CN104558676A - Preparation method of microporous polycaprolactone-polyacrylic sodium alginate resin - Google Patents
Preparation method of microporous polycaprolactone-polyacrylic sodium alginate resin Download PDFInfo
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- CN104558676A CN104558676A CN201410695562.2A CN201410695562A CN104558676A CN 104558676 A CN104558676 A CN 104558676A CN 201410695562 A CN201410695562 A CN 201410695562A CN 104558676 A CN104558676 A CN 104558676A
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- sodium alginate
- polycaprolactone
- blend
- polyacrylic acid
- acid sodium
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 46
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 46
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 16
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229920002125 Sokalan® Polymers 0.000 claims description 29
- 239000004584 polyacrylic acid Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 15
- 230000008961 swelling Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000002525 ultrasonication Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of microporous polycaprolactone-polyacrylic sodium alginate resin. The preparation method comprises the following steps: sequentially synthesizing polycaprolactone-polyacrylic sodium alginate resin by acrylic acid and sodium alginate; preparing polycaprolactone; preparing a polycaprolactone-polyacrylic sodium alginate resin blend; and preparing a microporous blend, thereby finally obtaining a product. The blend material provided by the invention can be used for improving the heat resistance of polycaprolactone and has a potential application value in expanding the application range of polycaprolactone and enhancing the product quality. In addition, the microporous blend material as a bracket material facilitates uniform distribution of cells in the whole bracket and further provides a relatively large specific surface area for a three-dimensional network structure formed by newly generated tissue compositions.
Description
Technical field
The present invention relates to degradable biological polymeric material field, particularly relate to the preparation method of a kind of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin.
Background technology
Polycaprolactone is a kind of novel biodegradable macromolecular material, can slowly degrade in earth, but depositing in atmosphere and do not observe a degraded in, can be used as plastic sheeting for farm use, wrapping material etc., is one of degradation property material of most possible industrialized mass use.But polycaprolactone major defect is that its fusing point is lower, and only have about 60 DEG C, therefore, the non-constant of resistance to heat distorsion, adds factor in price, just limits its promotion and application.Not enough in order to overcome these, adopting polyfunctional monomer or polymkeric substance and polycaprolactone to carry out blended, wishing by strengthening the thermal characteristics being cross-linked and improving blended rear polycaprolactone.
Polycaprolactone also has good biocompatibility, by animal body metabolism, therefore can also have very important using value at biomedical engineering field, as Co ntrolled release, the organizational project skeleton and orthopaedics immobilization material etc. of medicine.Polycaprolactone had both served physical support effect as tissue engineering bracket, again that cell cultivates the adhesion substances implanted with the later stage in vitro, therefore the design first-selection of timbering material must possess very large specific surface area and high hole, ensure that the cell of plantation obtains fully suitable space in process of growth, be conducive to cell to be uniformly distributed, be also conducive to newly-generated structural constituent and form three-dimensional net structure.
Summary of the invention
For above-mentioned Problems existing, the invention provides a kind of specific surface area large, facilitate the preparation method of the micropore shape polycaprolactone-polyacrylic acid sodium alginate resin of plant-growth.
In order to achieve the above object, the technical solution used in the present invention is as follows: the preparation method of a kind of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin, described preparation method is as follows: by vinylformic acid and sodium alginate successively through synthesis polyacrylic acid sodium alginate resin → prepare polycaprolactone-polyacrylic acid sodium alginate resin blend → prepare micropore shape blend, finally obtain product; Its detailed preparation method is as follows:
1) polyacrylic acid sodium alginate resin is synthesized: after vinylformic acid underpressure distillation removing stopper, dripping 7.5mol/L NaOH solution is 80-90% to degree of neutralization, add sodium alginate aqueous solution, initiator sodium persulfate aqueous solution is added after stirring, stir and be placed on 70 DEG C of baking oven reaction 3h, obtain block polyacrylic acid sodium alginate resin;
2) polycaprolactone-polyacrylic acid sodium alginate resin blend is prepared: become by polycaprolactone mass ratio to be the masterbatch of 3:5 with polyacrylic acid sodium alginate resin formulations, then on the double roller plastic-making device of 70 DEG C, plasticate 10 ~ 15 min, bottom sheet, the blend test piece be hot pressed in stainless steel mould;
3) prepare micropore shape blend: blend test piece adds swelling agent butanone, activate under ultrasonication, be warming up to 40 ~ 55 DEG C; The NaOH aqueous solution with 10% adjusts system pH to 10 ~ 13, rapid cool to room temperature after reaction 3 ~ 5 h, and the HCl aqueous solution adjustment system pH with 10%, to 2.2, is warming up to 40 ~ 55 DEG C, uses NaOH aqueous solution adjustment system pH to 7 after reaction 3 ~ 5 h; Through washing, sieving after completing reaction, drying obtains micropore shape blend.
In synthesis polyacrylic acid sodium alginate resin steps of the present invention, vinylformic acid, sodium alginate, Sodium Persulfate mass ratio are 80:1:0.01.Sodium alginate and vinylformic acid are formed in the process of multipolymer, sodium alginate also plays linking agent effect, under this mass ratio, polyacrylic acid sodium alginate resin can form desirable cross-linked structure, when sodium alginate add-on is too low, tridimensional network cannot be formed, in later stage swelling process, intensity is too low, and when sodium alginate add-on is too large, crosslinking copolymers density increases, solvent cannot enter in reticulated structure, affects swelling process.
Of the present inventionly prepare in polycaprolactone-polyacrylic acid sodium alginate resin blend step, the thickness of described blend test piece is 1 ~ 5mm.Roller adjustable distance due to plasticator in actual production process is 0 ~ 5mm, selects 1 ~ 5mm to facilitate later stage cutting operation, improves the production efficiency of integrated artistic.
Of the present inventionly prepare in micropore shape blend step, blend test piece and swelling agent mass ratio are 1:5-10; By the swelling agent of this kind of mass ratio, mainly ensure that blend test piece is immersed in swelling agent, the change of mass ratio is little on reaction impact, and quality very little can not submergence completely, then causes waste too much.
The invention has the advantages that: intermingling material of the present invention can improve polycaprolactone resistance toheat, in widening polycaprolactone range of application and improving the quality of products, there is potential using value.In addition, micropore shape intermingling material, as timbering material, is conducive to cell and distributes at whole stake body inner homogeneous, also provides larger specific surface area for newly-generated structural constituent forms three-dimensional net structure.
Accompanying drawing explanation
Fig. 1 is micropore shape blend electromicroscopic photograph in the embodiment of the present invention 1;
Fig. 2 is micropore shape blend electromicroscopic photograph in the embodiment of the present invention 2.
Embodiment
Illustrate that the present invention is described in further detail below in conjunction with embodiment and accompanying drawing.
embodiment 1:
30g vinylformic acid removes stopper through underpressure distillation, agitation and dropping 7.5mol/L NaOH solution to degree of neutralization is 80% at ambient temperature, add 50g/L sodium alginate aqueous solution 7.5mL, initiator 1mg/mL sodium persulfate aqueous solution 4mL is added after stirring, stir and be placed on 70 DEG C of baking oven reaction 3h, obtain block polyacrylic acid sodium alginate resin.Faint yellow particulate resins is obtained after pulverizing.
First become by polycaprolactone mass ratio to be the masterbatch of 3:5 with polyacrylic acid sodium alginate resin formulations, then on the double roller plastic-making device of 70 DEG C, plasticate 10min, and bottom sheet is hot pressed into the test piece that 2 mm are thick in stainless steel mould.
Blend test piece 3g adds swelling agent butanone 15g, activates under ultrasonication, is warming up to 50 DEG C.NaOH aqueous solution adjustment system pH with 10% is to 11, and rapid cool to room temperature after reacting 3 h, the HCl aqueous solution adjustment system pH with 10%, to 2.2, uses NaOH aqueous solution adjustment system pH to 7 after being warming up to 50 DEG C of reaction 3h.Complete through processes such as washing, screenings after reaction, by swelling agent recycling use.Drying obtains micropore shape blend.Blend is 88 DEG C through melting point detector test fusing point.
The result of the product obtained under Electronic Speculum as shown in Figure 1.
embodiment 2:
30g vinylformic acid removes stopper through underpressure distillation, agitation and dropping 7.5mol/L NaOH solution to degree of neutralization is 90% at ambient temperature, add 50g/L sodium alginate aqueous solution 8.5mL, initiator 1mg/mL sodium persulfate aqueous solution 3mL is added after stirring, stir and be placed on 70 DEG C of baking oven reaction 3h, obtain block polyacrylic acid sodium alginate resin.Faint yellow particulate resins is obtained after pulverizing.
First become by polycaprolactone mass ratio to be the masterbatch of 3:5 with polyacrylic acid sodium alginate resin formulations, then on the double roller plastic-making device of 70 DEG C, plasticate 10min, and bottom sheet is hot pressed into the test piece that 2 mm are thick in stainless steel mould.
Blend test piece 3g adds swelling agent butanone 18g, activates under ultrasonication, is warming up to 55 DEG C.NaOH aqueous solution adjustment system pH with 10% is to 12, and rapid cool to room temperature after reacting 5 h, the HCl aqueous solution adjustment system pH with 10%, to 2.2, uses NaOH aqueous solution adjustment system pH to 7 after being warming up to 55 DEG C of reaction 5 h.Complete through processes such as washing, screenings after reaction, by swelling agent recycling use.Drying obtains micropore shape blend.Blend is 86 DEG C through melting point detector test fusing point.
The result of the product obtained under Electronic Speculum as shown in Figure 2.
embodiment 3:by the structure of embodiment 1 and embodiment 2 gained, carried out performance test, the product performance in itself and prior art field contrasted, concrete contrast properties parameter is as shown in the table:
Micropore shape blend connectedness is drawn by ethanol specific absorption.Be immersed in ethanol by the micropore shape blend of drying, take out after 4h after drying surface liquid and weigh, infiltration front and back are of poor quality is ethanol specific absorption with the ratio of dry blends.Ethanol specific absorption is higher, and porous support connectedness is better.Can find out according to upper table result, the specific surface area of micropore shape blend and connectedness are all much better than commercially available untreated polycaprolactone.
It should be noted that, above-mentioned is only preferred embodiment of the present invention, is not used for limiting protection scope of the present invention, and equivalents done on the basis of above-described embodiment all belongs to protection scope of the present invention.
Claims (4)
1. the preparation method of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin, it is characterized in that, described preparation method is as follows: by vinylformic acid and sodium alginate successively through synthesis polyacrylic acid sodium alginate resin → prepare polycaprolactone-polyacrylic acid sodium alginate resin blend → prepare micropore shape blend, finally obtain product; Its detailed preparation method is as follows:
1) polyacrylic acid sodium alginate resin is synthesized: after vinylformic acid underpressure distillation removing stopper, dripping 7.5mol/L NaOH solution is 80-90% to degree of neutralization, add sodium alginate aqueous solution, initiator sodium persulfate aqueous solution is added after stirring, stir and be placed on 70 DEG C of baking oven reaction 3h, obtain block polyacrylic acid sodium alginate resin;
2) polycaprolactone-polyacrylic acid sodium alginate resin blend is prepared: become by polycaprolactone mass ratio to be the masterbatch of 3:5 with polyacrylic acid sodium alginate resin formulations, then on the double roller plastic-making device of 70 DEG C, plasticate 10 ~ 15 min, bottom sheet, the blend test piece be hot pressed in stainless steel mould;
3) prepare micropore shape blend: blend test piece adds swelling agent butanone, activate under ultrasonication, be warming up to 40 ~ 55 DEG C; The NaOH aqueous solution with 10% adjusts system pH to 10 ~ 13, rapid cool to room temperature after reaction 3 ~ 5 h, and the HCl aqueous solution adjustment system pH with 10%, to 2.2, is warming up to 40 ~ 55 DEG C, uses NaOH aqueous solution adjustment system pH to 7 after reaction 3 ~ 5 h; Through washing, sieving after completing reaction, drying obtains micropore shape blend.
2. the preparation method of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin as claimed in claim 1, it is characterized in that, in described synthesis polyacrylic acid sodium alginate resin steps, vinylformic acid, sodium alginate, Sodium Persulfate mass ratio are 80:1:0.01.
3. the preparation method of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin as claimed in claim 1, it is characterized in that, described prepares in polycaprolactone-polyacrylic acid sodium alginate resin blend step, and the thickness of described blend test piece is 1 ~ 5 mm.
4. the preparation method of micropore shape polycaprolactone-polyacrylic acid sodium alginate resin as claimed in claim 1, it is characterized in that, described prepares in micropore shape blend step, and blend test piece and swelling agent mass ratio are 1:5-10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239567A (en) * | 2020-08-31 | 2021-01-19 | 中国科学院兰州化学物理研究所 | Polycaprolactone/sodium alginate composite material and preparation method and application thereof |
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|---|---|---|---|---|
| CN1544526A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院长春应用化学研究所 | Biodegradable poly epsilon-caprolactone foam plastic and preparation method thereof |
| WO2008100556A2 (en) * | 2007-02-14 | 2008-08-21 | Drexel University | Alimentary protein-based scaffolds (aps) for wound healing, regenerative medicine and drug discovery |
| CN101264343A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Silk fiber reinforced polycaprolactone porous scaffold and preparation method thereof |
| CN104004219A (en) * | 2014-04-28 | 2014-08-27 | 安徽红太阳新材料有限公司 | Method for preparing hollow microspheres by using waste rubber |
-
2014
- 2014-11-27 CN CN201410695562.2A patent/CN104558676A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544526A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院长春应用化学研究所 | Biodegradable poly epsilon-caprolactone foam plastic and preparation method thereof |
| WO2008100556A2 (en) * | 2007-02-14 | 2008-08-21 | Drexel University | Alimentary protein-based scaffolds (aps) for wound healing, regenerative medicine and drug discovery |
| CN101264343A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Silk fiber reinforced polycaprolactone porous scaffold and preparation method thereof |
| CN104004219A (en) * | 2014-04-28 | 2014-08-27 | 安徽红太阳新材料有限公司 | Method for preparing hollow microspheres by using waste rubber |
Non-Patent Citations (2)
| Title |
|---|
| 吴和融等: "《高分子物理学》", 31 December 1990, 华东化工学院出版社 * |
| 张小红: ""聚丙烯酸/海藻酸钠高吸水性树脂的制备及生物降解性能"", 《化工学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112239567A (en) * | 2020-08-31 | 2021-01-19 | 中国科学院兰州化学物理研究所 | Polycaprolactone/sodium alginate composite material and preparation method and application thereof |
| CN112239567B (en) * | 2020-08-31 | 2021-08-31 | 中国科学院兰州化学物理研究所 | A kind of polycaprolactone/sodium alginate composite material and its preparation method and application |
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Application publication date: 20150429 |