CN105176031A - Blood compatibility polylactic acid self-reinforced material with surface being provided with bionic structure and preparation method thereof - Google Patents
Blood compatibility polylactic acid self-reinforced material with surface being provided with bionic structure and preparation method thereof Download PDFInfo
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- CN105176031A CN105176031A CN201510714151.8A CN201510714151A CN105176031A CN 105176031 A CN105176031 A CN 105176031A CN 201510714151 A CN201510714151 A CN 201510714151A CN 105176031 A CN105176031 A CN 105176031A
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Abstract
The invention discloses a blood compatibility polylactic acid self-reinforced material with the surface being provided with a bionic structure and a preparation method thereof. The method is characterized by comprising the steps that 0.05-5 parts of epoxy branching agent, 0.05-5 parts of acid anhydride branching agent, 0.05-1 part of catalyst and dried polylactic acid are together added into an internal mixer for reacting for 3-40 minutes at the temperature of 160-220 DEG C, so that a polylactic acid material with the 'strain hardening' extensional rheology characteristic is obtained; the polylactic acid material is subjected to injection molding to be made into a dumbbell-shaped tensile test sample with the width being 10 mm and the thickness being 4 mm, and the injection molding temperature is 170-220 DEG C; afterwards, the injection molding test sample is fixed to a solid-phase die drawing device capable of controlling the temperature and adjusting the speed and the die thickness, the test piece passes through a hot drawing die with the section thickness being smaller than that of the test sample at the drawing speed of 2.5-50 mm/min at the temperature of 60-150 DEG C for drawing orientation, after drawing reaches preset drawing multiplying power, cooling and unloading are carried out, the test sample is taken down, and accordingly the blood compatibility polylactic acid self-reinforced material with the surface being provided with the bionic structure is obtained.
Description
One. technical field
The present invention relates to the preparation method that a kind of surface has the blood compatibility poly(lactic acid) self-reinforced material of biomimetic features, belong to biological medical polymer material and processing of high molecular material technical field.
Two. background technology
Poly(lactic acid) is a kind of thermoplastic aliphatic's polyester of synthetic, its material acid derives from the renewable resources such as corn, cereal, nontoxic, nonirritant, there is excellent biocompatibility and complete biodegradability, be the degradable biomaterial that can be used for human body through FDA approval, be widely used in the materials such as operating sutures, controlled drug delivery system, fracture inside-fixture and tissue engineering bracket.
Along with developing rapidly of current clinical medicine, especially the widespread use of implanted artificial organs and Interventional Clinics, in cardiovascular systems, artificial heart valve, making assisted circulation of ventriculus cordis system, hemodialysis system, Interventional diagnosis and treatment air bag and conduit etc., increasing biomaterial and medicine equipment need material directly to contact with blood, therefore, blood compatibility has become one of of paramount importance performance index of biomaterial.But, there is a large amount of ester bonds in polylactic acid molecule structure, wetting ability is poor, does not possess the biological cells and tissues consistency that cell epimatrix material is good, and then reduce its blood compatibility and anticoagulant, make it be restricted as with the direct contact material application aspect of blood.On the other hand, because the firm matter of poly(lactic acid) is crisp, physical strength is not high, is difficult to meet the requirement that human part is repaired in some medical treatment, is therefore necessary to carry out modification to it, improves its blood compatibility, improve mechanical strength.
At present, relate to all kinds of patented technology with blood compatibility poly(lactic acid) of research preparation to mainly contain: poly(lactic acid) is carried out amination modified by CN102675674A, make positive charge on its surface band, again by LBL self-assembly N,O-Diacetylmuramidase and lentinan sulfate in its finishing, obtained poly-lactic acid material surface is made to have the blood compatibility of anti-microbial activity and improvement; CN103159947A utilizes the double bond of the amino in amination poly(lactic acid) and 2-acryloyl-oxyethyl phosphatidyl choline to carry out Micheal addition reaction, realizes the phosphatidyl choline biomimetic modification to poly(lactic acid), improves cell compatibility and the blood compatibility of material; CN104069743A utilizes Dopamine HCL at polylactic acid film surface construction active coating, causes zwitter-ion, on film surface, atom transfer radical polymerization occurs, zwitter-ion is grafted on polylactic acid film surface, improves film hydrophilic, reduce blood through resistance.In a word, improving, the report of the research in poly(lactic acid) blood compatibility is less, is mostly to introduce biologically active substance by carrying out finishing to poly(lactic acid) on its surface, increase the anticoagulation function that its wetting ability improves poly(lactic acid).
Relatively many to the activeness and quietness study on the modification of poly(lactic acid), such as CN104387733A, CN102675523ACN1760266, CN104312118A, CN1680487, CN1488673 etc., method of modifying is mainly divided into two large classes: a class is based on copolymerization, the chemical modification that is cross-linked, its Be very effective, but cost is higher, preparation process is more complicated.Another kind of method is blended and filling waits physically modified, by poly(lactic acid) and the flexible biological degradable material such as treated starch, poly-hexanodioic acid glycerine ester, polycaprolactone, polyolefin elastomer, polyamide elastomer and polyurethane elastomer etc., Mierocrystalline cellulose and crystallite thereof, the various natural fiber such as sisal hemp, flax, fibroin fiber, calcium metaphosphate whisker etc. are blended, to improve fracture toughness property and tensile strength.Because the physicochemical property such as polarity, crystallinity of poly(lactic acid) and packing material exist bigger difference, between complex components, consistency and low interface bond strength become the subject matter of these class methods, activeness and quietness limited efficiency.
Three. summary of the invention
The object of this invention is to provide the preparation method that a kind of surface has the blood compatibility poly(lactic acid) self-reinforced material of biomimetic features, be characterized in when without the need to carrying out surface biological process, adopt solid phase mouth closing mould stretching technology, strengthen the height-oriented fibrillation poly-lactic acid material of preparation by melt, while significantly improving its mechanical property, build the micro/nano level very low power biomimetic features of similar blood vessel, improve poly(lactic acid) blood compatibility, obtain the poly(lactic acid) self-reinforced material with good blood compatibility.
Object of the present invention is realized by following technical measures, and the preparation method that surface has biomimetic features blood compatibility poly(lactic acid) self-reinforced material comprises the following steps, and wherein said raw material mark, except specified otherwise, is parts by weight:
(1) there is the preparation of " strain hardening " draft flowing deformation characteristic poly-lactic acid material
0.05 ~ 5 part of epoxies branching agent, 0.05 ~ 5 part of anhydrides branching agent, 0.05 ~ 1 part of catalyzer are added in Banbury mixer together with the poly(lactic acid) of drying, at 160-220 DEG C, react 3 ~ 40min, be there is " strain hardening " draft flowing deformation characteristic poly-lactic acid material;
Wherein, epoxies branching agent is three epoxypropyl tricarbimides, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group p-aminophenol, N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl-methane, Phloroglucinol monomethyl ether triglycidyl ether, Pyromellitic Acid four glycidyl ether, 1,1 ', any one in 2,2 '-four (p-hydroxybenzene) ethane four glycidyl ether, Resorcinol formal four glycidyl ether, two Resorcinol formal four glycidyl ether;
Anhydrides branching agent is Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, mellophanic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Succinic anhydried, MALEIC ANHYDRIDE, dodecyl are for any one in MALEIC ANHYDRIDE, inner methylidyne tetrahydric phthalic anhydride, hexahydrophthalic anhydride, glycerine three trimellitic acid 1,2-anhydride, pentamethylene tetracarboxylic dianhydride;
Catalyzer is any one in stannous octoate, tin tetraphenyl, tin protochloride, antimonous oxide, butyl (tetra) titanate, lanthanum titanium complex catalyst;
(2) surface has the preparation of biomimetic features blood compatibility self-enhancement poly-lactic acid material
The poly-lactic acid material injection moulding that will be obtained by step (1), make the dumbbell shape tension specimen that width is 10mm, thickness is 4mm, injection temperature: 170 ~ 220 DEG C, then injection-molded test specimens is fixed on the solid phase mouth closing mould stretching device of temperature controllable speed governing, with the rate of extension of 2.5 ~ 50mm/min at 60 ~ 150 DEG C, it is made to be less than the thermal stretch mouth mould of sample by section thickness, carry out stretch orientation, to be tensioned reach predetermined stretching ratio after, cool, unload, take off sample, obtain and surperficial there is biomimetic features blood compatibility poly(lactic acid) self-reinforced material;
Wherein, thermal stretch mouth mould thickness is any one in 0.1mm, 0.25mm, 0.5mm, 0.75mm, 1mm, 1.25mm, 1.5mm, 1.75mm, 2mm, 2.5mm, 3mm.
Four, tool of the present invention has the following advantages
The present invention is directed to the problem that poly(lactic acid) blood compatibility and mechanical property are difficult to meet interplantation type bio-medical material related request, first the branching reaction in reacting processing is adopted to introduce long branched chain structure on polylactic acid molecule chain, improve melt strength, give the tensile properties of its " strain hardening ", widen poly(lactic acid) thermal stretch process window; Then when without the need to carrying out surface biological process, solid-phase thermal stretching technique is adopted to realize the height-oriented fibrillation of polylactic acid molecule, while increasing substantially its mechanical property, build the very low power and the ordered orientation state biomimetic features that are similar to microbial film and blood vessel, the surface tissue of regulation and control poly(lactic acid) and character, improve its blood compatibility, obtain the self-enhancement poly-lactic acid material with good blood compatibility.
Five, embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above to the present invention.
Embodiment 1
1g Phloroglucinol monomethyl ether triglycidyl ether, 1g mellophanic acid dianhydride, 0.5g stannous octoate are added in Banbury mixer together with dried poly(lactic acid) 1kg, at 180 DEG C, reacts 10min, be there is " strain hardening " draft flowing deformation characteristic poly-lactic acid material.
By the poly-lactic acid material injection moulding at 190 ~ 220 DEG C obtained by above-mentioned steps, make the dumbbell shape tension specimen that width is 10mm, thickness is 4mm, then injection-molded test specimens is fixed on solid phase mouth closing mould stretching device, in the thermal stretch mouth mould that 130 DEG C is 1mm with the rate of extension of 50mm/min by thickness, carry out stretch orientation, to be tensioned reach predetermined stretching ratio after, cool, unload, take off sample.
The poly-lactic acid material surface of preparation is 500nm by equally distributed width, be highly that the micro-nano groove biomimetic features of 100nm is formed, tensile strength can reach 140MPa, clotting time is true plasma prolongation 40s comparatively, and surface adhesion number of platelets reduces about 50% compared with the pure poly-lactic acid material before solid phase mouth closing mould stretching.
Embodiment 2
3g trihydroxymethylpropanyltri diglycidyl ether, 2g pentamethylene tetracarboxylic dianhydride, 1g antimonous oxide are added in Banbury mixer together with dried poly(lactic acid) 1kg, at 200 DEG C, reacts 20min, be there is " strain hardening " draft flowing deformation characteristic poly-lactic acid material.
By the poly-lactic acid material injection moulding at 170 ~ 200 DEG C obtained by above-mentioned steps, make the dumbbell shape tension specimen that width is 10mm, thickness is 4mm, then injection-molded test specimens is fixed on solid phase mouth closing mould stretching device, in the thermal stretch mouth mould that 100 DEG C is 0.5mm with the rate of extension of 25mm/min by thickness, carry out stretch orientation, to be tensioned reach predetermined stretching ratio after, cool, unload, take off sample.
The poly-lactic acid material surface of preparation is 800nm by equally distributed width, be highly that the micro-nano groove biomimetic features of 60nm is formed, tensile strength can reach 160MPa, clotting time is true plasma prolongation 50s comparatively, and surface adhesion number of platelets reduces about 50% compared with the pure poly-lactic acid material before solid phase mouth closing mould stretching.
Embodiment 3
5g glycerin triglycidyl ether, 5g pyromellitic dianhydride, 0.5g antimonous oxide are added in Banbury mixer together with dried poly(lactic acid) 1kg, at 220 DEG C, reacts 30min, be there is " strain hardening " draft flowing deformation characteristic poly-lactic acid material.
By the poly-lactic acid material that obtained by above-mentioned steps in 170 ~ 200 DEG C of injection mouldings, make the dumbbell shape tension specimen that width is 10mm, thickness is 4mm, then injection-molded test specimens is fixed on solid phase mouth closing mould stretching device, in the thermal stretch mouth mould that 110 DEG C is 0.25mm with the rate of extension of 5mm/min by thickness, carry out stretch orientation, to be tensioned reach predetermined stretching ratio after, cool, unload, take off sample.
The poly-lactic acid material surface of preparation is 1 μm by equally distributed width, be highly that the micro-nano groove biomimetic features of 50nm is formed, tensile strength can reach 170MPa, and the clotting time is true plasma prolongation 80s comparatively, and surface adhesion number of platelets reduces about 85% compared with the pure poly-lactic acid material before solid phase mouth closing mould stretching.
Claims (1)
1. surface has a preparation method for biomimetic features blood compatibility poly(lactic acid) self-reinforced material, it is characterized in that the method comprises the following steps:
(1) there is the preparation of " strain hardening " draft flowing deformation characteristic poly-lactic acid material:
0.05 ~ 5 part of epoxies branching agent, 0.05 ~ 5 part of anhydrides branching agent, 0.05 ~ 1 part of catalyzer are added in Banbury mixer together with the poly(lactic acid) of drying, at 160-220 DEG C, react 3 ~ 40min, be there is " strain hardening " draft flowing deformation characteristic poly-lactic acid material;
Wherein, epoxies branching agent is three epoxypropyl tricarbimides, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group p-aminophenol, N, N, N ', N '-four glycidyl group-4,4 ' diaminodiphenyl-methane, Phloroglucinol monomethyl ether triglycidyl ether, Pyromellitic Acid four glycidyl ether, 1,1 ', any one in 2,2 '-four (p-hydroxybenzene) ethane four glycidyl ether, Resorcinol formal four glycidyl ether, two Resorcinol formal four glycidyl ether;
Anhydrides branching agent is Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, pyromellitic dianhydride, mellophanic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, Succinic anhydried, MALEIC ANHYDRIDE, dodecyl are for any one in MALEIC ANHYDRIDE, inner methylidyne tetrahydric phthalic anhydride, hexahydrophthalic anhydride, glycerine three trimellitic acid 1,2-anhydride, pentamethylene tetracarboxylic dianhydride;
Catalyzer is any one in stannous octoate, tin tetraphenyl, tin protochloride, antimonous oxide, butyl (tetra) titanate, lanthanum titanium complex catalyst;
(2) surface has the preparation of biomimetic features blood compatibility poly(lactic acid) self-reinforced material:
The poly-lactic acid material injection moulding that will be obtained by step (1), make the dumbbell shape tension specimen that width is 10mm, thickness is 4mm, injection temperature: 170 ~ 220 DEG C, then injection-molded test specimens is fixed on the solid phase mouth closing mould stretching device of temperature controllable speed governing, with the rate of extension of 2.5 ~ 50mm/min at 60 ~ 150 DEG C, it is made to be less than the thermal stretch mouth mould of sample by section thickness, carry out stretch orientation, to be tensioned reach predetermined stretching ratio after, cool, unload, take off sample, obtain surface and there is biomimetic features blood compatibility poly(lactic acid) self-reinforced material;
Wherein, thermal stretch mouth mould thickness is any one in 0.1mm, 0.25mm, 0.5mm, 0.75mm, 1mm, 1.25mm, 1.5mm, 1.75mm, 2mm, 2.5mm, 3mm.
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| CN201510714151.8A CN105176031A (en) | 2015-08-17 | 2015-10-28 | Blood compatibility polylactic acid self-reinforced material with surface being provided with bionic structure and preparation method thereof |
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| CN201510714151.8A CN105176031A (en) | 2015-08-17 | 2015-10-28 | Blood compatibility polylactic acid self-reinforced material with surface being provided with bionic structure and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135204A (en) * | 2018-08-13 | 2019-01-04 | 四川大学 | A kind of self-reinforcing transparent PET/PC alloy and preparation method thereof |
| CN114605799A (en) * | 2022-03-24 | 2022-06-10 | 横店集团得邦工程塑料有限公司 | Transparent heat-resistant self-reinforced polylactic acid material and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| CN102453250A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing long chain branched polylactic resin by combining two-step functional group reaction |
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- 2015-10-28 CN CN201510714151.8A patent/CN105176031A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453250A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing long chain branched polylactic resin by combining two-step functional group reaction |
Non-Patent Citations (2)
| Title |
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| XIAOWEN ZHAO ET AL.: "Structure and blood compatibility of highly oriented poly(lactic acid)/thermoplastic polyurethane blends produced by solid hot stretching", 《POLYMER ADVANCE TECHNOLOGY》 * |
| ZHENGQIU LI ET AL.: "Fibrillation of chain branched poly (lactic acid) with improved blood compatibility and bionic structure", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109135204A (en) * | 2018-08-13 | 2019-01-04 | 四川大学 | A kind of self-reinforcing transparent PET/PC alloy and preparation method thereof |
| CN109135204B (en) * | 2018-08-13 | 2020-09-01 | 四川大学 | Self-reinforced transparent PET/PC alloy and preparation method thereof |
| CN114605799A (en) * | 2022-03-24 | 2022-06-10 | 横店集团得邦工程塑料有限公司 | Transparent heat-resistant self-reinforced polylactic acid material and preparation method thereof |
| CN114605799B (en) * | 2022-03-24 | 2024-01-30 | 横店集团得邦工程塑料有限公司 | Transparent heat-resistant self-reinforced polylactic acid material and preparation method thereof |
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Application publication date: 20151223 |