CN1651506A - Preparation method of nano-hydroxyapatite/polyvinyl alcohol composite hydrogel - Google Patents
Preparation method of nano-hydroxyapatite/polyvinyl alcohol composite hydrogel Download PDFInfo
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- CN1651506A CN1651506A CN 200310110815 CN200310110815A CN1651506A CN 1651506 A CN1651506 A CN 1651506A CN 200310110815 CN200310110815 CN 200310110815 CN 200310110815 A CN200310110815 A CN 200310110815A CN 1651506 A CN1651506 A CN 1651506A
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- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 302
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 239
- 238000002360 preparation method Methods 0.000 title claims abstract description 170
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 140
- 239000000017 hydrogel Substances 0.000 title claims abstract description 112
- 239000002131 composite material Substances 0.000 title claims abstract description 111
- 239000002002 slurry Substances 0.000 claims abstract description 171
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000013078 crystal Substances 0.000 claims abstract description 109
- 239000008367 deionised water Substances 0.000 claims abstract description 81
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 81
- 239000002904 solvent Substances 0.000 claims abstract description 81
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000007670 refining Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 274
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 121
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 104
- 238000000465 moulding Methods 0.000 claims description 88
- 238000003756 stirring Methods 0.000 claims description 85
- 235000011187 glycerol Nutrition 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims 2
- 239000003791 organic solvent mixture Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 description 130
- WHZWVUKPJBNTAK-UHFFFAOYSA-N hydroxy dihydrogen phosphite Chemical compound OOP(O)O WHZWVUKPJBNTAK-UHFFFAOYSA-N 0.000 description 83
- 239000012046 mixed solvent Substances 0.000 description 36
- 210000000845 cartilage Anatomy 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 210000004087 cornea Anatomy 0.000 description 8
- 210000001519 tissue Anatomy 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000002054 transplantation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007170 pathology Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011173 biocomposite Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 210000000981 epithelium Anatomy 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 206010023683 lagophthalmos Diseases 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000000278 osteoconductive effect Effects 0.000 description 1
- 230000002138 osteoinductive effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
Abstract
纳米羟基磷灰石/聚乙烯醇复合水凝胶的制备方法，包括：1.制备纳米羟基磷灰石晶体浆料；2.将固体聚乙烯醇精制纯化或配制聚乙烯醇溶液；3.将第一步所得与第二步所得混合；4.将第三步所得溶液冷冻－熔融成型，当其中不含有机溶剂时，直接得到纳米羟基磷灰石/聚乙烯醇复合水凝胶；当其中含有有机溶剂时，在去离子水中进行溶剂置换，得到纳米羟基磷灰石/聚乙烯醇复合水凝胶。The preparation method of nano-hydroxyapatite/polyvinyl alcohol composite hydrogel comprises: 1. preparing nano-hydroxyapatite crystal slurry; 2. refining and purifying solid polyvinyl alcohol or preparing polyvinyl alcohol solution; 3. The first step is mixed with the second step; 4. The solution obtained in the third step is frozen-melted, and when there is no organic solvent in it, the nano-hydroxyapatite/polyvinyl alcohol composite hydrogel is directly obtained; when the When an organic solvent is contained, solvent replacement is carried out in deionized water to obtain a nano-hydroxyapatite/polyvinyl alcohol composite hydrogel.
Description
Technical field
The present invention relates to the bio-medical composition field, relate in particular to a kind of allosome joint cartilage that is used for and transplant and substitute or allosome corneal transplantation and alternate bio-medical composition preparation method.
Background technology
The damage of joint cartilage and pathology are the common diseases of clinical orthopaedics, because self repair ability of body intrinsic articulation cartilage is limited, in case damage or pathology take place, are difficult to self-healing, and clinical treatment mainly is allosome cartilage transplantation and articular prosthesis displacement.But the donor source of cartilage transplantation is limited, artificial joint material commonly used at present is ultrahigh molecular weight polyethylene(UHMWPE) and metal compatibility, owing to be difficult to form liquid film lubrication, therefore cause the ultrahigh molecular weight polyethylene(UHMWPE) assembly to produce too much abrasive dust, this abrasive dust causes living tissue simplified reaction on every side and induces the loosening of articular prosthesis.Polyvinyl alcohol (PVA) hydrogel has snappiness, high chemical stability, is easy to moulding, has no side effect and the tissue excellent biological compatibility because of it, and have structure similar and mechanical property to joint cartilage, thereby be widely used at biomedical sector, as as slow-released carrier, tissue engineering bracket, artificial organs etc., also be one of first-selected artificial cartilage material, this kind artificial cartilage material has excellent biological compatibility and excellent friction characteristic.But the bonding properties of PVA cartilage prosthese and bone substrate is very poor, has influenced the fixing and repairing effect of cartilage.
In the CN02134218.0 patent of invention, a kind of nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel and preparation method are provided, can obtain the hydroxyapatite/polyvinyl alcohol composite hydrogel of the even mechanics excellent performance of microtexture.This Biocomposite material utilizes hydroxyapatite (Hydroxyapatite, HA or HAP) have the advantages that on the interface, to form very strong chemical bonding behind good biocompatibility and the implantable bone tissue, make biological compound water congealing glue material have osteoconductive and osteoinductive, to improve the bonding properties of artificial cartilage and bone substrate.But its preparation technology is complicated.
The artificial cornea support is a kind of tissue engineering bracket, and the key effect of stablizing artificial cornea with the tight joint and the support of host tissue that provides is provided.In U.S. Pat 5843185, a kind of artificial cornea that utilizes hydroxyapatite masonry rack making is provided, in implanting 12 lagophthalmos, observed 12 months, find cornea inoblast can grow into micropore and vascularization, implant does not have, and does not have and infects, no epithelium hyperplasia.But the hydroxyapatite intensity of using in this patented technology is low, and fragility is big, and it is cracked when thick to be machined to 2mm, is difficult to satisfy the artificial cornea backing thickness on the one hand and should be controlled at the following requirement of 1mm.
Goal of the invention
Purpose of the present invention is to provide a kind of nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel preparation method of even structure, compares with preparation method in the CN02134218.0 patent of invention, and its technology is simpler, and cost is cheaper.Utilize the nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel of this method preparation not only to can be used as the artificial cartilage material, when being used as the timbering material for artificial cornea,, be easy to processing, can process system 1mm because of its fragility is low.
Summary of the invention
Nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel can prepare by following two kinds of methods:
First method:
The first step: the preparation nano hydroxyl phosphorite crystal: liquid is the slurry of crystal weight per-cent 1～20%;
Second step: with the refining purifying of solid polyethylene alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, fully stir down at 90～120 ℃;
The 4th the step: utilize common processing molding method, with the 3rd the step gained freezing-melt molding, when wherein not containing organic solvent, directly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel; When wherein containing organic solvent, in deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
The described liquid of the first step can be water, or organic solvent, or the mixed solution of water and organic solvent, and organic solvent can be dimethyl sulfoxide (DMSO) or glycerine.
Second method:
The first step: the preparation nano hydroxyl phosphorite crystal: liquid is the slurry of crystal weight percentage concentration 1～30%;
Second step: the polyvinyl alcohol that will make with extra care purifying is dissolved in the solution, and the preparation weight percent is 1～35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60～120 ℃;
The 4th the step: utilize common processing molding method, with the 3rd the step gained freezing-melt molding, when wherein not containing organic solvent, directly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel; When wherein containing organic solvent, in deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Described liquid of the first step and described solution of the 3rd step can be water, or organic solvent, or the mixed solution of water and organic solvent.Organic solvent can be dimethyl sulfoxide (DMSO) or glycerine.
Because of artificial cartilage or artificial cornea timbering material require not contain or contain less organic solvent as far as possible, so if contain organic solvent in above-mentioned two kinds of preparation methods' the 4th step products obtained therefrom, just must in deionized water, carry out solvent exchange, remove organic solvent wherein after, just can obtain the finished product.
Be the nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel series product that obtain different moisture content, can carry out the processing that dehydrates in various degree to the nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel that obtains by above-mentioned two kinds of preparation methods, the various common methods that dehydrate (as lyophilize, vacuum-drying ... etc.) all applicable.
Embodiment
Below in conjunction with some specific embodiments the present invention is described in further detail.
First kind of preparation method's embodiment is as follows:
Embodiment 1
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of water is 1%: 99% slurry;
Second step: with the refining purifying of solid polyethylene alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and polyvinyl alcohol weight percent 25% fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding.Promptly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 2:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of water is 10%: 90% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and making the polyvinyl alcohol weight percent is 20%, fully stirs down at 100 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding.Promptly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 3:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of water is 20%: 80% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and making the polyvinyl alcohol weight percent is 10%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould,, promptly obtained nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel through freezing-melt molding.
Embodiment 4:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of dimethyl sulfoxide (DMSO) is 1%: 99% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and making the polyvinyl alcohol weight percent is 24%, fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 5:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of dimethyl sulfoxide (DMSO) is 10%: 90% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 15%, fully stirs down at 100 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 6:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of dimethyl sulfoxide (DMSO) is 20%: 80% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 5%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 7:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of glycerine is 1%: 99% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 22%, fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 8:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of glycerine is 10%: 90% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 13%, fully stirs down at 100 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 9:
The first step: the preparation nano hydroxyl phosphorite crystal: the weight percent of glycerine is 20%: 80% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 6%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 10:
The first step: the preparation nano hydroxyl phosphorite crystal: water: dimethyl sulfoxide (DMSO): the weight percent of glycerine is 1%: 20%: 69%: 10% slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 26%, fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 11:
The first step: the preparation nano hydroxyl phosphorite crystal: water: dimethyl sulfoxide (DMSO): the weight percent of glycerine is 10%: 20%: 60%: 10% slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 12%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 12:
The first step: the preparation nano hydroxyl phosphorite crystal: water: dimethyl sulfoxide (DMSO): the weight percent of glycerine is 20%: 20%: 50%: 10% slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 3%, fully stirs down at 110 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 13:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of dimethyl sulfoxide (DMSO) is 1%: 20%: 79% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 23%, fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 14:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of dimethyl sulfoxide (DMSO) is 10%: 20%: 70% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 18%, fully stirs down at 110 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 15:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of dimethyl sulfoxide (DMSO) is 20%: 10%: 70% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 9%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 16:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of glycerine is 1%: 89%: 10% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 21%, fully stirs down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 17:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of glycerine is 10%: 70%: 20% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 16%, fully stirs down at 110 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 18:
The first step: the preparation nano hydroxyl phosphorite crystal: water: the weight percent of glycerine is 20%: 70%: 10% a slurry;
Second step: with the refining purifying of polyvinyl alcohol;
The 3rd step: the second step gained polyvinyl alcohol is joined in the first step gained slurry, and the weight percent that makes polyvinyl alcohol is 8%, fully stirs down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Some embodiment of second kind of preparation method are as follows:
Embodiment 19
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding.Promptly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 20:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 20%;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 20% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step solution gained are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding.Promptly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 21:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding.Promptly obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 22:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 23:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 15%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 24:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 5% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 25:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 26:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 18%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 27:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 16% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 28:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 25% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 29:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 17%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 30:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 31:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 32:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 25%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 25% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 33:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 34:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 35:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 30% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and second step institute's solution must be mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 36:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 37:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 1%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 10% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 38:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 30%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 39:
The first step: the preparation nano hydroxyl phosphorite crystal: water is the slurry of hydroxyapatite crystal weight percent 20%;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step solution gained are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 40:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 5% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 41:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 5% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 42:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 43:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 44:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 15% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 45:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 14% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 46:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 47:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 22% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 48:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 10% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 49:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 11% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 50:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 20% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.。
Embodiment 51:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 52:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 20% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 53:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 20% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 54:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 55:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 19% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 56:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 14.5% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 57:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 58:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 20% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 59:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 16% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 60:
The first step: the preparation nano hydroxyl phosphorite crystal: the dimethyl sulfoxide (DMSO) weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 61:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 31% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.。
Embodiment 62:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 20% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 63:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: it is soluble in water to make with extra care purify poly (vinyl alcohol), and the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 64:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 9% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 65:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 24% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 66:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the dimethyl sulfoxide (DMSO), the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 67:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 68:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 20% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 69:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care purify poly (vinyl alcohol) and be dissolved in the glycerine, the preparation weight percent concentration is 20% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 70:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 21% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 71:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 20% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 72:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and water, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 73:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 74:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 20% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 17% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 75:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO), G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 76:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 17% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 77:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 26% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 78:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in G ﹠ W, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 79:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 1% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 35% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 60 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 80:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 11% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 1% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 90 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Embodiment 81:
The first step: the preparation nano hydroxyl phosphorite crystal: the glycerine weight percent is 30% slurry;
Second step: will make with extra care in the mixed solvent that purify poly (vinyl alcohol) is dissolved in dimethyl sulfoxide (DMSO) and glycerine, the preparation weight percent concentration is 11% polyvinyl alcohol solution;
The 3rd step: the first step gained slurry and the second step gained solution are mixed, fully stir down at 120 ℃;
The 4th step: the 3rd step gained is poured in the mould, through freezing-melt molding; In deionized water, carry out solvent exchange, obtain nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel.
Utilize the nanometer hydroxyapatite/polyvinyl alcohol composite hydrogel of the inventive method preparation, can be used as artificial cartilage equally and transplant and equivalent material with good biocompatibility.When being used as for artificial CF material, according to experimental result, the intensity that has overcome hydroxyapatite artificial cornea timbering material is low, and fragility is big, is difficult for shortcomings such as processing, it can be machined to 1mm.
Claims (9)
Priority Applications (1)
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268140A (en) * | 2011-05-19 | 2011-12-07 | 四川大学 | Method for freeze-dispersing nano clay in nano composite material |
| CN103087455A (en) * | 2011-10-27 | 2013-05-08 | 中国科学院化学研究所 | Preparation method and uses of biodegradable high mechanical strength organic/inorganic composite hydrogel |
| CN104548211A (en) * | 2014-12-19 | 2015-04-29 | 戴立军 | Orthopedics or dental filling material, dental implant and degradable artificial bone |
| CN105669084A (en) * | 2016-01-14 | 2016-06-15 | 徐州医学院附属医院 | Biomimetic material for shoulder joint and preparation method and application thereof |
| CN106620873A (en) * | 2016-11-17 | 2017-05-10 | 太原理工大学 | Composite hydrogel cartilage repair material and preparation method thereof |
| CN107602878A (en) * | 2017-10-09 | 2018-01-19 | 常州凯途纺织品有限公司 | A kind of preparation method of polyvinyl alcohol hydrogel |
| CN107670114A (en) * | 2017-10-07 | 2018-02-09 | 北京林业大学 | A kind of medical bio composite based on the enhancing of Eucalyptus nano micro crystal cellulose and preparation method thereof |
| CN107754019A (en) * | 2017-10-07 | 2018-03-06 | 北京林业大学 | One kind is based on Eucalyptus lignin modification hydroxyapatite/polyvinyl alcohol Biocomposite material and manufacture method |
| CN108409988A (en) * | 2018-04-20 | 2018-08-17 | 西北大学 | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel |
| CN112940294A (en) * | 2021-03-18 | 2021-06-11 | 中北大学 | PVA/HA double-network hydrogel and preparation method and application thereof |
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- 2003-10-31 CN CN 200310110815 patent/CN1279104C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102268140A (en) * | 2011-05-19 | 2011-12-07 | 四川大学 | Method for freeze-dispersing nano clay in nano composite material |
| CN103087455A (en) * | 2011-10-27 | 2013-05-08 | 中国科学院化学研究所 | Preparation method and uses of biodegradable high mechanical strength organic/inorganic composite hydrogel |
| CN103087455B (en) * | 2011-10-27 | 2015-04-01 | 中国科学院化学研究所 | Preparation method and uses of biodegradable high mechanical strength organic/inorganic composite hydrogel |
| CN104548211A (en) * | 2014-12-19 | 2015-04-29 | 戴立军 | Orthopedics or dental filling material, dental implant and degradable artificial bone |
| CN105669084A (en) * | 2016-01-14 | 2016-06-15 | 徐州医学院附属医院 | Biomimetic material for shoulder joint and preparation method and application thereof |
| CN106620873A (en) * | 2016-11-17 | 2017-05-10 | 太原理工大学 | Composite hydrogel cartilage repair material and preparation method thereof |
| CN107670114A (en) * | 2017-10-07 | 2018-02-09 | 北京林业大学 | A kind of medical bio composite based on the enhancing of Eucalyptus nano micro crystal cellulose and preparation method thereof |
| CN107754019A (en) * | 2017-10-07 | 2018-03-06 | 北京林业大学 | One kind is based on Eucalyptus lignin modification hydroxyapatite/polyvinyl alcohol Biocomposite material and manufacture method |
| CN107602878A (en) * | 2017-10-09 | 2018-01-19 | 常州凯途纺织品有限公司 | A kind of preparation method of polyvinyl alcohol hydrogel |
| CN108409988A (en) * | 2018-04-20 | 2018-08-17 | 西北大学 | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel |
| CN108409988B (en) * | 2018-04-20 | 2020-10-30 | 西北大学 | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel |
| CN112940294A (en) * | 2021-03-18 | 2021-06-11 | 中北大学 | PVA/HA double-network hydrogel and preparation method and application thereof |
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| CN1279104C (en) | 2006-10-11 |
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