CN109810440A - Its compound bone cement of a kind of PMMA/SCTP composite micro-powder and preparation method and application - Google Patents
Its compound bone cement of a kind of PMMA/SCTP composite micro-powder and preparation method and application Download PDFInfo
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- CN109810440A CN109810440A CN201711236976.9A CN201711236976A CN109810440A CN 109810440 A CN109810440 A CN 109810440A CN 201711236976 A CN201711236976 A CN 201711236976A CN 109810440 A CN109810440 A CN 109810440A
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Abstract
The present invention relates to a kind of PMMA/SCTP composite micro-powder with core-shell structure, core is methylmethacrylate copolymer (PMMA), and shell is tripolyphosphate calcium sodium (SCTP).The preparation step of the complex microsphere is first to prepare copolymer microsphere, then deposits tripolyphosphate calcium sodium on copolymer microsphere surface under the action of template, coats, obtains PMMA/SCTP composite micro-powder.The composite micro-powder is used to prepare compound bone cement.
Description
Technical field
The present invention relates to a kind of organic/inorganic nano powder with core-shell structure, more particularly to a kind of PMMA/SCTP
The compound bone cement of its preparation of the preparation method and application of composite micro-powder and the composite micro-powder.
Background technique
Bone cement is a kind of for filling bone or implantation spatium interosseum or bone cavity and with the biomaterial of self-solidifying characteristic.Bone water
Mud mainly has polymethyl methacrylate (PMMA) bone cement and two kinds of calcium phosphate bone cement.Wherein, PMMA bone cement is facing
Good application effect is achieved on bed, but PMMA itself is biologically inert, it cannot be in conjunction with bone tissue.On the contrary, calcium phosphate
There is class bone cement biocompatibility, biological degradability can promote synosteosis, cell close to bone tissue in terms of composition
Adherency and new bone formation.
Patent CN1927416 is related to a kind of composite porous calcium phosphate bone cement and preparation method thereof.The bone cement is by phosphoric acid
Calcium bone cement solid phase powder and the 3-hydroxybutyric acid-co-3-hydroxyvaleric acid copolymer (PHBV) handled by 60Co x ray irradiation x
Microballoon and solidify liquid form.Patent CN101716379 be related to include solid phase and liquid phase double-solidified composite calcium phosphate bone cement, Gu
It mutually include calcium phoshate bone cement powder and oxidant;Liquid phase includes deionized water, water soluble crosslinkable polymer, reducing agent.Specially
Sharp CN1821143 provides a kind of preparation method of calcium phosphate cement composite material.(1) calcium phosphate, calcium carbonate and calcium monohydrogen phosphate
Through high temperature solid state reaction synthesis, only the pulvis containing hydroxyapatite and type alpha tricalcium phosphate, powder mix sucrose by weight 2: 1
Crystal mixes, as solid phase;(2) acrylic acid-itaconic acid copolymer fluid is prepared, as liquid phase;(3) solid phase is weighed by weight 3: 1
And die forming is inserted in liquid phase, mixing, mixes human gene recombination in each mold in calcium phosphate bone cement harmonic process
The calcium phosphate bone cement material of compound BMP-2 can be obtained in Bone Morphogenetic Protein-2.
Patent CN105315478 is related to a kind of with nano-calcium phosphate coating polymethyl methacrylate (PMMA) being substrate
Copolymer and its method for coating.Method includes that the PMMA of synthesis hydroxyl side group is the copolymer microsphere of substrate, makes calcium salt and phosphorus
Acid solution is reacted with PMMA for the pendant hydroxyl groups on the copolymer microsphere of substrate, and is made on the polymer microballoon of PMMA substrate
Nano-calcium phosphate applicator thicken.
Summary of the invention
The present invention provides a kind of PMMA/SCTP composite micro-powder, the composite micro-powder has core-shell structure, and the core is first
The copolymer microsphere of base methyl acrylate (MMA) and function monomer, crosslinking agent, the shell is tripolyphosphate calcium sodium (SCTP).
On the other hand, the present invention provides a kind of methods with SCTP cladding PMMA copolymer microsphere.PMMA is synthesized first
Copolymer microsphere, then allows calcium chloride and sodium tripolyphosphate reactant salt, and assembles under the action of template and be coated on PMMA
On copolymer microsphere, PMMA/SCTP composite micro-powder is obtained.
Furthermore the present invention provides a kind of compound bone cements using the PMMA/SCTP composite micro-powder.
A kind of PMMA/SCTP composite micro-powder of the present invention, preparation method includes the following steps:
(1) compound emulsifying agent is prepared, mix monomer, while the potassium peroxydisulfate water that compound concentration is 0.1%~10% are prepared
Solution;
The compound emulsifying agent includes lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, amber
Sour di-isooctyl base sodium sulfonate, OP series emulsifier, Tween series emulsifier, Span series emulsifier, polyvinyl alcohol, carboxylic first
One of base cellulose or any combination;
The mix monomer includes methyl methacrylate, function monomer and crosslinking agent, wherein methyl methacrylate, function
Can monomer, crosslinking agent weight ratio be 1: 0.05~0.2: 0.001~0.1;
The function monomer is hydroxymethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyl butyl propyleneglycol
Acid esters, hydroxymethyl methacrylate, hydroxyethyl meth acrylate, hydroxypropyl methacrylate, hydroxyl butyl methyl propylene
Acid esters, one of or any combination, the crosslinking agent be double methyl methacrylate triethylene glycol ester, the bis- methyl-props of bisphenol-A-
One of olefin(e) acid ethylene oxidic ester;
(2) sequentially added into reaction kettle 100 parts of deionized waters, 0.5 part~10 parts compound emulsifying agents, 6 parts~30 parts it is mixed
Monomer is closed, while heating up and emulsifying, nitrogen filled protection;After being warming up to 80 DEG C, 0.1 part~1 part persulfate aqueous solution, reaction is added
After 15min~60min, 20 parts~90 parts mix monomers at the uniform velocity are added dropwise simultaneously in 2h~3h and 0.1 part~2 parts potassium peroxydisulfates are molten
Liquid;After dripping, continue insulation reaction 2h~3h;It is cooled to room temperature, is repeatedly centrifugated, deionized water flush cycle,
Obtain methylmethacrylate copolymer microballoon;
The diameter of the methylmethacrylate copolymer microballoon is between 0.02 μm~3 μm.
(3) at room temperature, 100 parts of deionized waters, 1 part~20 parts methyl methacrylate copolymers are sequentially added into reaction kettle
Object microballoon, 0.2 part~4 parts templates, stirring is to dissolving, with sodium hydroxide tune pH value to 7.5~8.5;It is water-soluble that calcium chloride is added
Liquid is 2: 1 addition tripolyphosphate sodium water solutions according to the molar ratio of calcium constituent and sodium element, instead after stirring 15min~45min
0.3h~2h is answered, 1h~2h, filtering are aged, ethanol washing is lyophilized, obtains PMMA/SCTP composite micro-powder;
The template is tyrosine, glycine, aspartic acid, glutamic acid, 6-aminocaprolc acid, maltodextrin, second two
One of amine tetraacethyl, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate;
The PMMA/SCTP composite micro-powder partial size is between 0.02 μm~200 μm;Tripolyphosphate calcium sodium can also continue to
It is deposited in microsphere surface.
A kind of compound bone cement is prepared with the PMMA/SCTP composite micro-powder.The compound bone cement is by powder
Part and liquid portion composition, powder section PMMA/SCTP composite micro-powder as described in 65 parts~75 parts, 0.1 part~3 parts
Initiator and 24 parts~32 parts barium sulfate are uniformly mixed and form, and the liquid portion is by 90 parts~99.5 parts methyl methacrylates
Ester, 0.5 part~10 parts promotors and 60ppm~200ppm hydroquinone are uniformly mixed and form.
The initiator is one of benzoyl peroxide, dilauroyl peroxide;
The promotor is N, N- dimethyl-p-toluidine, n,N-Dimethylaniline, N- methyl-N- (2- ethoxy)-
One of p-toluidine.
The powder section and the liquid portion are individually enclosed in sterile chamber after aseptic process, using preceding pressing
It is mixed according to powder section with the weight ratio 1.5~4: 1 of liquid portion.
PMMA copolymer contains hydrophilic hydroxyl, calcium ion and tripolyphosphate ions binding under the action of template
It can be deposited in PMMA copolymer microsphere surface, and then assembled, cladding, it is compound micro- to form PMMA/SCTP for separating, washing, freeze-drying
Powder.SCTP has biocompatibility and activity, can assign bone-cement biological activity as main ingredient.
Specific embodiment
Embodiment 1
The compound emulsifying agent of neopelex, OP-10 and polyvinyl alcohol are prepared by 1: 1: 0.15 weight ratio;It presses
1: 0.1: 0.02 weight ratio prepares methyl methacrylate, hydroxyethyl meth acrylate, three second of contracting of methacrylate two
The mix monomer of diol ester;The persulfate aqueous solution that compound concentration is 1%.
100 parts of deionized waters, 4.5 parts of compound emulsifying agents, 15 parts of mix monomers are mixed, start stirring, simultaneously
Heating forms lotion, pH value is transferred to 8 with ammonium hydroxide, nitrogen filled protection;80 DEG C are warming up to, it is molten that 6 parts of potassium peroxydisulfates are added dropwise in 15min
After reacting 30min, 30 parts of mix monomers and 12 parts of potassium persulfate solutions are added dropwise in liquid simultaneously in 2h;After being added dropwise, after continuation of insurance
Temperature reaction 3h.It is down to room temperature, is centrifugated three times, 1000 parts of deionized water wash cycles, obtains methyl methacrylate
Copolymer microsphere.Using Scanning electron microscopy, methylmethacrylate copolymer microsphere average grain diameter 32.7nm is measured.
100 parts of deionized waters, 5 parts of methylmethacrylate copolymer microballoons, 0.5 part of L- paddy are sequentially added into reaction kettle
Propylhomoserin, stirring is to dissolving, with sodium hydroxide tune pH value to 8;The calcium chloride water that 10 parts of concentration are 50% is added, stirring
The tripolyphosphate sodium water solution that 8.3 parts of concentration are 50% is added after 20min, reacts 1.5h, is aged 1.5h, filters, ethanol washing,
Freeze-drying, obtains PMMA/SCTP composite micro-powder;Using Scanning electron microscopy, measures PMMA/SCTP composite micro-powder and be averaged grain
Diameter 108nm.
73 parts of PMMA/SCTP composite micro-powders, 2 parts of benzoyl peroxides, 25 parts of barium sulfate are uniformly mixed, as powder portion
Point;By 96.4 parts of methyl methacrylates (hydroquinone containing 100ppm), 3.6 parts of N, N- dimethyl-p-toluidine is uniformly mixed,
As liquid portion.Sterilization treatment is carried out respectively, is taken powder section and liquid portion according to 3: 1 ratio, is stored in nothing respectively
In bacterium cryopreservation tube.
Embodiment 2
The compound emulsifying agent of lauryl sodium sulfate and Span-60 is prepared by 1: 1.5 weight ratio;By 1: 0.2: 0.01
Weight ratio prepares the mix monomer of methyl methacrylate, hydroxy ethyl methacrylate, ethyleneglycol dimethyacrylate;It prepares dense
The persulfate aqueous solution that degree is 1%.
100 parts of deionized waters, 3 parts of compound emulsifying agents, 5 parts of mix monomers are mixed, stirring is started, rises simultaneously
Temperature forms lotion, pH value is transferred to 8 with ammonium hydroxide, nitrogen filled protection;80 DEG C are warming up to, 6 parts of potassium persulfate solutions are added dropwise in 15min,
After reacting 30min, 55 parts of mix monomers and 10 parts of potassium persulfate solutions are added dropwise simultaneously in 2h;After being added dropwise, continue to keep the temperature
React 3h.It is down to room temperature, is centrifugated three times, 1000 parts of deionized water wash cycles, it is total to obtain methyl methacrylate
Polymers microballoon.Using Scanning electron microscopy, 0.46 μm of methylmethacrylate copolymer microsphere average grain diameter is measured.
100 parts of deionized waters, 5 parts of methylmethacrylate copolymer microballoons, 1 part of ethylenediamine are sequentially added into reaction kettle
Tetraacethyl disodium, stirring is to dissolving, with sodium hydroxide tune pH value to 8;The calcium chloride water that 25 parts of concentration are 50% is added, stirs
The tripolyphosphate sodium water solution that 21 parts of concentration are 50% is added after mixing 20min, reacts 2h, is aged 2h, filtering, ethanol washing is frozen
It is dry, obtain PMMA/SCTP composite micro-powder;Using Scanning electron microscopy, PMMA/SCTP composite micro-powder average grain diameter is measured
2.59μm。
70 parts of PMMA/SCTP composite micro-powders, 2 parts of benzoyl peroxides, 28 parts of barium sulfate are uniformly mixed, as powder portion
Point;By 98.1 parts of methyl methacrylates (hydroquinone containing 100ppm), 1.9 parts of N, N- dimethyl-p-toluidine is uniformly mixed,
As liquid portion.Sterilization treatment is carried out respectively, is taken powder section and liquid portion according to 3: 1 ratio, is stored in nothing respectively
In bacterium cryopreservation tube.
Claims (6)
1. a kind of PMMA/SCTP composite micro-powder is characterized by having that core-shell structure, the core are methyl methacrylate and function
The copolymer of monomer, crosslinking agent, the shell are tripolyphosphate calcium sodium.
2. a kind of PMMA/SCTP composite micro-powder as described in claim 1, be characterized in that preparation method the following steps are included:
(1) compound emulsifying agent is prepared, mix monomer, while the persulfate aqueous solution that compound concentration is 0.1%~10% are prepared;
The compound emulsifying agent includes lauryl sodium sulfate, dodecyl sodium sulfate, neopelex, succinic acid two
Different monooctyl ester base sodium sulfonate, OP series emulsifier, Tween series emulsifier, Span series emulsifier, polyvinyl alcohol, carboxymethyl are fine
Tie up one of element or any combination;
The mix monomer includes methyl methacrylate, function monomer and crosslinking agent, wherein methyl methacrylate, function list
Body, crosslinking agent weight ratio be 1: 0.05~0.2: 0.001~0.1;
The function monomer is hydroxymethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate, hydroxyl butylacrylic acid
Ester, hydroxymethyl methacrylate, hydroxyethyl meth acrylate, hydroxypropyl methacrylate, hydroxyl butyl methyl acrylic acid
Ester, one of or any combination;
The crosslinking agent is ethyleneglycol dimethyacrylate, methacrylate diglycol ester, methacrylate
One of Triethylene Glycol, bisphenol-A-glycidyl Methacrylate;
(2) 100 parts of deionized waters, 0.5 part~10 parts compound emulsifying agents, 6 parts~30 parts mixing lists are sequentially added into reaction kettle
Body, while heating up and emulsifying, nitrogen filled protection;After being warming up to 80 DEG C, 0.1 part~1 part persulfate aqueous solution, reaction is added
After 15min~60min, 20 parts~90 parts mix monomers at the uniform velocity are added dropwise simultaneously in 2h~3h and 0.1 part~2 parts potassium peroxydisulfates are molten
Liquid;After dripping, continue insulation reaction 2h~3h;It is cooled to room temperature, is repeatedly centrifugated, deionized water flush cycle,
Obtain methylmethacrylate copolymer microballoon;
(3) at room temperature, it is micro- that 100 parts of deionized waters, 1 part~20 parts methylmethacrylate copolymers are sequentially added into reaction kettle
Ball, 0.2 part~4 parts templates, stirring is to dissolving, with sodium hydroxide tune pH value to 7.5~8.5;Calcium chloride water is added, stirs
After mixing 15min~45min, it is 2: 1 addition tripolyphosphate sodium water solutions according to the molar ratio of calcium constituent and sodium element, reacts 0.3h
~2h, is aged 1h~2h, filtering, and ethanol washing is lyophilized, obtains PMMA/SCTP composite micro-powder;
The template is tyrosine, glycine, aspartic acid, glutamic acid, 6-aminocaprolc acid, maltodextrin, ethylenediamine tetraacetic
One of acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate.
3. a kind of PMMA/SCTP composite micro-powder as claimed in claim 1 or 2, is characterized in that methylmethacrylate copolymer
The diameter of microballoon is between 0.02 μm~3 μm.
4. a kind of PMMA/SCTP composite micro-powder as claimed in claim 1 or 2, be characterized in that partial size 0.02 μm~200 μm it
Between.
5. a kind of compound bone cement, is characterized in that being made of powder section and liquid portion, the powder section by 65 parts~
75 parts of a kind of PMMA/SCTP composite micro-powder, 0.1 part~3 parts initiators and 24 parts~32 parts sulphur as described in Claims 1 to 4
Sour barium be uniformly mixed forms, the liquid portion by 90 parts~99.5 parts methyl methacrylates, 0.5 part~10 parts promotors and
60ppm~200ppm hydroquinone is uniformly mixed and forms;
The initiator is one of benzoyl peroxide, dilauroyl peroxide;
The promotor is N, N- dimethyl-p-toluidine, n,N-Dimethylaniline, N- methyl-N- (2- ethoxy)-p- first
One of aniline.
6. a kind of compound bone cement as claimed in claim 5 is characterized in that the powder section and the liquid portion pass through
Be individually enclosed in sterile chamber after aseptic process, using it is preceding according to the weight ratio 1.5~4: 1 of powder section and liquid portion into
Row mixing.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111330074A (en) * | 2020-03-20 | 2020-06-26 | 松山湖材料实验室 | Modified bone cement material and preparation method thereof |
CN111467564A (en) * | 2020-03-25 | 2020-07-31 | 西安理工大学 | Self-expansion composite bone cement and preparation method thereof |
-
2017
- 2017-11-21 CN CN201711236976.9A patent/CN109810440A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111330074A (en) * | 2020-03-20 | 2020-06-26 | 松山湖材料实验室 | Modified bone cement material and preparation method thereof |
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: 20190528 |