate and coating method thereof Download PDFInfo
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- CN105315478A CN105315478A CN201510751166.1A CN201510751166A CN105315478A CN 105315478 A CN105315478 A CN 105315478A CN 201510751166 A CN201510751166 A CN 201510751166A CN 105315478 A CN105315478 A CN 105315478A
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Abstract
The present invention relates to a copolymer using nano calcium phosphate coated polymethyl methacrylate (PMMA) as a substrate and a coating method thereof. The method comprises compounding copolymer microspheres using PMMA including a hydroxyl pendant group as a substrate, reacting calcium salt and phosphoric acid solution with the hydroxyl pendant group of the PMMA-based copolymer microspheres, and increasing the thickness of nano calcium phosphate coatings of the PMMA-based copolymer microspheres.
Description
the cross reference of related application
It is No.US62/123 that application claims enjoys sequence number, 108, the applying date is on November 5th, 2014, is entitled as rights and interests and the benefit of the U.S. Provisional Patent Application of " multipolymer that the polymethylmethacrylate (polymethylmethacrylate; PMMA) that nano-calcium phosphate applies is substrate ", this U.S. Provisional Patent Application quotes in full at this, for reference.
Technical field
The present invention relates to and there is the multipolymer that bioactive polymethylmethacrylate (PMMA) is substrate, the preparation technology of this multipolymer, and as the purposes of bioactive filler in orthopaedics application, dental applications, polymer application and Chemical activator.
Background technology
Bone filler is that a kind of being used for is filled or the material of alternative bone/tooth.Acrylic resin bone cement to may be injected in human body and hardens in human body, and wherein adopt the acrylic resin bone cement of PMMA to be solid phase, the acrylic resin bone cement adopting methyl methacrylate monomer is liquid phase.Acrylic resin bone cement has widespread use in arthroplasty and vertebroplasty.
PMMA self is biologically inert, and cannot be attached on bone.Alternately, such as can add calcium phosphate (CaP) for PMMA provides biological activity.CaP is the mineral race containing calcium ion and phosphate anion.CaP has biocompatibility and biodegradability, and it is the main mineral composition of bone.CaP has shown and can improve synosteosis, cell adhesion and New born formation.
Summary of the invention
The present invention can provide the method be coated to by nano-calcium phosphate on copolymer microsphere that polymethylmethacrylate (PMMA) is substrate.Due to PMMA be substrate multipolymer on there is pendant hydroxyl groups, calcium phosphate accumulates formation by chemical reaction in time on multipolymer.
An aspect wherein, provides that a kind of to adopt nano-calcium phosphate to apply PMMA be the method for the copolymer microsphere of substrate.The method can comprise: synthesis is the copolymer microsphere of substrate containing the PMMA of multiple pendant hydroxyl groups, make calcium salt and phosphoric acid solution and PMMA be substrate copolymer microsphere on pendant hydroxyl groups react, and make PMMA be substrate copolymer microsphere on nano-calcium phosphate applicator thicken.
On the other hand, provide nano particle, its PMMA including nano-calcium phosphate coating is the copolymer microsphere of substrate.The diameter of this nano particle is about 10nm-1000nm.This nano particle can be used for bone cement, bone filler or tooth and fills.
On the other hand, provide micron particle, its PMMA including calcium phosphate coating is the copolymer microsphere of substrate.The diameter of this micron particle is about 1 μm-100 μm.This micron particle can be used for bone cement, bone filler or tooth and fills.
The copolymer microsphere that the PMMA that nano-calcium phosphate applies is substrate can be used as bone cement provides bioactive main component.Advantage of the present invention comprises: be directly chemically bonded to by bioactive calcium phosphate on the copolymer microsphere that PMMA is substrate, in the scope from nano-scale to submicron-scale, control coating thickness, and the further polymerization of the copolymer microsphere that nano-calcium phosphate is applied becomes possibility.
Accompanying drawing explanation
Can understand the detailed description to each embodiment in the following disclosure better in conjunction with accompanying drawing of the present invention, in accompanying drawing, the identical label of same structure represents.In accompanying drawing:
Fig. 1 to show in the present invention coated with nano calcium phosphate on the copolymer microsphere that PMMA is substrate;
The SEM image of Fig. 2 to be PMMA be microballoon (P) of substrate;
The SEM image of Fig. 3 to be PMMA be microballoon (PH-1) of substrate;
The SEM image of Fig. 4 to be PMMA be microballoon (PH-0.5) of substrate;
Fig. 5 is the PMMA of nano-calcium phosphate coating is that the microballoon (PH-0.5) of substrate is at the SEM image of mixing after 1 day;
Fig. 6 is the PMMA of nano-calcium phosphate coating is that the microballoon (PH-0.5) of substrate is at the SEM image of mixing after 2 days;
Fig. 7 is the PMMA of nano-calcium phosphate coating is that the microballoon (PH-0.5) of substrate is at the SEM image of mixing after 3 days;
The EDX that Fig. 8 shows the PMMA of the nano-calcium phosphate coating of mixing in Fig. 5 after 1 day is the microballoon of substrate analyzes;
The EDX that Fig. 9 shows the PMMA of the nano-calcium phosphate coating of mixing in Fig. 6 after 2 days is the microballoon of substrate analyzes;
The EDX that Figure 10 shows the PMMA of the nano-calcium phosphate coating of mixing in Fig. 7 after 3 days is the microballoon of substrate analyzes;
Figure 11 shows the solidifiability (settingproperties) of bioactive bone cement;
Figure 12 is the SEM image that bioactive bone cement immerses in DMEM after three days; And
The EDX that Figure 13 shows immersing the apatite layer of DMEM after tri-days analyzes.
Embodiment
The present invention can provide the method be coated to by nano-calcium phosphate with on polymethylmethacrylate (PMMA) copolymer microsphere that is substrate, thus is formed and have the multipolymer that bioactive PMMA is substrate.Due to PMMA be substrate multipolymer on there is pendant hydroxyl groups, form the calcium phosphate accumulated in time by chemical reaction.The copolymer microsphere that the PMMA that nano-calcium phosphate applies is substrate can be used as bone cement provides bioactive main component.
Fig. 1 shows the embodiment of coating method of the present invention.The method can comprise: the PMMA of synthesis hydroxyl side base is the copolymer microsphere of substrate, make calcium salt and phosphoric acid solution and PMMA be substrate copolymer microsphere on pendant hydroxyl groups react, to form nano-calcium phosphate, and make PMMA be substrate copolymer microsphere on nano-calcium phosphate applicator thicken.
PMMA by letex polymerization effect synthesis hydroxyl side base is the copolymer microsphere of substrate.Letex polymerization effect is a kind of radical polymerization effect started with the emulsion incorporating water, monomer and tensio-active agent.Monomer can be any compound containing the one or more methacrylate functional monomer of substrate (also can be called to be methacrylic ester be).Monomer can be selected from but be not limited to next group compound: methyl methacrylate (MMA), 2-hydroxy ethyl methacrylate (HEMA), 3 acrylic acid-2-hydroxy propyl ester, allyl methacrylate(AMA), 2-[3-(2H-benzotriazole-2-base)-4-hydroxyphenyl] β-dimethyl-aminoethylmethacrylate, butyl methacrylate, 3-chlorine-2-hydroxyl propyl methacrylate, β-dimethyl-aminoethylmethacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, methacrylate, hydroxy ethyl methacrylate, hydroxy methyl methacrylate, Rocryl 410, 2-hydroxyl-3-{3-[2, 4, 6,8-tetramethyl--4,6, 8-tri-(propyl glycidyl ether)-2-cyclotetrasiloxane] propoxy-} propyl acrylate (2-hydroxy-3-{3-[2, 4,6,8-tetramethyl-4, 6,8-tris (propylglycidylether)-2-cyclotetrasiloxanyl] propoxy}propylmethacrylate), 2-methoxymethyl ethyl propenoate, and triethylene glycol dimethacrylate.Potassium persulphate can be used to start polymerization.In aqueous, potassium persulphate decomposes to provide free radical.Methyl methacrylate and other methacrylic esters are the monomer generation Raolical polymerizable of substrate, thus generation PMMA is the copolymer microsphere of substrate.
PMMA is that the copolymer microsphere of substrate should comprise pendant hydroxyl groups, to react with calcium salt and phosphoric acid solution.Correspondingly, at least some monomer used in letex polymerization mechanism should have oh group.The such calcium phosphate of hydroxylapatite is formed by Wet Method Reaction method based on following stoichiometric equation:
10Ca(OH)
2+6H
3PO
4→Ca
10(PO
4)
6(OH)
2+18H
2O。
In calcium hydroxide and phosphatase reaction process, the pendant hydroxyl groups on the microballoon that PMMA is substrate can provide alternative Ca
10(PO
4)
6(OH)
2the site of upper hydroxy functional group.PMMA be substrate copolymer microsphere on the alternative calcium phosphate forming process of pendant hydroxyl groups in oh group.Calcium ion and the sustainable PMMA of being accumulated in of phosphate anion are on the pendant hydroxyl groups of the copolymer microsphere of substrate.The copolymer microsphere being finally substrate at PMMA forms nano-calcium phosphate applicator, and wherein nano-calcium phosphate applicator is by Chemical bond effect, is attached on copolymer microsphere that PMMA is substrate.
In the present invention, nano-calcium phosphate by with PMMA be substrate copolymer microsphere on pendant hydroxyl groups generation chemical reaction formed.The diameter of nano-calcium phosphate is about 10nm-1000nm.The PMMA that nano-calcium phosphate applies is the copolymer microsphere of substrate can be the nano particle that diameter is about 10nm-1000nm.Nano-calcium phosphate applicator can be accumulated in time, and can form micron particle subsequently.The PMMA including nano-calcium phosphate coating is the diameter that the micron particle of the copolymer microsphere of substrate can have about 1 μm-100 μm.
The copolymer microsphere that the PMMA that nano-calcium phosphate applies is substrate can be used as bone cement provides bioactive main component, and the copolymer microsphere that the PMMA of nano-calcium phosphate coating is substrate can be polymerized further.Figure 10 and Figure 11 shows the evidence that bone cement small pieces (pellet) can be formed with phosphatic rock, shows that this material has biological activity; Described bone cement small pieces use the copolymer microsphere that the PMMA of nano-calcium phosphate coating is substrate to prepare.The PMMA that nano-calcium phosphate applies is that the copolymer microsphere of substrate can be used for orthopaedics application, dental applications, polymer application and Chemical activator.
Below with reference to various example and be described in detail with reference to the attached drawings the present invention.
Example 1, the PMMA of synthesis hydroxyl side base is the copolymer microsphere of substrate
The PMMA being contained one or more pendant hydroxyl groups by letex polymerization effect synthesis is the copolymer microsphere of substrate.In general, mix multiple monomer (methyl methacrylate or other there is the methacrylate monomer of pendant hydroxyl groups (such as, 2-hydroxy ethyl methacrylate)), distilled water and potassium persulphate, and to heat 3 hours in nitrogen atmosphere at 80 DEG C.Then, this mixture centrifugal and cleaning with distilled water.Use the microballoon that lyophilizer this PMMA dry is substrate.
The PMMA summarizing synthesis in table 1 is the type of the microballoon of substrate.
Scanning electronic microscope (scanningelectronmicroscopy, SEM) is used to characterize the microballoon (P, PH-1 and PH-0.5) that PMMA is substrate.Fig. 2-4 shows the SEM image that PMMA is the microballoon of substrate.
Example 2, PMMA is the nano-calcium phosphate applicator on the copolymer microsphere of substrate
Be microballoon (PH-0.5) and the calcium hydroxide of substrate with distilled water mixing PMMA in beaker.Syringe pump is used dropwise in reaction mixture, to add phosphoric acid with the speed of 0.139ml/hr.After with the addition of all phosphoric acid, reaction mixture is mixed 1,2 and 3 day respectively.After the mixing is complete, centrifugal and freeze drying mixt.
The PMMA being observed nano-calcium phosphate coating by scanning electronic microscope (SEM) is the copolymer microsphere of substrate, and by energy dispersion X-ray (energydispersiveX-ray, EDX) analyze nano-calcium phosphate coating PMMA be the copolymer microsphere of substrate.The PMMA of nano-calcium phosphate coating is that the microballoon of substrate is fixed on silicon chip, and is coated with carbon and observes for SEM.Fig. 5-7 respectively illustrates the SEM image of reaction product mixing after 1,2 and 3 day.Nano-calcium phosphate applicator is thickened along with mixing period prolongation.As seen in figs. 8-10, carry out energy dispersion X-ray (EDX) analysis to the sample that the PMMA of the nano-calcium phosphate coating of 1 day, 2 days and 3 days is the microballoon of substrate, this analysis shows exists Ca2+ oscillations and phosphorus signal.Therefore confirm to there is calcium and phosphorus on the microballoon that PMMA is substrate.
Formed by phosphatic rock and test the biological activity that the PMMA confirming nano-calcium phosphate coating is the copolymer microsphere of substrate., first determine the Solidification Parameters (settingparameter) of bioactive bone cement herein, the PMMA that described bioactive bone cement is applied by nano-calcium phosphate is that the copolymer microsphere of substrate is formed.Copolymer microsphere, 36g methyl methacrylate monomer, 1.04g benzoyl peroxide and 1.30gN, the N-dimethyl-p-toluidine that the PMMA of 36g nano-calcium phosphate coating is substrate is used to form bioactive bone cement.And some other formulas can be used to obtain bioactive bone cement, and the PMMA that this bioactive bone cement comprises nano-calcium phosphate coating is the copolymer microsphere of substrate, to obtain the different solidifiabilities of the bioactive bone cement corresponding to special formulation.
All compounds mix in beaker, the amount temperature of use temperature measurement subsequently.What Figure 11 showed bioactive bone cement solidifies figure, and wherein found that bioactive bone cement 17 minutes time, start to solidify after being mixed with all compounds, the top temperature measured is 54 DEG C, and this temperature is lower than commercially available PMMA bone cement.
These compounds also solidify in a mold, form small pieces (diameter: 9.5mm; Highly: 5mm).Take out bone cement after solidification.The capacity be kept at by small pieces (n=6) containing 10ml Du Shi improved culture medium (Dulbecco ' sModifiedEagle ' sMedium, DMEM) is in 20ml bottle.Bottle to be kept in 37 DEG C of water-baths 3 days.Small pieces are taken out, with dry in atmosphere after distilled water cleaning after 3 days.The pure PMMA small pieces prepared by the microballoon (P) with aforementioned PMMA being substrate are when comparing.Use the bioactive bone cement small pieces of sem observation.SEM image has been shown in Figure 12.On bioactive bone cement, define apatite layer, but do not observe apatite layer on pure PMMA cement.Carry out EDX analysis to apatite layer, this analytical results illustrates in fig. 13.Thus confirm to define phosphatic rock.In PMMA control group, do not observe phosphatic rock, and analyzed by EDX and Ca2+ oscillations and phosphorus signal do not detected.This phosphatic rock can show that PMMA that nano-calcium phosphate applies is that the copolymer microsphere of substrate has biological activity.
Claims (20)
1. bioactive polymethylmethacrylate (PMMA) multipolymer that is substrate, is characterized in that, comprise the copolymer microsphere that PMMA is substrate, and is coated in the nano-calcium phosphate on surface that described PMMA is the copolymer microsphere of substrate.
2. PMMA as claimed in claim 1 is the multipolymer of substrate, and it is characterized in that, described nano-calcium phosphate is coated on the copolymer microsphere that described PMMA is substrate by Chemical bond effect.
3. PMMA as claimed in claim 2 is the multipolymer of substrate, and it is characterized in that, described PMMA is that the copolymer microsphere of substrate comprises multiple pendant hydroxyl groups; By with described PMMA be substrate copolymer microsphere on described multiple pendant hydroxyl groups generation chemical reactions form described nano-calcium phosphate.
4. PMMA as claimed in claim 2 is the multipolymer of substrate, and it is characterized in that, described PMMA is that the copolymer microsphere of substrate comprises multiple pendant hydroxyl groups; One or more one of them hydroxyl serving as described nano-calcium phosphate of described multiple pendant hydroxyl groups, to be attached to described nano-calcium phosphate on the surface of the copolymer microsphere that described PMMA is substrate.
5. PMMA as claimed in claim 1 is the multipolymer of substrate, and it is characterized in that, the monomer being substrate by methacrylic ester by emulsion polymerization prepares the copolymer microsphere that described PMMA is substrate.
6. PMMA as claimed in claim 1 is the multipolymer of substrate, and it is characterized in that, described PMMA is the multipolymer of substrate is the nano particle that diameter is roughly 10-1000nm.
7. PMMA as claimed in claim 1 is the multipolymer of substrate, and it is characterized in that, described PMMA is the multipolymer of substrate is the micron particle that diameter is roughly 1-100 μm.
8. PMMA as claimed in claim 1 is the multipolymer of substrate, and it is characterized in that, the diameter of described nano-calcium phosphate is roughly 10-1000nm.
9. apply a method for the copolymer microsphere that polymethylmethacrylate (PMMA) is substrate with nano-calcium phosphate, it is characterized in that, comprising:
Synthesis is the copolymer microsphere of substrate containing the described PMMA of multiple pendant hydroxyl groups; And
Make calcium salt and phosphoric acid solution and described PMMA be substrate copolymer microsphere on described multiple pendant hydroxyl groups react, form nano-calcium phosphate applicator with on the copolymer microsphere that is substrate at described PMMA.
10. method as claimed in claim 9, is characterized in that, generate by emulsion polymerization the copolymer microsphere that described PMMA is substrate, and the monomer comprising one or more methacrylate functional is for described emulsion polymerization.
11. methods as claimed in claim 10, it is characterized in that, described monomer is selected from but is not limited to next group compound: methyl methacrylate, 2-hydroxy ethyl methacrylate, 3 acrylic acid-2-hydroxy propyl ester, allyl methacrylate(AMA), 2-[3-(2H-benzotriazole-2-base)-4-hydroxyphenyl] β-dimethyl-aminoethylmethacrylate, butyl methacrylate, 3-chlorine-2-hydroxyl propyl methacrylate, β-dimethyl-aminoethylmethacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, methacrylate, hydroxy ethyl methacrylate, hydroxy methyl methacrylate, Rocryl 410, 2-hydroxyl-3-{3-[2, 4, 6, 8-tetramethyl--4, 6, 8-tri-(propyl glycidyl ether)-2-cyclotetrasiloxane] propoxy-} propyl acrylate, 2-methoxymethyl ethyl propenoate, and triethylene glycol dimethacrylate.
12. methods as claimed in claim 9, is characterized in that, at described PMMA be substrate copolymer microsphere on form described nano-calcium phosphate applicator and comprise:
Be the copolymer microsphere of substrate and described calcium salt with PMMA described in a dissolution with solvents, to obtain the first mixture;
Described phosphoric acid solution is added, to obtain reaction mixture in described first mixture; And
Continue the described reaction mixture of mixing, and centrifugal described reaction mixture, to isolate the copolymer microsphere that the described PMMA that is coated with nano-calcium phosphate is substrate from described solvent.
13. methods as claimed in claim 9, it is characterized in that, the diameter of described nano-calcium phosphate is roughly 10-1000nm.
14. methods as claimed in claim 9, is characterized in that, also comprise make described PMMA be substrate copolymer microsphere on described nano-calcium phosphate applicator thicken.
15. 1 kinds of nano particles, is characterized in that, the polymethylmethacrylate comprising nano-calcium phosphate coating is the copolymer microsphere of substrate; Wherein said nano particle adopts method according to claim 9 to obtain, and the diameter of described nano particle is roughly 10-1000nm.
16. 1 kinds of micron particle, is characterized in that, the polymethylmethacrylate comprising nano-calcium phosphate coating is the copolymer microsphere of substrate; Wherein said micron particle adopts method according to claim 9 to obtain, and the diameter of described micron particle is roughly 1-100 μm.
17. 1 kinds of nano particle according to claim 15 application in bone cement, bone filler or tooth are filled, wherein said nano particle provides biological activity.
18. 1 kinds of micron particle according to claim 16 application in bone cement, bone filler or tooth are filled, wherein said micron particle provides biological activity.
19. 1 kinds of polymethylmethacrylates according to claim 1 are the application of multipolymer in bone cement, bone filler or tooth are filled of substrate, and the multipolymer that wherein said polymethylmethacrylate is substrate provides biological activity.
The polymethylmethacrylate of 20. 1 kinds of nano-calcium phosphate coatings is the application of copolymer microsphere in bone cement, bone filler or tooth are filled of substrate, and the copolymer microsphere that the polymethylmethacrylate of described nano-calcium phosphate coating is substrate provides biological activity; Wherein, the polymethylmethacrylate that described nano-calcium phosphate applies is that the copolymer microsphere of substrate is prepared by method according to claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| US201462123108P | 2014-11-07 | 2014-11-07 | |
| US62/123,108 | 2014-11-07 | ||
| US14/933,019 US20160129148A1 (en) | 2014-11-07 | 2015-11-05 | Nano-calcium phosphate-coated polymethylmethacrylate-based co-polymer and coating process of the same |
| US14/933,019 | 2015-11-05 |
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| WO2018019208A1 (en) * | 2016-07-25 | 2018-02-01 | 薪创生命科技有限公司 | Novel formula for synthesizing bone replacement material, and manufacturing method and application method thereof |
| CN110835381A (en) * | 2018-08-15 | 2020-02-25 | 漯河医学高等专科学校 | Composite microsphere with three-layer core-shell structure, preparation method and composite bone cement using composite microsphere |
| CN111467564A (en) * | 2020-03-25 | 2020-07-31 | 西安理工大学 | Self-expansion composite bone cement and preparation method thereof |
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| CN102695751A (en) * | 2009-09-28 | 2012-09-26 | 组织再生医疗公司 | Porous materials coated with calcium phosphate and methods of fabrication thereof |
| CN103467756A (en) * | 2013-09-18 | 2013-12-25 | 中国矿业大学 | Method for preparing chitosan/hydroxyapatite composite microspheres |
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| WO2002092021A1 (en) * | 2001-05-16 | 2002-11-21 | 3M Espe Ag | Self-adhesive dental materials |
| US20030071387A1 (en) * | 2001-10-15 | 2003-04-17 | Beitelshees Carl P. | Continuous method for formation of three dimensional burls in a solid surface material |
| CN101560320A (en) * | 2009-05-14 | 2009-10-21 | 浙江理工大学 | Composite material coating polymer microsphere surface with copper oxide, and preparation method thereof |
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| WO2018019208A1 (en) * | 2016-07-25 | 2018-02-01 | 薪创生命科技有限公司 | Novel formula for synthesizing bone replacement material, and manufacturing method and application method thereof |
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| US11110205B2 (en) | 2016-07-25 | 2021-09-07 | Novus Life Sciences Limited | Formula for synthesizing bone replacement material, and manufacturing method and application method thereof |
| CN110835381A (en) * | 2018-08-15 | 2020-02-25 | 漯河医学高等专科学校 | Composite microsphere with three-layer core-shell structure, preparation method and composite bone cement using composite microsphere |
| CN111467564A (en) * | 2020-03-25 | 2020-07-31 | 西安理工大学 | Self-expansion composite bone cement and preparation method thereof |
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Application publication date: 20160210 |